CN1092266C - Leather coloring process, leather coloring apparatus, and colored leather produced by such process - Google Patents

Abstract

Provided is a leather coloring process for carrying out coloring on a natural leather or a natural leather having been subjected to degreasing, the process comprising the step of carrying out ink-jet coloring on at least a partial area of the natural leather.

Description

Leather coloring process, leather coloring apparatus and by the colored leather of this explained hereafter

The present invention relates to a kind of technology and equipment, be used on a leather, printing an image.Particularly, the present invention relates to a kind of leather coloring process and leather coloring apparatus, also can simplify its operation and make operation high-speed so that on leather, form fine image.The present invention also relates to the leather behind this colored leather, produced and by the processing leather and fur products that this leather obtained.

The present invention also relates to the coloring process that on leather, undertaken by dyeing, coating or similar fashion, and particularly relate to and to realize that simplify and high-speed a kind of improved leather coloring process, the invention still further relates to colored leather, even this colored leather also can not cause the damage of painted image when the mechanical external force that painted back leather is subjected to image curvature for example or rubs such, and relate to a leather system device, it is included in painted back by the goods that processing leather obtained, for example wallet and sack.

Usually according to following explained hereafter leather.At first, rawhide or be subjected to by immersion, fleshing, unhairing, liming, cutd open layer, scudding and the preliminary preparatory process formed of washing by the crust that the animal peeling is obtained then is the tanning operation; For example utilizing, chromium compound and the so various types of tanning agents of vegetable tanning agent carry out described process hides, (handle fur usually so that make rawhide or crust up to tanning obtained, but unhairing not) has flexibility and heat resistance, after this by the dyeing and the operation that oils that neutralize, dye and oil (or filler) formed, be arranging process at last, this operation by water squeezing, stretching, extension, drying, regulate, draw soft, the drying that stretches, deburring, grain correction, coating and test.After being subjected to these operations processing, obtain final leather and fur products.

Leather and fur products can be utilized in various fields, fully shows the feel that leather is intrinsic.For example, in very large range utilize these scopes of these leather and fur productss to comprise: pin is with goods footwear for example, clothes, the body decorations product are gloves and belt for example, and travel items for example wraps, leather trunk (or suitcase) and wallet, industrial parts is belt and liner for example, and furniture is chair and automobile seat surface for example, and writes tool, musical instrument, Kendo (Japanese fence) article or the like.In such every field, can use rawhide or the crust of various animals and can adopt various method for leather-making.Therefore, the range of these Application Areass makes it different according to using desired durability degree and fastness.Use for these, in recent years,, not only leather and the sheepskin needs by the formed surface configuration of embossing constantly changed because the style of life is various, and to the needs of multicolor image also in continuous variation.

In this case, can use dyestuff or coating to carry out painted to leather by general dyeing or few applying.Nearly all these coloured materials are dyestuff or the coating that is used for the dyeing of textile material so far, and according to the kind and the tanning mode of rawhide or crust.Select suitable coloring process.Use these application always.For example, for example batik (Battick) is arranged, put forward dyeing and the imitative such method of stamp of knitting.Yet because leather has various characteristics according to its kind, practical operation still depends primarily on experience under actual conditions.Even when leather during with monochrome coloring, painted its operation of the leather of some kind was needed through a very long time, and require the complicated operations step, perhaps need repeatedly to repeat same step.So, the dyeing of a large amount of production same design or leather is dyed very fine image or multicolor image is unusual difficulty always.

Simultaneously, because follicular orifice (pore of rawhide) or be present in various wrinkles in the rawhide originally, the grain on the surface of leather, particularly so-called natural leather has scrambling or big concave surface.If leather is colored under this state, coloring agent gathers on that part significantly, so that produces very dense coloured part.When in that leather is smoothed so that when leather is colored eliminate scrambling or big concave surface in treatment step after, it fully smoothly is very difficult wanting to make the surface, so leather can be spotty staining or colourless when initial manipulation.In order to overcome such shortcoming, often need to improve the operation of many steps or several times dual-staining and cleaning.Here, importantly, it is difficult obtaining required state and the required tone of dyeing.The problem that the result exists is the leather and fur products that the tone with variation can only be provided.

When thirsting for its product, should have in total trend of high-grade sensation as daily living article and ornament use, if can easily obtain to have the goods that are formed at lip-deep very fine image, leather and fur products also more the highland enjoy leather intrinsic high-grade sensation, if and can form multicolor image or on leather, easily carry out local stamp, the stamp leather is range applications extensively.

Yet as stated before, hitherto known dyeing and coating technique require a lot of steps, so its operation certainly will take a long time, so that keep colorant density and fastness.In addition, leather is so far mainly with monochrome dyeing, therefore, in order to show multicolor image on leather, needs in layer bonding always or makes many leathers of different pigment dyeings.See on same leather even the pigment of some kind can show, but quantity is still restricted.Under any circumstance, the dyeing or the mode of gluing usually are different concerning every kind of pigment, and dyeing or gluing are manual operations always under many situations, so experience has occupied bigger factor.Like this, the past is mainly undertaken by know-how the dyeing of leather, and it is difficult therefore making its automation always, and the result causes high cost.

Simultaneously, when being shown on the leather,, image require it to have higher rate degree because having higher fine degree when multicolor image.Particularly, WATER RESISTANCE is big problem, and this is faced with image and forms the caused following point in back.

In the arranging process of leather, particularly in pretreated each step, adopt the coating of following gluing and interior gluing and permeable and filming water-base widely.Though carry out emulsion oil-filling or oiling after painted, the image of stamp has many chances that directly contact with water.On the other hand, most of coloured materials are water miscible, and the common image waterproof of can not saying so.Thereby, when carrying out so a kind of arranging process, unsatisfactoryly be, if can only form the multicolor image words, and during housekeeping operation, when being present in coloured material in the image and dissolving in the water that in Treatment Solution, contains, may be because density reduces or loss cause the image damage.

When multicolor image is shown on the leather, wish higher fine image, the variation of the coloring solution of Shi Yonging characteristic on leather for this purpose, just, how coloring solution infiltrates in the leather on the leather thickness direction or how coloring solution is distributed on the leather surface, and this quality for the image that influence will be put in order is very important always.

Except above-mentioned these problems clearly, Process for producing leather needs multiple processing means and operation for a long time at it from common dyeing up to each step of arrangement floating coat.Particularly, dyeing is that leather immerses the processing in a large amount of dye baths, therefore, must clean the deposit of residue dye bath or make leather drying so that remove the moisture content that immerses within it after processing.This processing institute's time spent is the longest.In addition, these problems also relate to the mobile and location of the leather of wanting processed.So the step operation continuous with integral body is very difficult from dyeing up to these steps of coating.Therefore, should solve the problem that this processing needs a lot of times.In view of producing in enormous quantities and the many variety production of small lot, the problem of required time is crucial.And the handling problem of the residue dye bath that produces from the dip dyeing method and the problem that is used for dry thermal source all can not be ignored.

Except the theme that relates to coloring process, also exist the problem that painted leather processing is become the goods this respect, wherein, should be noted that moving of leather, stretch and cutting, and resembling friction or crooked such mechanical external force, to be applied to painted surface be very possible.In order to prevent the damage of these factors to painted image, precautionary measures are prior excessive use coloured materials, so that form image on painted surface, perhaps carry out surface maintenance processing immediately after painted.

When on leather, forming polychrome, during high little close image, owing to may run off or nonhomogeneous density and to make coloured material bonding in large quantities when image forms be difficult.When a large amount of formation painted when image like this, consider the problem that distribute continuous time in dealing with step separately, the direct processing that is used for the surface protection of colored surface also is difficult at process management.

Therefore,, must be noted that the processing of leather itself, otherwise can cause that when producing in enormous quantities efficient reduces, cause expensive in order to prevent above-mentioned mechanism's external force.

Consider the above-mentioned problems in the prior art and made the present invention.An object of the present invention is to provide with low-cost and can be rapid painted and can on leather, form the technology of multicolor image leather by easy steps.Thereby to the frontier of making a kind of unprecedented use printing and dyeing leather.

For this reason, the invention provides by ink discharge device leather is sprayed technology and the equipment that trickle ink droplet forms painted image.

Another main purpose of the present invention provides leather coloring process and the leather coloring apparatus that adopts under these circumstances, the waste that this can solve the problem that leather itself causes and can be avoided coloured material, obtain high picture quality simultaneously, high fine and highly water-fast leather.

Another object of the present invention provides a leather coloring process and leather coloring apparatus, according to very significant discovery to characteristic intrinsic in the leather, these characteristics are necessary facing to the color fixing agent, described characteristic is because the present invention to how obtaining the research done of height resistance to water just finds, and is not studied in the past always.

Further purpose of the present invention is when forming multicolor image by ink discharge device on leather, relies on the infiltration of each ink droplet and the stable state of disperseing obtains the pattern of high fine and good durability, and does not rely on dot density.

Another object of the present invention is when forming image by ink discharge device, realizes even also can not cause in arranging process the technology of image damage, so can obtain high fine multicolor image and promptly form image.For this reason, need to rethink the universal method that is used to produce leather, to realize continued operation and automation from being different from viewpoint in the past.

Another purpose of the present invention provides a kind of technology, can reduce when the processing leather goods restriction to treatment conditions, when being processed into leather and fur products, keeps the high reliability of image.

Can reach above-mentioned purpose by the present invention.

As first embodiment, the present invention mainly provides the natural leather that is used for to natural leather or has been subjected to ungrease treatment to carry out painted leather coloring process, and this technology comprises that at least one regional area to natural leather carries out the painted step of ink-jet.

As another pattern of first embodiment, the present invention also provides an ink-jet leather coloring apparatus, it comprise a kind of when according to during the chrominance signal ink-jet according to the type that will be subjected to the natural leather of colored leather, be used for changing the device of China ink amount; A kind of ink discharge device; And a kind of being used for under the contacted state of ink discharge device be not sent to the conveyer of the painted areas of ink discharge device with natural leather.

As the another pattern of first embodiment, the invention provides the leather or the leather and fur products that carry out the ink-jet colored leather by aforesaid first embodiment.

As second embodiment, the present invention mainly provides has the leather coloring process that makes the painted step of image on to the natural leather that is subjected to tanning, and this technology comprises:

Spraying pigmented step uses that leather is sprayed the liquid China ink contain coloured material is painted to realize with the corresponding drop form of given information;

Impregnation step applies leather and can react with the black coloured material of the liquid that sprays with droplet-like and can infiltrate coloured material fixative in the leather, so that this fixative infiltrates in leather.

As another pattern of second embodiment, the invention provides by the technology of aforesaid second embodiment and carried out leather or leather and fur products that the ink-jet colored leather is handled.

As the 3rd embodiment, the present invention mainly provides the leather coloring process that is used for forming image on leather, and this technology comprises:

Preliminary step applies and can adjust agent with the ink penetration of black shape coloured material reaction the surface of leather on by the painted zone that will form image at least;

Painted step is adjusted in the zone of agent by an ink discharge device visual painted on the leather surface applying ink penetration at least;

The step of next applies the visual color-fixing agent that can react with the black shape coloured material in the leather at least to leather surface made the painted zone of image by ink discharge device on.

As another pattern of the 3rd embodiment, the present invention also provides the equipment that is used for realizing above-mentioned leather coloring process.This equipment comprises and is used for leather is carried out painted forming the ink discharge device of image on leather, and is used for by ink discharge device leather being applied the modifying device of the image improvement agent that can improve image in fact.

As the another pattern of first embodiment, the invention provides the leather or the leather and fur products that have carried out the ink-jet colored leather according to above-mentioned technology.

To significantly see from the following description of the present invention other than good model, characteristics and embodiment.

Fig. 1 has described the process that leather that the embodiment of the invention 1 carried out is handled.

Fig. 2 has described the main composition of the ink-jet leather coloring apparatus that is used for embodiments of the invention 1.

Fig. 3 has described the formation that can be used for ink gun of the present invention.

Fig. 4 has described the formation that can be used for color ink gun of the present invention.

Fig. 5 has described the main composition of the ink-jet leather coloring apparatus that is used for embodiments of the invention 2.

Fig. 6 has described the ink-jet colored leather in the example 3 of the present invention in theory.

Fig. 7 is made up of Fig. 7 A and 7B, has described the system of the ink-jet colored leather in the example 4 of the present invention in theory.

Fig. 8 is the flow chart of the leather coloring process in the embodiments of the invention 5.

Fig. 9 has described the member that is used for fixing a leather in the ink-jet leather coloring apparatus that is used for embodiments of the invention 5.

Figure 10 has described the main composition of the ink-jet leather coloring apparatus that is used for example 9 of the present invention.

Figure 11 has described the ink-jet leather coloring apparatus among Figure 10 and how to have operated.

Figure 12 is a flow chart, and a technology is shown, it comprise the preparation of leather and colored leather and to the improvement of leather up in example 10 of the present invention, obtaining leather and fur products.

The integral body of another embodiment that Figure 13 has described the ink-jet leather coloring apparatus of the operation that is used for Figure 12 constitutes.

Figure 14 A-14C is a schematic diagram, is illustrated in when imposing on China ink on the leather by the ink-jet leather coloring process in the operation of Figure 12 the state of ink droplet in leather.

Figure 15 A and 15B are schematic diagrames, and the state of ink droplet in the leather is shown when being provided with operation by Figure 12 and imposing on China ink on the leather.

Figure 16 has described another embodiment of the ink-jet leather coloring apparatus that is used for embodiments of the invention 11.

Figure 17 has described the main composition of the ink discharge device in the ink-jet leather coloring apparatus shown in Figure 16.

Figure 18 has described another embodiment of the ink-jet leather coloring apparatus that is used for embodiments of the invention 12.

Figure 19 has described the another of the ink-jet leather coloring apparatus that is used for the embodiment of the invention 13

Embodiment.

First embodiment

Be in the representative mode of representative with the first embodiment of the present invention according to above-mentioned main purpose, the present invention relates to be used for carrying out painted leather coloring process on the natural leather or on the natural leather of degreasing, this technology is included on the regional area of natural leather carries out the painted step of ink-jet.According to the present invention, can solve all problems that in general leather coloring technology, exist, and regional area can enter required colored state to carry out local multi-color coloring.Certainly, the present invention also can be applied to whole leather to realize that on whole zone ink-jet is painted.This application of the present invention is admittedly.

In another representational pattern of the first embodiment of the present invention, leather coloring process involved in the present invention be included in partially skimmed or degreasing to than on the natural leather of low degree to the zone of partially skimmed or degreasing to carrying out the painted step of ink-jet than the zone of low degree.According to the present invention, its advantage is to carry out the ink-jet colored leather with high efficiency.Particularly by degreasing to than the zone of low degree, its advantage is from the viewpoint of the recovery of leather state, can carry out painted at short notice.

In another representative pattern of the first embodiment of the present invention, leather coloring process of the present invention be included in form after the black receiving layer partially skimmed or degreasing on than the natural leather of low degree to partially skimmed or degreasing to carrying out the painted step of ink-jet than the zone of low degree.According to the present invention, the existence of black receiving layer can obtain leather self dyeing and high density dyeing all sidedly, and black receiving layer itself can be fixed on the leather.Therefore, whole leather has high-quality.In another representative pattern in first embodiment, the present invention with a kind of like this characteristics is used for carrying out painted leather coloring process on the natural leather or on by the natural leather of degreasing, and this technology is included on the regional area of the natural leather that forms black receiving layer carries out the painted step of ink-jet.That is to say as the present invention best provide the natural leather that has formed black receiving layer on it.Such leather coloring process is more practical.

More progressive pattern as the first embodiment of the present invention, the present invention carries out painted leather coloring process on the natural leather of degreasing or natural leather, this technology comprises that to being heated to temperature be that 60 ℃ or following natural leather carry out the painted step of ink-jet.According to the present invention, can carry out colored leather with good efficiency, and can not cause the damage of leather self owing to heating.In this case, can realize that by the bubble jet system that proposes by Canon Inc. ink-jet is painted, wherein utilize film boiling, at this moment, though China ink also is heated, but China ink reaches the leather in the state that is in 60 ℃ or following (57 ℃-58 ℃), and colored leather can be under the state that more improves.

In the utility mode of the equipment of the first embodiment of the present invention, the present invention is the ink-jet leather coloring apparatus, and it comprises a kind of type that is used for according to the natural leather that will be colored, the device of the change China ink amount when according to the chrominance signal ink-jet; A kind of ink discharge device and a kind of being used for under the ink discharge device state of contact be not sent to the conveyer of the painted areas of ink discharge device with natural leather.According to the present invention, except the invention that relates to technology, the China ink amount that imposes on the leather can also be changed to suitable amount, and therefore, colored leather can be in the state that more improves.

As the of the present invention improved pattern that relates to equipment, it can realize automation and masstone, and ink-jet leather coloring apparatus of the present invention comprises a master computer can exporting the multi-color coloring signal that carries out colored leather on natural leather; A polychrome ink discharge device; Be used for according to will be, change the device of China ink amount when receiving the multi-color coloring signal during ink-jet by the type of the natural leather of colored leather; And with under the contacted state of ink discharge device natural leather be not sent to the conveyer of the painted areas of ink discharge device.

The present invention never is limited to above-mentioned invention, and it can comprise by above-mentioned any intermediate products and final products that the present invention obtained.The present invention also can comprise above-mentioned of the present invention any desirable function combination, and it has painted to the leather ink-jet by ink discharge device, dry up to these steps of emulsion oil-filling also to comprise an ink-jet colored leather system.

Leather involved in the present invention mainly refers to natural leather, and it is by fellmongering tanning and obtaining then.After animal was processed, the rawhide of material was used as byproduct to start with, and usually a large amount of what be suitable for is ox for example, pig, horse, goat, the such food in one's mouth of sheep and the deer thing that floats.In addition, for example such bird skin of ostrich and for example green turtle, monitor Yi, the skin of the reptile that boa class and crocodile are such also can be used as leather.The present invention never is limited to these.With regard to tannage, adopted always so far the whole bag of tricks is also arranged, from these methods, select suitable tannage according to shape of products that is obtained as final leather and fur products and purposes.As tannage, common method is chrome tanning and vegetable tanning at present.In addition to these, the whole bag of tricks of the following stated is suitable for.

Tannage at first rough segmentation becomes to utilize the method for inorganic type inorganic tanning agent, as is typically chrome tanning, and utilize the method for agent of organic type vegetable tanning or syntans, as be typically vegetable tanning, and the method for utilizing the grease type tanning agent.In addition, adopt at present extensively some of these tannages mixed mutually and carry out mixed tannage system.

Among above tannage, utilize the method for inorganic tanning agent to comprise chrome tanning, aluminum tanning, zirconium tanning, titanium tannage and ferric salt are tanned.Utilize the method for organic type tanning agent to comprise vegetable tanning and aldehyde tannage.These methods also comprise utilization, naphthalene class syntans for example, and syntans that phenols syntans and resin tanning agent are such and grease tanning agent are as being typically the tannage of chamois leather.

Now, as be used in the present invention's the ink-jet system, image is by being divided into 300dpi densely, the above point of 360dpi or 600dpi constitutes, and these each points can be hit on the natural leather as medium with the painted shape that from small nozzle, sprays, that therefore, can carry out fast that each look drips is painted.In addition, uniform color tone can be obtained, therefore, the overall uniform image can be obtained.Have again,, always keep evenly absolute in that supporting place at the level and smooth place of leather surface and the leather back side is unnecessary because the ink-jet coloring system is that contact medium does not carry out painted coloring system.And the polychrome drop can adhere in a step, so the time that the leather that is carried out is subsequently handled also can be very short.

In the ink-jet coloring system, carry out colored leather when when some nozzles of ink discharge device come ink-jet, relatively moving with respect to leather, wherein, dot density can be very high, and can improve the definition in colored leather zone.In addition, according to the present invention, because ink-jet system only can form the monochrome that will be formed by ink-jet or the image or the mark of secondary color with particular color in the specific part zone on leather surface, therefore local specific region can form zone emphatically or color is softened regional.Particularly, use guard shield or analog can make the pre-treatment step that only is used for local specific region produce the zone, thus the zone that more can give prominence to the ink-jet colored leather.As another advantage of leather surface being carried out the ink-jet colored leather, even when resembling the so non-smooth of follicular orifice and wrinkle when being present in leather surface, can only control the amount of ink-jet in described part, so for other part (smooth or periphery), neither can produce non-homogeneous paintedly, also can not produce non-staining phenomenon.If on the other hand, leather surface is uniform, by on the master computer of system, programming or image processing can be regulated or changes the China ink amount that will give, therefore can obtain desirable Density Distribution or grade, and can all eliminate the shortcoming that exists in the general leather pattern-printing.

Above-mentioned ink-jet system so far essential record on the paper of plane.Yet, when using plane paper to write down, sign in the minimizing of dissolving again, the loss (pigment between) of dyestuff in dye bath, saturating look, increase of set time or the like has limited maximum ink injection amount.Therefore, under normal conditions, maximum ink injection amount is usually designed at 16-28nl/mm under the situation of water-based ink ²Scope in.Yet under the situation of leather coloring process of the present invention, existence can be executed the good situations of China ink in a large number, and this depends on the condition of protozoic kind or tanning.Numeral shows, ink injection amount is the twice of normal conditions or more, is approximately 16-50nl/mm ²When having black receiving layer, colored leather can carry out and more stable with more high-grade.Especially to be lower than when carrying out highly dense stamp corresponding to the stamp speed of stamp frequency, when for example carrying out two double density leather pattern-printings with 1/2 painted speed, when carrying out double exposure, same posting field when repeating writing scan several times, can obtain more improvement maybe when the control ink-jet head driving so that when increasing ink ejection amount.

Except above, technology of the present invention can further comprise the step of the emulsion oil-filling (making leather have pliability by making leather absorb oil) that is undertaken by ink discharge device.In this technology of the present invention, also comprise fat liquored step, can make coloured part have higher density and higher-strength, therefore also can obtain the toughness that can compare with the toughness that obtained in the common dyeing.Simultaneously, adopt vegetable oil to carry out this emulsion oil-filling usually, and can be provided for this fat liquored Treatment Solution, so also can shorten the time of this processing greatly by ink discharge device.

So far, the China ink that is used for the ink-jet coloring system imposes on paper, and contains a large amount of water usually.In the present invention, China ink is not limited to these kinds China ink, and according to the type of leather and because its characteristic that the processing of being carried out before painted changes, optional usefulness has the various China inks of suitable component, comprises the China ink that contains nonvolatile solvent.As ink-jet system, can adopt any charging control types, the spraying system of employing piezo-electric device carries out painted and adopts the spraying system of electro-heat equipment all is feasible.Wherein, because can be with the painted head of High Density Packaging, using the spraying system of electro-heat equipment is preferably.

In better embodiment of the present invention, this technology or equipment also can comprise makes China ink quicken structure, step or the device that mixes in leather.In particular, make leather surface have low moisture adsorbability, colored leather zone degreasing to higher degree, perhaps can be added black receiving layer.One of above-mentioned any or its some combination can both improve colored leather efficient.As the material of black receiving layer, be under the situation of water-soluble type at the black solvent that uses, be preferably water-soluble resin, for example polyvinyl alcohol, polyvinylpyrrolidone and cellulose.This black receiving layer can be made up of single mixing of planting material or two or more materials, perhaps can be individual layer or two-layer more than.Can provide black receiving layer by the whole bag of tricks, for example a method is by excellent coater, and roller coat glassware, frictioning blade or analog remove and apply the aqueous solution, the method that also has the half tone method of colouring and will form the bonding contact of above-mentioned any material of film.

Provide a heater for leather surface being had than low moisture adsorbability, being preferably.Under situation of the present invention, low-temperature heat is preferably, can stop for example dissolving of leather protein of dissolving of component.Particularly, the dissolving of its shown collagen is tending towards causing contraction for high-grade leather, the change of characteristic and the reduction of quality, in the former step that continues further treatment articles to improve the characteristic of leather.Therefore, in the present invention who heats, leather is heated, and makes leather self remain on 60 ℃ or following temperature, better is about 50 ℃, in temperature before the ink-jet colored leather and afterwards or in the process at colored leather for the highest.As being used for heater of the present invention, can adopt following method, a method is from the side heating leather relative with a side of carrying out colored leather (colored leather side) by a heating plate; Be to heat leather from the colored leather side on the other hand by warm-up mill, or heating means, undertaken by a blowning installation with the temperature control function that can keep above-mentioned predetermined temperature.

In the present invention, on the colored surface of the leather that is subjected to ink-jet colored leather of the present invention, can form a protective layer.As using material, polyamide is often used as top coat.This also is preferably in the present invention.Be preferably, the protective layer that can stop black coloured material to flow and can present light resistance or corrosion resistance is provided.

As being used for painted coloured material, can adopt general dyestuff and coating.In the middle of these materials, for common leather coloring, coating is always by more general and also more effectively be used for putting in order step.Under the situation of the colored leather that is undertaken by the ink-jet coloring system, coloured material need not be confined to dyestuff or coating since coating normally be insoluble to solvent and leather itself to this non-coloring characteristic also, when using, they are preferably distributed by synthetic resin with emulsion form.On the other hand, under the situation of using dyestuff, can be used easily during the great majority in them are water-soluble apace or pure.The dyestuff that can use can comprise all kinds, and just uses quite easily as long as they are the dyestuffs that are widely used in protein fibre.ACID DYES for example, the metal complex direct dyes, basic-dyeable fibre, mordant dye, acid mordant dyes and soluble vat dye, they are widely used in the common colored leather.In addition to these, also can use direct dyes, cation dyes, SULPHUR DYES, naphthol dye, oxidation dye, DISPERSE DYES and REACTIVE DYES, they are mainly used in cellulose fibre or polyesters.When these dyestuffs are used for colored leather, focus on and consider its resistance to water, absorption of perspiration, the such characteristic of solvent resistance and light resistance, therefore, in these dyestuffs, the metal complex direct dyes are best.For other dyestuff, in order to make these characteristics more satisfactory, can use the dyestuff mixed processing after painted or can reduce the processing of dye activity again.Have again,, can mix and use dyestuff and coating in order to produce these characteristics.Embodiment 1

Fig. 1 has described an example of the leather handling procedure that adopts in the first embodiment of the present invention, and this program comprises rawhide through preparatory process, the tanning operation, and painted operation and arranging process are up to obtaining leather and fur products.Fig. 2 has described the main composition of the colored leather device of the equipment that is used for the ink-jet colored leather.The colored leather of this example is described with reference to Fig. 1 and 2, according to the present invention below program carry out.

In producing, it is prepared by the tannage that carries out usually as the leather of coloring medium.Step up to this stage can reach degree as described below substantially: at first, the rawhide of handling animal for example ox, horse and pig to remove dirt, subcutaneous conjunctive tissue and hair, cut open layer then so that rawhide is divided into desirable thickness, then be to remove (pushing away agent washes one's face) tallow and coloring matter, after this wash with water with the cleaning pelt.And then be the tanning operation like this behind the preparatory process that carries out, after removing lime (deliming) and washing with water, and tanning rawhide again after in immersing soft acidic aqueous media.Tannage is divided into chrome tanning and vegetable tanning substantially, provides different hydrophilies according to its ion characteristic for dyestuff.Usually, carrying out under the situation of chrome tanning, the goods of having handled have the hydrophily of anionic dye, and have the affinity of cation dyes under the situation of carrying out vegetable tanning.Can suitably select the type of tanning according to the state of the leather of having processed and the kind that is used for painted dyestuff.

In this example, horse skin is used as rawhide.Rawhide is subjected to above-mentioned preparatory process earlier and handles, and after this carry out chrome tanning and handle, be painted preliminary treatment subsequently, it is by dehydration, and shaving and disacidify neutralization are to obtain to be used for painted rawhide.In order to ensure the hydrophily of coloured material in follow-up ink-jet is painted, rawhide also will be subjected to using the filling of the urea liquid of casein to handle.The filler that this step is used is the solution that is generally used for leather coloring.Also can use the solution of acrylates or urethane.The rawhide of Chu Liing to have the corresponding to size in long limit with the A3 size, is after this made the leather 1 of formation like this so that the coloring medium transmission passage by ink-jet leather coloring apparatus 3 by size cutting like this.

The colored leather of following such acquisition that leather carried out will be described here.The leather 1 that has cut as mentioned above is arranged on the upstream side of the direction of transfer of paired transfer roller (transmits driven roller 23 and transmits loose roll 24), and described transfer roller is used for transmitting the colored leather medium in the ink-jet leather coloring apparatus 2.After the ink-jet colored leather has been ready to and has begun to carry out painted step, at first, the transmission loose roll 24 that transmits driven roller 23 and follow its rotation begins to rotate, with transmit driven roller 23 and be connected the leather of placing 1 mutually and be stretched and enter in the pressure contact sections of the paired transfer roller that is rotating, so leather 1 automatically feeds conveyer.Then, handle the painted assembly of an ink-jet that is provided with on the transmission passage synchronously with the transmission of leather 1, so that carry out painted to leather 1 according to pictorial data.Painted finished after from the painted leather 1 of ink-jet leather coloring apparatus output by air dry.This finishes painted step this moment after painted leather 1 application of these steps resembles fish oil or the such grease of vegetable oil carries out emulsion oil-filling.The emulsion oil-filling step of carrying out here can adopt general any method.In the present embodiment, adopt rotary drum, use, under 55 ℃, carry out supernatant liquid and refueled 30 minutes by the mixed olive oil prepared solution.Like this, obtain leather with flexibility and intensity.

The colored leather that this mode is produced further is transferred into the arranging process of being made up of stretching, extension, deburring and polishing, carries out the necessary processing of various uses subsequently to obtain leather and fur products.

Below use description to ink-jet leather coloring apparatus 2 of the present invention.Fig. 2 has described the formation of the ink-jet leather coloring apparatus that is used for this example.The major part of example.Among Fig. 2, base 26 is equipped with whole painted chuck 22, this chuck 22 by 4 ink reservoirs 21 and painted 3 of 4 ink-jet that are used for spraying respectively 4 kinds of colors of ink forms and is made as one, and 4 ink reservoirs 22 are marked with China ink, green grass or young crops, magenta and 4 kinds of colors of ink of Huang respectively.China ink (A)-(D) shown in below these ink reservoirs are equipped with.In following, " % " is weight " % ", unless otherwise specified.

The preparation of China ink (A):

ACID DYES (C.I. acid brown 13) 2%

ACID DYES (C.I. acid orange 67) 1.5%

ACID DYES (C.I. acid blue 9 2) 0.5%

Thiodiglycol 5%

Isopropyl alcohol 3%

Potassium sulfate 0.01%

Sodium metasilicate 0.001%

Ferric sulfate 0.0005%

Nickelous sulfate 0.0003%

Zinc sulfate 0.0003%

Water balance

Mix above all components, regulate the mixture that obtained to PH8.2, stirred then 2 hours, use fluorine hole filter F P-100 (commercial name subsequently with NaOH; Provided by Sumitomo Electronics Industries Ltd, this is with following described identical) filter to obtain ink-jet colored leather China ink (A).

The preparation of China ink (B)

ACID DYES (C.I. Blue VRS 85) 9%

Thiodiglycol 23%

Triethylene glycol monomethyl ether 6%

Potassium chloride 0.05%

Potassium silicate 0.001%

Iron chloride 0.0005%

Zinc chloride 0.0003%

Water balance

Mix all above components, regulate obtaining mixture with NaOH, stirred then 2 hours, filter to obtain ink-jet colored leather China ink (B) with fluorine hole filter F P-100 subsequently to PH8.3.

The preparation of China ink (C):

ACID DYES (C.I. acid red 266) 7%

Thiodiglycol 15%

Diethylene glycol (DEG) 10%

Tetraethylene glycol dimethyl ether 5%

Potassium chloride 0.04%

Sodium sulphate 0.01%

Sodium metasilicate 0.001%

Iron chloride 0.0005%

Nickel chloride 0.0002%

Water balance

Mix all said components, the mixture that regulate to obtain with NaOH stirred 2 hours then to PH7.9, filtered to obtain ink-jet colored leather China ink (C) with fluorine hole filter F P-100 subsequently.

The preparation of China ink (D):

ACID DYES (C.I. acid yellow 11 0) 7%

Thiodiglycol 24%

Diethylene glycol (DEG) 11%

Potassium chloride 0.004%

Sodium sulphate 0.002%

Sodium metasilicate 0.001%

Iron chloride 0.005%

Water balance

Mix all said components, regulate the gained mixture to PH8.4, stirred then 2 hours, filter to obtain ink-jet colored leather China ink (D) with fluorine hole filter F P-100 subsequently with NaOH.

How following description operates the ink-jet leather coloring apparatus of this example.In this example, as shown in Figure 2,, provide a feeding disc 25 that tilts, make it just in time to insert and transmit driven roller 23 and transmit between the loose roll 24 for tanning and the leather 1 that cuts into intended size are stably fed the ink-jet painted areas.In this state, be driven rotationally owing to transmitting the direction of driven roller 23 with arrow A, leather 1 was led the contact pressing part of transfer roller in pairs, then ran to ink-jet colored leather zone forward.When not carrying out painted or during the painted head restoring original position of ink-jet, carriage 26 is designed to be positioned at the original position (not shown).

Before beginning is painted, the carriage 26 that is positioned at position shown in the accompanying drawing (original position) moves along the carriage axis of guide 27 according to the instruction of painted beginning, during this period, the China ink of four kinds of colors sprays from many nozzles of the painted head of ink-jet according to chrominance signal, and the while is according to the read output signal timing of linear encoder.Like this, in the painted width d of colored surface, form stamp.By this painted scanning, China ink is pressed tusche, blue or green China ink, and the order of magenta ink and Huang Mo is sprayed on colored surface to form many points.In case finish discharge capacity according to pictorial data in the end of colored surface, carriage 26 turns back to original position, carries out ink-jet again along next bar line.After first painted the finishing and beginning for the second time painted before, transmit driven roller 23 and rotate so that transmit leather 1 with painted width d.Like this, for painted repeat of the painted head of each scanning ink-jet of the transmission of carriage and leather in painted width d, up to the image forming of finishing on the colored surface.Finish painted in, by the painted leather of conveyer output, and a platen 28 that has formed the plane colored surface simultaneously during painted tilts along outbound course, this will help the output at the rear portion of equipment.In order to help this output, can be provided with at the downstream side of painted areas and to resemble the such device of positive discaling roll.

With regard to leather, its thickness can change according to the kind of rawhide and the mode of preparation and tanning operation.Therefore, more effective is that a mechanism is set, and this mechanism adjusts the ink ejection face of whole chuck 22 and the distance before the platen 28 according to the difference of carrying out the degree of depositing of painted leather.

Fig. 3 has described the formation of the ink gun 3 that is used for ink-jet.One end of wire substrate 30 and the wire of heating plate 31 partly interconnect.At the other end of wire substrate 30, corresponding with electric energy one heat converter that is used to receive the signal of telecommunication of carrying from body equipment, many buffers are set.Like this, the signal of telecommunication that sends from main equipment can be provided to electric energy-heat converter separately.Be used for wire substrate 30 backs on the supporting plane and the supporting base 32 that is made of metal base plate as the ink-jet color applicator.One stage clip 33i) has a member, this member has the bend that cross section is roughly U-shaped, so that be pressed in to linear elasticity on the area in the zone of ink-jet outlet of top board 34 of groove, described top board 34 is provided with some grooves to form the inwall of nozzle, what ii) be made of metal is arranged on the pawl that hook the dewatering orifice in the supporting base 32, and a pair of back leg that iii) is used for accepting the power on the stage clip that acts on metal support seat 32.Because the power of this stage clip, wire substrate 30 with have the top board 34 of groove to be assembled into the pressure contact condition.In order to support,, wire substrate 30 usefulness adhesives or analog assemble by being bonded together.

End feeding China ink pipe 35 is provided with a filter 36.One feeds black member 37 is made by molded, and has the top board 34 of groove integrally to have a general orifice plate 341 and the runner of feeding black hole.By two pin (not shown) are extended through respectively in two holes 38 and 39 of supporting base 32 and with they hot melts, be fixed to simply on the supporting base 32 thereby will feed black member 37.When they are fixed, with the clearance seal between orifice plate 341 and hello the black member 37, preferably by groove 321, with the clearance seal between the front end of orifice plate 341 and supporting base 32 in supporting base 32 settings.

Four-head became the structure of whole ink-jet carriage 22 when Fig. 4 was illustrated in ink reservoir and has been removed, wherein, can spray tusche respectively, blue or green China ink, and the above-mentioned four-head 3 and a support 50 of magenta ink and four kinds of China inks of Huang Mo are assembled into one.Four-head is assemblied in the support 50 with given interval, and is fixed in this state, and promptly the direction of having arranged by nozzle is regulated position separately.In the present embodiment, with its position separately of the machinery standard plane regulating of shower nozzle, so the accuracy of the mutual ink droplet impingement position of each color can improve.In order to improve this precision more, measure the data that the ink droplet impingement position obtained temporarily when being assembled to actual ink-jet under the state on the support and can directly regulate composite coloured ink droplet impingement position according to described shower nozzle.Reference number 51 is represented the lid of support, and numeral 53 connector that to be buffers of will be on the wire substrate 30 being provided be connected with the signal of telecommunication that sends from the main body coloring apparatus.Four shower nozzles of whole assembling are not only to handling favourable but also be effectively for the compound ink droplet impingement position that improves described shower nozzle, and also very effective for the quantity that reduces the holding wire that links to each other with the main body coloring apparatus.For example, four shower nozzles are shared resemble the such holding wire of GND line connect can make on the substrate 52 shared, directly to reduce the quantity of line.And if integrated circuit substrate is set, painted holding wire also can be made shared, drives so can cut apart by the time for each shower nozzle.The minimizing of electric connection line quantity is effective for the equipment with holding wire such as tinting machine or many nozzles high speed tinting machine.

As mentioned above, can adopt the ink-jet leather coloring apparatus to carry out general staining procedure, so, comprising dehydration in general manner, the dyeing course of taking time most among the dyeing of skiving and disacidify neutralization and the emulsion oil-filling can only be finished in the dozens of minutes, and universal method so far almost will be spent one day time.And also can carry out the polychrome arrangement without plate.

Embodiment 2

Fig. 5 illustrates another form of ink-jet leather coloring apparatus, and the unnecessary example that leather is cut into a standard-sized equipment is shown.According to the kind of the rawhide that begins, leather has different size, the many areas that have greater than the A3 size in the middle of them.In the present embodiment now, provide the ink-jet leather coloring apparatus 6 of size that colored leather can be carried out and be not considered as the leather of colored leather medium.

In equipment shown in Figure 5, the basic operation of dyeing is identical with the described leather coloring apparatus of Fig. 1, except on base 62 and 63, be provided with have big metering-orifice and large-sized feed ink assembly 61 and be designed to can the large scale ink gun 60 of a large amount of ink-jets, base 62 and 63 is located at ink-jet colored leather zone respectively so that equipment is suitable for large-sized coloring medium (leather).They connect through a pipe 64, so that China ink is fed to ink gun 60 from feeding ink assembly 61.According to the signal that is sent to ink gun 60 from conveyer, these two bases move back and forth to scan by the arrow C shown in the accompanying drawing along the guide rail 67 and the guide rail 68 that are assembled on the support 66 respectively, simultaneously, from ink gun 60, begin ejection according to the picture intelligence China ink, so that painted on leather 7.

The colored leather that operation as described below is to use this ink-jet leather coloring apparatus to carry out.At first, make rawhide,, be used for the leather of colored leather with preparation the stage of same way as processing before dyeing among this rawhide and the embodiment 1 with ox-hide.One end at leather back suitably placed on the platen 69 (its mating part now is shown).After this, the ink-jet timing signal that is used for each hole of ink gun produces from picture intelligence, and picture intelligence is the image signal generator that is provided with from respectively.Be applied on the conveyer 65, be sprayed onto leather thereby be used in painted China ink) on.Then, the every run-down of ink gun, leather just moves painted width by the direction of arrow B.Repeat this operation subsequently, painted zone 71 in turn is presented on the leather 7, extends to the whole surface of leather 7 at last, thereby finishes painted.

The leather shape that comes from the tanning operation is normally uneven, and its edge also is set as straight line.Therefore, if leather is pressed original state by ink-jet leather coloring apparatus shown in Figure 5, the China ink that forms image just may be ejected at the outside of leather surface.As a result, thus cause China ink to be directed onto the surface of having polluted platen on the platen 69.If this phenomenon takes place, when next leather can be stained by then carrying out when painted the back of this colored surface, perhaps spray China ink on the platform branch and become dry and form deposit thereon and hinder leather on platen, smoothly to move, the error that causes transmitting leather.In order to prevent these problems, can will scribble adhesive and before leather places the ink-jet leather coloring apparatus, adhere on the non-staining surface of leather at the segregative a slice paper in painted intact back.Also can increase processing promptly during shading operations, when each scanning of base, detect the two ends of platen epithelium leather, thereby the part from stretching out the edge outside be towards deleting the master drawing image data.

Through painted leather 7 with example 1 in same way as be subjected to emulsion oil-filling and handle, then, be sent to arranging process so that leather processing become leather and fur products.

According to above-mentioned example, after tanning, will not be cut to standard size by leather, thus more effective and more promptly carry out painted step.So just can handle leather with free way.

Embodiment 3

Fig. 6 illustrates that schematically utilizing the ink-jet coloring apparatus to use the present invention carries out colored leather fat liquored operation afterwards.Here, all steps of the step before painted, that is, preparatory process, the tanning operation, dehydration, skiving neutralizes up to disacidify, and is identical with step in the example 1, omits description to these steps at this.The painted leather that is used for that has been subjected to up to the disacidify neutralization procedure is cut into the A3 size, and it is directed to by ink-jet is painted carries out painted colored leather zone 1001.The available equipment identical with the equipment of use in the example 1 carries out colored leather in this colored leather zone 1001.Painted and then be admitted to drier 1002 with the ink-jet leather coloring apparatus from the leather of this equipment output, 50 ℃ of dry 1 minute images down herein with fixing painted formation.

After this, leather is sent to emulsion oil-filling device 1003, refuels processing.When using ink-jet here, grease is flown upward, the situation when its dot density needn't be provided with than the formation image is fine and closely woven.Consider from these aspects, can adopt the ink-jet system of electrical heating energy heat exchanger, that is, by the ink-jet system that piezo-electric device flies upward ink droplet, be preferably the ink-jet coloring system that adopts the electrical heating energy converter, this described in painted aforesaid.In this emulsion oil-filling device, after using grease, carry out conversion process again.According to this example, consider the performance when spraying, the Treatment Solution that is used for this oiling is preferably the solution with low relatively viscosity.In this example, use 25 ℃ under, viscosity is the castor oil of 100CP.Be subjected to this fat liquored leather and then be sent in the arranging process, thereby obtained leather and fur products.

As mentioned above,, can shorten the painted time that is spent with oiling certainly, and all steps that relate to dyeing are easy to carry out automatically as a continuous process, to cause the process cost minimizing owing to dye and fat liquored operation with the ink-jet leather coloring apparatus.Example 4

Fig. 7 A and 7B illustrate an a kind of object lesson of system, in this system, use the present invention and can process various leathers with identical device in the step of colored leather.In this example, unite three kinds of ink-jet leather coloring apparatus are installed, therefore, can in a system, carry out painted multiple leather.At first, concerning the leather of desiring to carry out colored leather, the necessary data of colored leather, promptly, the kind of rawhide, the tannage that in the tanning step, adopts, leather thickness, the method (these methods are carried out before colored leather) of processing colored surface (filler processing), the size of the colored surface when colored leather or area, temperature and humidity etc. preestablish by leather performance data preset device 1011, and simultaneously, the user handles this equipment by keyboard on the console or switch.Based on predetermined like this data, in an arithmetic unit 1012, automatically determine to be suitable for most the program of colored leather.One CPU1014 is connected on this arithmetic unit 1012, so can control its processing.Be preset in data in the leather performance data preset device 1011 to be stored in-RAM1016 (random access memory) in.These data, the stored information of-ROM1015 (read-only memory) (in this ROM1015 according to the situation of various leathers with the data organization program of the processing method that is fit to) and the data of painted visual holder 1017 are used for realizing arithmetic operation, and the result who is obtained outputs to colorize method determinant 1013.In this colorize method determinant 1013, the mode of assembling leather when the driving situation comprises colored leather, be used for the kind of the ink gun of colored leather, the scanning times of ink gun, the mode that is used for painted scanning is (under the situation of multi-color coloring, the order of color, distance that each look China ink sprays or the like) basic composition of painted image, be used for kind (type of dyestuff or coating and contain dyestuff or the type of the coloring solution of coating) of the coloured material of colored leather or the like, be determined and be output thus.These specified datas are sent to handles the necessary power source of ink-jet leather coloring apparatus, and simultaneously its stored information be presented at-CRF1019 on so that the user can confirm.Here, must change as the user under the situation of colorize method, can increase by a feedback circuit, like this, can further import data to change tentation data through a keyboard 1018.According to the colored leather operation of determining as mentioned above, any ink-jet leather coloring apparatus 1020-1022 is sent signal.Leather suitably places on the ink-jet leather coloring apparatus of determining like this, so just can realize colored leather in the best way on leather.

Below the formation of these ink-jet leather coloring apparatus will be described respectively.Handle ink-jet leather coloring apparatus 1020 by the mode described in example 1 and 2, its details of Therefore, omited.In the ink-jet leather coloring apparatus 1021, the leather transfixion, and mobile ink gun and on its whole colored surface scanning painted to carry out, this equipment is suitable for its colored surface and has complicated shape or uneven leather.This ink-jet leather coloring apparatus 1022 is fit to large-sized colored leather, and the transfixion of leather solid outside this equipment, and after entering painted feasible state, drive this equipment.In the time before colored leather, can not handling leather well, also can use this equipment.These equipment can be used for monochrome or multi-color coloring equally.In addition, can repeatedly carry out a series of ink-jet colored leather steps to same leather.

The leather that adopts any ink-jet leather coloring apparatus 1020-1022 to finish the ink-jet colored leather passes through drying nest 1023 and emulsion oil-filling part 1024, after this is sent to arranging process, is processed to end article at this leather.

In above-mentioned example, can automatically select coloring process, therefore, can optionally carry out colored leather to multiple leather.Like this, can realize the production of small lot as required with low cost.

In above-mentioned example, after the ink-jet colored leather, also can further carry out the fixing processing of image, be used for dye-fixing agent of textile printing or the like in the step after colored leather is finished and before the emulsion oil-filling.In order to carry out drying fast after colored leather, the ink-jet leather coloring apparatus also optionally disposes a heater or blows hot air device at its painted leather equipped at outlet port.In addition,, can use general treated cation of carrying out or basic treatment according to the characteristic of coloured material in order before colored leather, to quicken the bonding of coloured material, and also can be to the leather humidification before colored leather.These all are effective means.

Also effectively designing described equipment makes it and can regulate in ink-jet colored leather zone and China ink amount is injected in selection according to the type of leather.It should be noted that in addition, in the above-mentioned example that provides, described ink-jet colored leather step, wherein, in the example that provides, the ink gun run-down.The present invention never is limited to such example, and it comprises repeatedly repeats same step the same part of leather is carried out the example of double exposure color.

As mentioned above, though so far to the painted expensive always work and time of leather, and carry out multi-color coloring difficulty always, and can realize the leather coloring process of polychrome according to example 1-4, and the processing time is short, is easy to automation.This can process in a large number, also can be with the small lot batch manufacture various products to satisfy the careful needs in market.Second embodiment

To formation of the present invention be described at first target of above-mentioned concrete technical theme below.

As the main feature of the second embodiment of the present invention, leather coloring process of the present invention has the step of printing an image on the natural leather that is subjected to the tanning processing, and this leather coloring process comprises:

One spraying pigmented step, the liquid ink that contains coloured material to be ejected on the leather painted to realize with the corresponding droplet profile of the information that provides;

One impregnation step, can react with the liquid ink coloured material that sprays with droplet profile and can infiltrate in the leather that the coloured material fixative imposes on the leather so that fixative infiltrates in the leather.

In the second embodiment of the present invention, preferably the coloured material in the liquid ink comprises a kind of anion coloured material, and the coloured material fixative in impregnation step comprises a kind of liquid that contains cationic substance; Perhaps, the coloured material in liquid ink comprises a kind of anion coloured material, and the coloured material fixative in impregnation step is the liquid that contains a kind of cationic substance, and this liquid also contains the material of a kind of sun from high molecular.

In another embodiment of the present invention, before the colored leather step, the colored leather surface preferably has been subjected to tanning, and has black receiving layer so that liquid ink is permeated with a kind of form of hope; Perhaps impregnation step is carried out simultaneously with spraying pigmented step, or after spraying pigmented step, carry out.

According to a second embodiment of the present invention, this technology comprises by liquid ink is come spraying pigmented step that leather is carried out to be ejected on the leather to form an image with the corresponding droplet profile of given information, and can react with the coloured material that sprays with droplet-like and the coloured material fixative that can infiltrate in the leather imposes on the leather so that this fixative infiltrates the impregnation step in leather.This causes following advantage.

Enter at liquid ink and leather and to contact so that to adhere to or to infiltrate in wherein the process, perhaps adhere to fully or permeate with in leather coloring or after this in liquid ink, the coloured material that in this liquid ink, contains and infiltrated in the leather and exist coloured material color-fixing agent wherein to be in contact with one another, and it is insoluble that coloured material is become, that is, coloured material is fixed.Therefore, though after this water or analog adhere to attempt on the leather coloured material is dissolved again or can not take place when making it mobile yet since density reduce or glow due to image damage.Because this mechanism, the coloured material color-fixing agent under any circumstance all is effective, no matter in advance this color-fixing agent is imposed on and be subjected in the spraying pigmented leather still permeating in that China ink was penetrated into it in leather in spraying pigmented operating period, and it being applied infiltration after spraying pigmented finishing, they all are effective.For this reason,, spraying pigmented step of liquid ink or coloured material color-fixing agent impregnation step can be at first carried out, perhaps this two step can be carried out simultaneously according to the order of each step.To the temporal difference between two steps also without limits.Can obtain same effect in all cases.

Just as explained above, impregnation step promptly, becomes droplet-like to spray liquid ink and is preferably undertaken by spraying pigmented system.The coloured material that is generally used for the ink-jet coloring system comprises various types of dyestuffs and coating.Great majority in them present anionic nature, just the degree difference.Therefore, when having and those of coloured material opposite polarity, when being cationic materials with the coloured material fixative that acts in the impregnation step of the present invention, coloured material and coloured material fixative are in contact with one another by electric suction, between them, take place by the reaction due to the ions binding, therefore, can be more firmly fixing coloured material and become insoluble.This anionic materials comprises ACID DYES, direct dyes, and metal is in conjunction with direct dyes and REACTIVE DYES and some coating.Under the situation of dyestuff, the great majority in them be easy to water-soluble or alcohols in, and be easy to use.On the other hand, under the situation of coating, they are insoluble in the solvent usually, and itself does not have dyeability concerning leather, and therefore, when using, they preferably form with full resin and disperse supernatant liquid.Also can mix and use these dyestuffs and coating.

For leather, because they were the internal that watches for animals and muscle and the crust self breathed originally, so they have very big moisture.They have very high water imbibition thus.

Carry out painted leather preferably water squeezing and dry leather after the tanning by ink-jet system.Even they have passed through these step process, owing to the original character that has under the state of rawhide, they also have moisture more or less under the leather state.Therefore, as long as the coloured material color-fixing agent contains anionic species and forms liquidly, then no matter select above-mentioned which kind of form, the coloured material color-fixing agent can both infiltrate in the leather, and the coloured material color-fixing agent is imposed in the leather.And the coloured material color-fixing agent can be well contacts to obtain desirable effect with coloured material in the China ink.

In carrying out the second embodiment of the present invention, fixing in order to improve by the credit rating or the quickening of the formed image of colored leather, the infiltrative black receiving layer of the adjustment liquid China ink that provided before the step of colored leather is effective, usually concerning leather, have various according to the kind of animal and the type of tannage.So, when the atomizing of liquids China ink when forming image, how China ink permeates and how to be distributed on the colored surface and make a world of difference after China ink reaches colored surface and before image is fixed.Like this, use leather, form the characteristic that desirable image provides the best because the existence of black receiving layer can be them for some.These can make image fixed point itself painted on leather and its density is increased, and itself can be easily fixed to black receiving layer on the leather.Therefore, the quality of skin amount is improved.When painted area was the part, from keeping highdensity viewpoint, black receiving layer was more effective.

In leather, in natural leather, because hide surface, particularly the hair follicle hole on unborn various wrinkles or the grain makes leather become irregular or still has these phenomenons of big concave surface in rawhide more precisely.If carry out paintedly in this state,, thereby cause not high enough density because these phenomenons exist China ink will clearly gather those parts.In addition, when having made leather level and smooth in treatment step, when eliminating after irregular place or the big concave surface leather coloring, it also is difficult smoothly preferably that the surface is accomplished.Therefore, the existence of black receiving layer also is effective for reducing such phenomenon.The China ink receiving layer also is effective for any external force suffered in the arranging process that keeps image to carry out after painted with opposing.Identical among black receiving layer in the present embodiment and first embodiment.

As the special and better technology of the second embodiment of the present invention, the present invention is a kind of technology with step of seal matter image on the natural leather that is subjected to tanning, and this technology comprises:

Spraying pigmented step, the liquid ink that will contain the anion coloured material is to be ejected on the leather with the corresponding droplet-like of given information, and is painted to realize;

Impregnation step, to mainly be not less than 2 by having molecular weight, 000 to being not more than 200,000 cation high molecular material and have molecular weight and be not more than 1, the coloured material color-fixing agent that the mixture of 000 cationic substance is formed imposes on the leather, so that this fixative is penetrated in the described leather, wherein, described material can react with the coloured material that sprays with droplet-like and can infiltrate among the leather.

Such as the aforementioned, in the present invention, decide to induce reaction between the agent at anion coloured material and coloured material look by ionic bond.Have been found that, for this reaction takes place effectively, the coloured material color-fixing agent preferably can mainly be not less than 2 by having molecular weight, 000-is not more than 2000,000 polymer substance and have molecular weight and be not more than 1, the mixture of 000 cationic substance is formed, and wherein said material can react with the coloured material that sprays with droplet-like and can infiltrate in the leather.In the following description, for simplicity, have molecular weight and be not less than 2,000-is not more than 200,000 cation high molecular quantity of material is known as " cationic high-molecular material ", is not more than 1,000 cationic substance and is known as " CATION lower-molecular substance " and have molecular weight.

Mechanism by the caused special reaction of these materials below will be described.

As the phase I of reaction, be used for the liquid ink of colored leather, interact by anion between them and cause association with dissolving or the anion coloured material that contains of dispersity and the CATION lower-molecular substance that in the coloured material color-fixing agent, contains, coloured material is separated from liquid phase.Then, as the second stage of reaction, the associated matter of coloured material and CATION lower-molecular substance is attracted to another component of coloured material color-fixing agent, on the cation high molecular material, so, big by the gathering change of the formed coloured material that associates.Simultaneously, the aggregation of formed coloured material has very large viscosity here, so that no longer flows with the motion of liquid medium.Like this, these aggregations are varied to water-insoluble basically, thereby make coloured material perfect fixing in the image that forms.

The CATION lower-molecular substance, i.e. one of key component of coloured material color-fixing agent has the function that forms associated matter owing to ionic interaction between it and the coloured material, and the reaction speed that this associated matter forms must be very high.Example as the CATION lower-molecular substance that can satisfy this requirement, it comprises primary, the compound of the second month in a season or tertiary amines, especially lauryl amine, coconut amine, the acetate esters or the hydrochloride of the fragrant amine of stearmide or China fir, the quaternary ammonium type compound, especially chlorination bay trimethyl ammonium, chlorination lauryl dimethyl base hexadecyldimethyl benzyl ammonium, zephiran chloride tributyl ammonium and benzalkonium chloride, pyridiniujm compounds, especially chlorination cetyl pyrrole form sediment and bromination cetyl pyrrole forms sediment the imidazoline type cationic compound, as, 2-heptadecyl hydroxyethyl imidazole quinoline, and the oxirane border of senior alkylamines adds thing, as, the ethoxy Stearyl Amine, these all are preferred examples.

In addition, as this CATION lower-molecular substance, also can use the amphoteric surfactant in certain PH scope with cationic characteristic.As its example, it can comprise amino acid surfactant, R-NH-CH ₂-CH ₂-COOH compounds, and betaine compounds, especially carboxylic phenols surfactant, for example, stearic dimethyl betaine and bay dihydroxy ethyl betaine, and the amphoteric surfactant of sulfate, xanthate or phosphoric acid salt.When using these amphoteric surfactantes, must adjust them, so that when having the PH that is not higher than isoelectric point when coloring solution in the leather mixes.

More than show and have the example that molecular weight is not less than 1,000 CATION lower-molecular substance.Being used for material of the present invention is not necessarily limited in these examples.In the present invention, molecular weight is that those materials of 100-700 have the excellent surface activity in the cationic substance of low-molecular-weight scope, and also can with the coloured material fast reaction.Because the existence of this low molecular weight substance (monomer), this color-fixing agent and permeability is arranged when color-fixing agent imposes on the leather.

As for the cation high molecular material, it is as other components of the key component of coloured material color-fixing agent, this material is such as the aforementioned, its effect is the insoluble of the coloured material that causes owing to solid-fluid separation applications with the size of the aggregation that increases the coloured material that is formed by this associations and raising of the associated matter of coloured material in the adsorption liquid China ink and CATION lower-molecular substance, consequently reaches water-fast purpose.As the cation high molecular examples of substances that satisfies this requirement, can use water-soluble cationic macromolecule such as polyallylamine salt, polyene third inkstone, chloro dimethyl two allyl ammoniums, polyamine Sulfonates, polyvinylamine salt and chitinous acetate (Chitinic acetate) example is not limited only to this.Also can use the material that is generally nonionic, part is in conjunction with CATION thereon.For example, they comprise the copolymer that vinylpyrrolidone and aminoalkyl alkanisation quaternary salt form, and the copolymer of acrylamide and the formation of aminomethyl alkylation acid amides quaternary salt.Certainly, example is not limited only to this.These materials are comparatively ideal to should be water miscible, also can be dispersibility, as latex and emulsion class.Except water-soluble material, also can adopt other dielectric materials, here as long as material does not produce destruction to leather.Unrestricted to above-mentioned example.These cation high molecular materials are as long as molecular weight is not less than 2,000, and being preferably is 2,000-200, and 000, be applied to the present invention and just have effect.When molecular weight during greater than this scope, infiltration will become inhomogeneous in leather, thereby it is membranaceous to make these materials be part, perhaps since itself and coloured material react and form unsuitable gathering.Specifically, when these material molecule amounts are about 1,000,000 o'clock, just form and be coated with stratiform, so, not only the feel of leather is bad, and the aggregation of coloured material can be only intensive in surface layer part, and since in arranging process this aggregation of effect of mechanical external force can come off, cause crocking with activation.

The coloured material color-fixing agent can optionally add surfactant in addition to these by under the situation about constituting as the cation high molecular material and the CATION lower-molecular substance of key component in aforesaid better technology.For example, such surfactant can comprise higher alcohol oxirane additives, alkylphenol/oxirane additives, aliphatic acid/oxirane additives, polyol fatty acid ester/oxirane additives, high-carbon alkylamine/oxirane additives, fatty acid amide/oxirane additives, the oxirane additives of fats and grease class, propylene glycol/oxirane additives, fatty glyceride, pentaerythritol fatty ester, sorbierite and fatty acid esters of sorbitan, sucrose fatty ester, polyalcohol Arrcostab, and fatty acid amide and alkanolamine.

The better characteristics of this leather coloring process are to be that the per unit area of leather is not less than 0.01g/m with the solids content ²-be not more than 5g/m ²Scope in amount apply above-mentioned coloured material color-fixing agent, be more preferably with the leather per unit area and be not less than 0.05g/m ²-be not more than 3g/m ²Amount in the scope applies.In addition, the leather that has been subjected to tanning is the leather of crossing in conjunction with the tanning whitening, and should preferably adopt aluminum tanning in conjunction with tanning, zirconium tanning, and the combination of titanium tannage or silica tanning is tanned, and except such tanning, the coloured material color-fixing agent preferably applies by an ink gun.

By the method for the mensuration surplus that usually is suitable for, can determine to contain aforesaid coloured material color-fixing agent and be applied to amount on the leather.The unit are of the colored surface of leather (when the surface has the irregular place of particulate, be used for unit are of the present invention be meant with projected area represent and do not comprise the area at these irregular places) be assumed to be 1m ², under rational condition, described amount is calculated by solids content and is determined be not less than 0.01g/m ²-be not more than 5g/m ²Scope in.Be more preferably and be not less than 0.05g/m ²-be not more than 3g/m ²Scope in.If should measure less than 0.01g/m ², then color-fixing agent can not be so that all coloured materials are assembled when liquid ink arrives leather, some slightly difference depend on the China ink amount that applied and the state of leather.If should measure greater than 5g/m ², can stop the infiltration of China ink in leather partly.On the other hand, when it is being not less than 0.05g/m ²-be not more than 3g/m ²Scope in the time, image self is more stably remained under the good quality, and coloured material can be fixed and held at very high level.According to another viewpoint, this coloured material color-fixing agent needn't put on the whole surface of leather, also is effectively when being applied at least a portion, and these parts are the injected bonding parts of liquid ink.Just as described, for leather, the characteristic that is called as feel is very important, therefore, preferably the amount of the coloured material fixative that applied is adjusted in minimum zone.From this viewpoint, when less than 0.01g/m ²-be not more than 5g/m ²Scope in can make this feel be in better state when adjusting this amount.

In addition, according to this state that is applied to the coloured material color-fixing agent on the leather, the second embodiment of the present invention is characterized in that causing the infiltration of fixative.This does not also mean that infiltration must be well-proportioned on the thickness direction of leather, it can become intensive shape near this surface, perhaps can more or less present a gradient in the distribution of coloured material color-fixing agent.Even in such state, can not bring influence to its function.

When applying the coloured material color-fixing agent with the amount in this scope, known be coated with or spray method and device can be used for this method or device.More particularly, they can comprise the method that is coated with of utilizing excellent coater or wing, and utilize the method that is coated with of scraper or brush, spray method of carrying out with spray gun and the method for spraying fixative in the colored leather process from the ink gun of special use.Particularly, when color-fixing agent in the ink-jet colored leather sprays from an ink gun, can control spraying pigmented material color-fixing agent and make it not to be applied on the part that is provided with image, therefore, it can be applied and be suppressed to necessary minimum degree.

When by spraying system leather being sprayed colored leather, though the leather that will be colored is unrestricted, the color that forms is influenced by the base leather might produce change, and therefore, the best chi of color of base grass may be near white.As after tanning, making base leather color become all methods of white, so far being known in method of the prior art is aluminum tannage, silica tannage, zirconium tanning method or similar method, bound formaldehyde is tanned and aluminum tanning, the combination tannage of chrome tanning and zirconium or similar method, and the method that makes the variable color of base leather or behind vegetable tanning, bleach by the whitewash of use resemble titanium dioxide.Preferably can adopt any one in these methods.

Other pattern as the second embodiment of the present invention; the present invention also comprises leather and the leather and fur products that has carried out the ink-jet colored leather through above-mentioned leather coloring process and leather coloring apparatus; also comprise leather and leather and fur products with a protective layer, it can make the colored surface of carrying out the leather of ink-jet colored leather have the durability of improvement.

Embodiment 5

The example that carries out colored leather with 6 pairs one leathers of the ink-jet leather coloring apparatus shown in Fig. 57 is described hereinafter with reference to Fig. 8.

Make rawhide with sheepskin, make it to stand the processing of common preparatory process, follow by the formaldehyde tanning.After this, being subjected to the processing of water squeezing and skiving like this by the rawhide of tanning, adopting plumbous tanning agent to be tanned then, is to carry out emulsion oil-filling with olive oil subsequently.Being subjected to sheep that this combination tans is dried and prepares to be used for colored leather.The leather of producing with this method has high-flexibility and high whiteness, and by the painted suitable multi-color coloring of ink-jet.Secondly, concerning this leather, use spray gun on the whole grain of leather, sprays below shown in coloured material color-fixing agent (a), be used for the leather 7 of colored leather subsequently in two minutes with acquisition with about 50 ℃ heated-air drying.

Coloured material fixative (a):

Benzalkonium chloride 2%

Polyallylamine hydrochloride 5%

(molecular weight: 30,000)

Water 93%

In the leather 7 after handling like this, above-mentioned coloured material color-fixing agent (a) infiltrates its inside, and the amount that applies described color-fixing agent is 0.1g/m ²In addition, compare with handling preceding leather, this coloured material color-fixing agent (a) is according to not damaging feel and whiteness.

Below the colored leather that leather 7 that 6 pairs of ink-jet leather coloring apparatus shown in Figure 5 have used this coloured material color-fixing agent (a) to handle carries out is handled in explanation.Because being used for the leather of this example is sheep, it has very high pliability and extendability, and it is placed on the transmission supporting member and after this is fixed on the ink-jet leather coloring apparatus 6.Fig. 9 has described leather and how to be provided with.Here, one transmits supporting member 8 comprises a wafer 81, and this film 81 is made by vulcanizate, have low percentage elongation, and the side on whole surface scribbles the quite weak grain mixture 82 of cohesiveness.The purpose that 82 in this adhesive is used for connecting securely leather 7 so that can not comes off, thus it can have be used for preventing leather owing to own wt comes off necessary viscosity.Like this, painted when removing leather after having finished this adhesive will never damage leather.

Then this leather is carried out the ink-jet colored leather.Here the Mo Shimo of required usefulness (E)-(H), every kind of China ink has composition as follows. China ink (E): C.I. reactive black 5 (reactive dye) 13% thiodiglycol 15% diethylene glycol (DEG) 15% calcium chloride 0.002 water balance China ink (F): C.I. reactive blue 72 (reactive dye) 13% thiodiglycol 25% triethylene glycol monomethyl ether 4% water balance China ink (G): G.I. Reactive Red 24 (reactive dye) 10% thiodiglycol 16% diethylene glycol (DEG) 10% tetraethylene glycol dimethyl ether 4% water balance China ink (H): C.I. reactive yellow 95 (reactive dye) 10% thiodiglycol 26% diethylene glycol (DEG) 9% water balance

Mix all these components and obtain various China inks, stirred the mixture two hours, filter with fluorine hole filter F P-100 then.

Be arranged on the ink-jet leather coloring apparatus 6 in order to overlay the leather 7 that transmits on the supporting member 8, as shown in Figure 9, an end that transmits the back (side that leather is not stacked) of supporting member 8 suitably is placed on the platen 69 (not shown mating part).After this, picture intelligence produces on the conveyer 65 from being applied to by the image signal generator that separate to be provided with to be used for the ink-jet timing signal in each hole of ink gun 60, is used for painted China ink and is directed onto leather 7.Then, the every run-down of ink gun, leather just moves painted width by the direction of arrow B.Then repeat this operation, painted zone 71 is presented on the leather 7 with that, and the whole surface of last topped leather 7 is finished painted.The colored surface of the leather of Huo Deing has very high fine golden image like this.In addition, because leather itself is tending towards suction under the situation of sheep, China ink can permeate well, and can carry out clear paintedly, and does not have undesirable loss.

After finishing this colored leather, bonding leather 7 and transmission supporting member 8 are removed from ink-jet leather coloring apparatus 6, then leather 7 are peeled off from this transmission supporting member 8.In this state, being sprayed on the dyestuff that contains in coloured material color-fixing agent (a) and the China ink that sprays on the leather 7 reacts so that dyestuff becomes insoluble in water.This leather just is in the state that is sent to common arranging process like this.

After this, painted leather is sent to the arranging process that carries out usually.In order to carry out this arrangement, at first, painted leather is coated water-base polyurethane emulsion.Because the effect of the common painted material fixative of dyestuff (a) has been water-fast in water, so can not be damaged fully, then leather is coated and is comprised nylon resin or caseic sorted material, be to push up with japanning to be coated with subsequently to finish this operation, when such arrangement, sheep is made with the leather and fur products that high printings degree and polychrome design, and in the processing of sheepskin without any variation.

Embodiment 6

Adopt with example 5 in used identical sheepskin remove from office as epidermis, but must not be assigned on its leather by any coloured material color-fixing agent, the operation that the ink-jet colored leather carries out before is identical with example 5.After colored leather is finished, have 7 colored surface from the sheep of carrying supporting member 8 to remove, its lip-deep China ink is just by oven dry and by complete fixation, and coloured material color-fixing agent (b) is by being prepared as follows.

The coloured material color-fixing agent:

Benzalkonium chloride 2%

Polyallylamine hydrochloride (molecular weight: 50,000) 5%

Water 93%

Be sprayed onto equably on the colored surface of sheep by its coloured material color-fixing agent (b) of spray gun, the solids content that makes its coloured material color-fixing agent is 0.8g/m ², then following dry 3 minutes at 50 ℃.Give under the situation of coloured material color-fixing agent in that colored leather is after-applied, consider to prevent that drop from preferably adopting and have full-bodied Treatment Solution.Therefore, in the present embodiment, fixed higher of the gram-molecular weight of the high gram molecule material of CATION.

Then, the mode in the example 5 of the painted sheep of handling is like this put in order.The sheepskin that for this reason obtains is organized and keeps its just painted state afterwards, comprising glowing of non-binding material in feel, image density, picture tone and the image leather.

Embodiment 7

Adopt the identical sheepskin in the example 5 to make leather, the coloured material color-fixing agent should be prepared as follows in addition.Make ink-jet leather coloring apparatus shown in Figure 5 into such form, promptly another ink gun assembly is added in the ink gun 60, and so relatively form, another distribution cavity also add and place ink-feeding device 61.Add the chamber of China ink in ink-feeding device 61 be filled shown in component the coloured material color-fixing agent and be connected with additional ink gun assembly by a pipe so that the coloured material color-fixing agent also can with the same manner injection of four chromatic inks.

Coloured material color-fixing agent (C):

Benzalkonium chloride 1%

Polyallylamine hydroxide (molecular weight: 10,000) 1%

Thiodiglycol 10%

Diethylene glycol (DEG) 10%

At this moment, different with example 5 and 6 is, it is lower that the molecular weight of cation high molecular material is set up, but also added the injection auxiliary components, consider will be from ink gun spraying pigmented material color-fixing agent, should make solution viscosity low as much as possible.

At this with under forming, any coloured material color-fixing agent is not fitted on its leather, carry out the ink-jet colored leather according to the same manner of example 5.Support is back and forth driven when operating its leather pattern-printing, and coloured material color-fixing agent (C) also sprays from above additional ink gun assembly simultaneously altogether, and it is applied on the printed surface.Under this form situation, China ink almost produces on its colored surface simultaneously with the reaction of coloured material fixation figure (C), after colored leather is finished, has a colored surface from carrying supporting 8 sheep that take out like this, and dyestuff thereon is fixed.

Mode according to example 5 is put in order the painted sheepskin that obtains like this, and so the sheep of arrangement has very fine image as the colored leather goods and can not cause the problem that non-binding material glows in feel, image chroma, picture tone and the image leather.Embodiment 8

, handle as rawhide with adult ox-hide, carry out chrome tanning subsequently through common preparatory process.Then, the skin of tanning then will add the white that contains titanium oxide and dye layer material, thereby obtain white leather through water squeezing and shaving like this, and the leather that obtains like this is through emulsion oil-filling and drying, and the preparation colored leather.For this ox-hide leather, the hard and difficulty that stretches of its feel, therefore can on the ink-jet leather coloring apparatus of Fig. 5, carry it, so in this example, its leather is placed directly on the ink-jet leather coloring apparatus shown in Figure 5, and conveying supporting member 8 that need not be shown in Figure 9, before leather is placed on it, following coloured material color-fixing agent (d) is added on the graining of leathering, should guarantee that drying is after 3 minutes down at 50 ℃, and the solids content of its coloured material color-fixing agent (d) is 1.0g/m ²

Coloured material color-fixing agent (d):

Zephiran chloride tributyl ammonium 3%

Polyamine sulfone (molecular weight: 50,000) 6%

Water 91%

The back of the body end (muscle then) of the ox-hide leather (9) that so obtains suitably places (its bonding part is not shown) on the plate shown in Figure 5 69.Then, the same manner according to example 5 carries out the colored leather operation.

After finishing colored leather, leather 7 is removed ink-jet leather coloring apparatus 6, and at this moment, the coloured material color-fixing agent that is sprayed onto on the leather 7 reacts with the dyestuff that is included in the ink-jet, it is water-fast that its dyestuff is become, thereby the leather of this state can be transported in the common arranging process.

In its arranging process, adopt screening formula dyestuff device to dye respectively and add, at first to dye and add the water base sorted material that mainly contains cruel element, next dyes and adds the sandwich material that comprises synthetic resin, and after stain adds the top layer lacquer, finishes arrangement with the flatiron pressurization subsequently.This claims the leather and fur products of putting in order to can not see disturbed image, does not also have feel to change fully, and this is owing to apply the cause of coloured material color-fixing agent before colored leather.Therefore can obtain polychrome leather and fur products clearly.

Embodiment 9

Figure 10 part shows the ink-jet leather coloring apparatus, and it is to form like this, can carry out colored leather and coloured material color-fixing agent and spray in same equipment, and can finish a series of such operations continuously.Here label 9 is represented the ink-jet leather pattern-printings, the leather that label 10 expressions are colored.This ink-jet leather pattern-printing equipment is pressed the same manner operation of example 5 substantially, and the ink gun 90 of ejection China ink comprises and is arranged on 4 ink gun assemblies in the device, and has many nozzles of the following arrangement.Its ink gun 90 also is the monolithic devices rack form, wherein nozzle component directly is connected with the black case 91 that is installed in China ink, the internal insulation of its black case 91 becomes to be equipped with respectively the chamber of 4 black, blue or green, pinkish red and yellow look China inks, so that ink can directly not be passed to ink gun 90 by pipe.Among Figure 10, the chamber that black, blue or green, pinkish red and yellow China ink is housed respectively indicates mark K, C, M, Y respectively.Its ink gun 90 and black case 91 install on the slide 92, according to the signal that is transported to from the transmitter (not shown) the ink gun 90, its slide 92 moves back and forth along seeking rail 93 and 94 in illustrated arrow C direction, and begin to spray China ink downwards from ink gun 90 according to pattern signal simultaneously, on leather 10, can finish stamp like this.Then, along with moving back and forth of slide, its leather is transferred continuously along the arrow E direction, up to finish stamp on whole surface.Here the China ink of Shi Yonging be have following component China ink (I) to (L).

China ink (I):

C.I. food China ink 2 (dyestuff) 9%

Thiodiglycol 10%

The oxirane additives 0.05% of acetylene ethylene glycol

Water balance

China ink (J)

C.I. sour blue 9 (a kind of dyestuffs) 2.5%

Thiodiglycol 10%

The oxirane additives 0.05% of acetylene ethylene glycol

Water balance

China ink (K)

C.I. sour red 289 (dyestuffs) 2.5%

Thiodiglycol 10%

The oxirane additives 0.01% of acetylene ethylene glycol

Water balance

China ink (L)

C.I. directly yellow 82 (dyestuffs) 2%

Thiodiglycol 10%

The cyclohexane additives 0.05% of acetylene ethylene glycol

Water balance

By mixing all components, mixture being stirred 2 hours, then adopt fluorine hole filter EP-100 that it is filtered.

Equally, comprise that the ink gun 95 of an ink gun assembly and a connected case 96 are contained on the slide 97, along the reciprocating motion of arrow D direction, its upstream parallel with the vibration-direction of above-mentioned slide 92 and dress dry leather 10 throughput directions.The coloured material color-fixing agent (C) that example 7 exemplifies is housed in its case 96, and it is transported to ink jet print head 95.Simultaneously operating along with the ink gun 90 that on leather 10, carries out colored leather, be fit in the time, its slide 97 is reciprocating along the identical speed of guide rail 98 and 99 slide 92, here shower nozzle 95 disposes like this, and its coloured material color-fixing agent (C) can be sprayed onto downwards on the colored surface of leather 10 from all nozzles.Like this, in this example, China ink and coloured material color-fixing agent all spray with direction vertically downward.

Be used to carry the device of leather 10 to have as shown in figure 11 mechanism, it has comprised ink-jet leather coloring apparatus 9 shown in Figure 10.Particularly its transport has an adsorbent equipment 11, and it is lived the non-staining of leather surface one side draught by suction.This adsorbent equipment 11 has a mechanism in 12 motions of direction E shown in Figure 11 upper edge rail.In order to carry out the colored leather operation, at first leather 10 is put on the adsorbent equipment 11, produce suction within a certain period of time by a drive source (not shown) then, thereby catch leather securely, and make its open and flat adsorbed state that reaches simultaneously by suction.Then, adsorbent equipment 11 with the reach of the direction of arrow E up to the front end of leather 10 near ink gun 90, begin shading operations at this.Then, whenever slide 92 makes a round trip, place leather 10 on the adsorbent equipment 11 to move past the painted width of an ink gun 90 continuously forward in the arrow E direction.In shading operations,, be sprayed onto dyestuff on the colored surface this moment by fixation and become insoluble from ink gun 99 ejection coloured material color-fixing agent.After a series of colored leathers and spray colouration material color-fixing agent were finished, the leather 10 on the adsorbent equipment 11 was sent to drying oven 13, for example descends dry 3 minutes at 50 ℃, thereby the unnecessary solvent component in the coloured material color-fixing agent is evaporated.After adsorbent equipment 11 leaves drying oven 13, discharge attraction complete operation to leather 10.

Under such structure, need behind chrome tanning, the ox-hide leather that is obtained to be carried out colored leather.Leather by coloring apparatus 10 is by according to the same method for sorting of example 8 colored leather being put in order in turn.Owing to formed black receiving layer before colored leather, Zheng Li leather has the very high pattern of fine and closely woven degree for this reason.In addition owing in colored leather, having applied the coloured material color-fixing agent, so can in arranging process, not destroy pattern.Can the feel of leather not had problems in addition.Because applying and all being continued operation up to drying of colored leather, coloured material color-fixing agent can be shortened the processing time like this.

If adopt such equipment to carry out colored leather, leather is regulated easily, in addition simple and reliable process.In addition, the application that is coated with the black receiving layer that adds formation and the coating in arranging process can systematization so that on same streamline, carry out, can realize automation effectively to the processing of its leather.

As mentioned above, according to a second embodiment of the present invention, spend a large amount of labours and time so far and in polychrome design inconvenient colored leather, now can realize by the atomizing of liquids China ink, particularly realize by ink-jet system.In addition, the load of WATER RESISTANCE in the arranging process is disturbed solve by applying effective coloured material color-fixing agent.Leather coloring process that obtains like this and equipment can obtain the height clear pattern, and shortened the whole processing time, therefore under the situation that does not limit common leather use, obtain having the leather and fur products of first-rate quality pattern and high product quality, this may mean and will develop towards the direction of unavailable new leather and fur products always.Simultaneously, can make the multiple product of small lot and satisfy the different needs in market.The 3rd embodiment

The purpose of third embodiment of the invention is to constitute a leather coloring process or equipment, can effectively carry out the painted or formation multicolor patterns in part to leather by ink discharge device.Another purpose is to overcome the problem owing to making great efforts to new technical field to bring.

Third embodiment of the invention at first relates to a leather coloring process, is used for painted formation pattern on leather, and its technology comprises:

One previous steps, to leather surface on face, apply at least by painted formation pattern can with the ink penetration conditioning agent of black coloured material reaction;

One painted step goes out pattern by ink discharge device to leather surface is painted on the face that applies the ink penetration conditioning agent at least;

One final step is to leather surface, at least to by applying the pattern fixative that can react with black coloured material on the painted face that goes out pattern of ink discharge device on leather.

As the preferred embodiment of above-mentioned colored leather, formerly apply the ink penetration conditioning agent in the step, the absolute magnitude on its unit are is littler than the absolute magnitude on the unit are that applies the pattern color-fixing agent in the step in the end; The unit are absolute magnitude that in the end applies black color-fixing agent in the step is than little by the absolute magnitude that applies black coloured material unit are in the colored leather step; Formerly apply in the step ink penetration conditioning agent and in the end step be not less than the absolute magnitude that in painted step, applies black coloured material per surface area by the summation of the unit are absolute magnitude that applies the pattern color-fixing agent; Ink penetration conditioning agent before title in the step is same material with pattern color-fixing agent in step in the end.

Third embodiment of the invention also relates to a leather coloring process, forms pattern by stamp on leather, and its technology comprises:

One final step is to leather surface, at least to apply the pattern color-fixing agent that can react with black coloured material by the painted face that goes out pattern of ink discharge device; And

The absolute magnitude that applies the unit are of described ink penetration conditioning agent in described previous steps is not more than at described final step by the absolute magnitude that applies pattern color-fixing agent unit are.

Third embodiment of the invention also relates to a leather coloring process, forms pattern by stamp on leather, and its technology comprises:

One final step is to leather surface, at least to apply the ink penetration conditioning agent that can react with black coloured material on the leather on the painted face that goes out pattern by ink discharge device; And

The absolute magnitude of the described ink penetration conditioning agent unit are that applies in described previous steps is not more than the absolute magnitude of the pattern color-fixing agent unit are of dispensing in described final step.

Relate to the leather of third embodiment of the invention and paintedly mainly limit as above.

In this leather embodiment, if relate to leather coloring process, it will comprise layer arrangement of carrying out usually of dying, in this case, coating material needn't contain coloured material, and the form that wherein contains the existence that is difficult for volatile material can be considered to be similar to the form of the existence of above-mentioned coloured material.

The inventor has done further deep research to the characteristic that is sprayed onto the painted drop China ink on the leather, phenomenon below they have found as a result, be that they find, in order to make pattern quality even, be color even and form round point shape, necessary is to keep the infiltration thickness of China ink certain on the leather thickness direction, after painted the finishing of this external application China ink, for dyestuff and the stable pattern that so forms that applies the q.s that can satisfy the characteristic requirement, importantly make coloured material to pattern, forming with ink discharge device in the process of pattern, particularly in the process of the pattern that forms with ink-jet system, producing suitable reaction.

In order to make China ink reach best figure or China ink is spread at the superficial layer upper surface in its thickness direction infiltration, even China ink is the state of scattering on superficial layer, effectively the control China ink reaches the later time of leather, then, in coloured material, constitute the dissolving of black component or the evaporation of dispersant, be cured up to coloured material and close and in this fixation.Yet because water is widely used as solvent or dispersant usually, its China ink needs the regular hour to evaporate after arriving on the leather.Before such evaporation is finished, China ink permeates continuously and enters leather inside, at this simultaneously, coloured material infiltrates too continuously, the existence of any contiguous ink dot with do not exist, and in leather the difference of position, all influenced black characteristic, therefore make the existence of the coloured material of each point become inhomogeneous.The connotation of the ink penetration of the following stated is the thickness direction infiltration of China ink at leather, and the connotation that China ink scatters is the superficial layer diffusion of China ink at leather.

In order to prevent such inhomogeneities, preferably quicken evaporation of water in the China ink, for this purpose, people attempt the China ink that arrives on the leather is increased heat.Yet, being difficult for the continuous high temperature heating if considered leather, this is not a preferable methods just.Therefore, in the infiltration of regulating above-mentioned China ink or when scattering, adopt the most handy chemical method of physical method of heating to replace.By this method, make China ink arrive leather after, be contained in solvent or dispersant in the coloured material catalysis China ink in the Miboin body, so that finish non-solubilizing reaction or aggreation at the appointed time.

Behind the colored leather, in order to apply the enough colors and the stable pattern that can satisfy characteristic, effective method is a fixing coloured material well on leather.When attempting to reach this effect, can consider to adopt various means, for example tanning and emulsion oil-filling, they can make the physical property of whole leather change.But, for some special leather, then need consider the difficulty when processing method is selected, prevent destroyed or the like the problem of the intrinsic feel of leather essence.Yet if such change only produces on painted of surface, so such problem can be eliminated.Preferably make the coloured material in the China ink carry out chemical reaction, firm or stable apace, promptly " fix " by means so.

For this reason, for the stable pattern that forms, the means that they obtain are, carry out ink-jet colored leather step front and back by ink-jet, being applied to the component that China ink is reacted by the coloured material that contains on the leather surface common or painted part.In other words, considered such practical work, promptly had ionic component and be widely used in that they are included in the black sweat of ink-jet system in the coloured material, among the colored leather material that also is used to use always, because the effect of chemical bond can cause that coloured material carries out chemical reaction.Pattern described herein is included in the whole surface of leather and formed pattern on the part surface of leather.As described below, as the representative that is this coloured material of the widely used a kind of anionic dye of multiple coloured material, and the ionic bond between anionic dye then is the representative of this chemical reaction.

Such anionic dye has been described in a second embodiment, in this omission.Much less, if following ionic imputed opposite, then can adopt the CATION coloured material.

In invention,, can be applied to the ink penetration conditioning agent on the leather earlier, as the step before the colored leather in order to regulate the China ink permeability and the scattering property of leather relatively.The result, in subsequent steps, China ink arrive ink penetration behind the leather or the process of scattering in, produced ion combination reaction between coloured material in the China ink and the ink penetration agent, so that it is insoluble that the solvent that is present in China ink or the painted material in the dispersant are become, or become and have the attribute that disperses grain pleat line.Ions binding degree between coloured material and the ink penetration agent has produced required state, and it can regulate the form and the density of the each point that constitutes pattern.At this, ions binding degree or degree of ionization, that is, the quantity in the ink penetration conditioning agent can be according to the amount or the degree of ionization of the ink penetration agent that applies, the current potential number in the Jimo Osmolyte regulator and changing.

The ink penetration conditioning agent can preferably opposite with anionic dye cation dyes.This preferable material should be the material that is easy to dispose, and they can promptly be stored in the leather and can keep its cationic characteristic in leather, for example can select from the water-soluble cationic material.For such cationic substance is applied on the leather, at first its material is made the aqueous solution, then can will add or be sprayed onto on the leather.Subsequently, its aqueous solution infiltrate the inside of leather gradually and from the colored leather surface diffusion into the surface to its inside, simultaneously solvent moisture content constantly evaporates.At this moment, the probability that cationic substance has on the leather thickness direction is along increasing gradually towards its surperficial direction.

Here, coloured material and cationic substance contact with each other and work, and therefore, formerly the individual layer face of the ink penetration agent on the leather surface and absolute magnitude are littler than the unit are absolute magnitude of China ink on leather surface in the step, and they can well work like this.This also can not cause the bonding of useless material in the leather, thereby not hindering the intrinsic feel of leather and not hindering under the situation of the coloured material look in the leather itself, can regulate the infiltration of coloured material.In addition, because this effect, can particular restriction apply after the ink penetration agent and carry out the time of leather ink-jet before painted, for example, can be after applying the ink penetration agent and to carry out ink-jet after the intensive drying painted, also can be after applying the ink penetration agent solvent just to carry out ink-jet in evaporating course painted, i.e. evaporation just in time occur in ink-jet painted before, or when applying, take place.Any of these mode all can adopt.

By above-mentioned previous steps and colored leather step, on leather surface, form pattern.People wish that the pattern former state remains, and make it behind colored leather, and the high-resolution pattern still is present in the arranging process that carries out subsequently and finished product production process subsequently.In order to make image have better coloring and stable as the step behind the colored leather, the pattern color-fixing agent is added on the colored leather, owing to apply the pattern color-fixing agent like this, with coloured material reaction and ions binding, make the fixedly reinforcement of the coloured material in the colored leather face of established pattern on leather, thereby colored pattern is stabilized.Therefore, the face of dispensing pattern color-fixing agent is only limited to painted.

In the effect of this generation also owing to the contacting of coloured material and cationic substance (being similar to the ink penetration conditioning agent), therefore without particular restriction carry out leather after and apply time before the pattern color-fixing agent.For example, can carry out the back and through the after-applied pattern color-fixing agent of intensive drying in that the leather ink-jet is painted, also can be when common in the ink penetration process, that is, just in time at the after-applied pattern conditioning agent of ink-jet colored leather.Any of these mode all can adopt.

Yet, in the end in the step, the pattern color-fixing agent is combined with the coloured material particle is better, must apply the pattern color-fixing agent of capacity.Therefore, formerly be applied to the unit are absolute magnitude S of the ink penetration conditioning agent on the leather surface in the step ₁The unit are absolute magnitude S of the pattern color-fixing agent of dispensing to the leather surface in the step in the end ₂Preferably has such relativeness, i.e. S ₁＜S ₂, so that the formation of pattern is played more effective effect.In order formerly various leathers or pattern to be played more effective effect, the S on leather in step and the best step ₁+ S ₂Amount preferably is not less than the absolute magnitude of the coloured material unit are that contains in the China ink that applies in the colored leather step.At this moment the pattern color-fixing agent that applies can not exert an influence to the feel of leather, because each position that it only rests on coloured material and is arrived, the applied amount of the two only accounts for very little amount with respect to leather weight in addition.

As mentioned above, the purpose of ink penetration conditioning agent and pattern color-fixing agent, cationic substance all is to make they and coloured material to produce ionic reaction.Cationic substance will illustrate below especially.

At first, can select from the material that can quicken the liquid infiltration that comprises surfactant at the illustrational CATION lower-molecular substance of second embodiment, this is second

Illustrated among the embodiment.

In addition, can increase and the coloured material bonding, make the molecule of coloring material form polymeric material, can choose from the cation high molecular material, just in time second embodiment is illustrational like that.

These ink penetration conditioning agents and pattern color-fixing agent can suitably be selected from above illustrational material group, singly add respectively to apply or two or more components are applied, as long as they are suitable for having the leather of pattern.Because ink penetration conditioning agent and pattern color-fixing agent all are to produce ion combination reaction, so they can have the component that differs from one another also identical component can be arranged.Known various types of surfactant and adhesive also can preferably add, the viscosity that can regulate them according to the kind and the required function of used leather, volatility or the like.

They can be by applying such as being coated with the method that adds and spray.Specifically, can adopt roller coating device or spray gun, they are easy to the solution amount that is applied is regulated, and also can use the injection apparatus that comprises ink gun.

The other method of embodiments of the invention is a kind of leather coloring process, and it is used for painted formation pattern on leather, and this technology comprises, painted step goes out pattern by a kind of ink discharge device is painted on leather; And comprise and change progressively rapid, utilize ink discharge device that the pattern that is formed at leather is improved substantially; These steps are carried out basically continuously successively.

Still a kind of like this leather coloring process of above-mentioned technology is characterized in that, it revises step is continuous substantially step, which comprises at least an improvement step that adopts ink discharge device to carry out, and it improves step and comprises the arrangement coating; Between painted step and improvement step, a force drying step is set; Ink discharge device is an ink-jet system; Specifically, the used leather of the present invention is a leather that is prepared into like this, make rawhide or skin through comprising the tanning step of heavily tanning step, neutralize subsequently, emulsion oil-filling, water squeezing, stretching, extension and dry, regulate, draw soft, stretch dry, deburring after again, make leather smooth and have certain feel; By ink discharge device China ink is sprayed onto the grain side of leather and the side in the muscle side at least.

Tightly add step and consider the technical theme of long-term customary operation and obtained these features from dying to make, and found improved design from dying the needs of making the various habitual steps of arrangement.In habitual step, system of dying and interpolation all adopt Treatment Solution to carry out usually, consider this point, the colored leather step is now by ink discharge device, promptly finished by ink-jet system, such processing method simply and continuous substantially and can stably be made the multicolor patterns of high-resolution.

Ink gun during operation in the ink-jet system of common usefulness scans in the certain hour section, in this time period, will drive signal and deliver to each nozzle, and the ink droplet of controlling each nozzle sprays time and spray volume, in other words, leather has passed through preparatory process and has carried out tanning and tanning again, but no dyeing still, also refuel without Over emulsfication, stretch, regulate etc., make that leather is preliminary smooth and certain feel is arranged, these steps are carried out after its colored leather step, promptly earlier by the painted shape pattern of ink-jet system, then layer is dyed in arrangement, promptly improve step, to improve the surface that forms pattern, these steps can be carried out substantially continuously.

When the ink-jet colored leather, China ink only is directed onto and will forms the part of pattern, and forms adhesion especially, infiltrate in the leather, so the part that the coloured material in the China ink never adheres to and pattern is irrelevant.Like this, the feel of the surface state of leather or drying regime do not demonstrate great changes before and after the colored leather, therefore can improve processing, promptly after the colored leather step, are coated with ink-jet system and add.This has just improved productivity and efficient, has alleviated the pressure of evaporating solvent, owing to will use this step of a large amount of dyeing to carry out.And consider the amount of treatment fluid, this will be of value to the ink droplet of accurate control from the ejection of ink gun nozzle.Therefore eliminated the waste relevant, simplified adjusting being coated with the added-time, thereby shortened the time coating layer thickness with solution amount.In addition, owing to carry out colored leather with the form of China ink, rinse out unreacted coloured material after necessity hardly, thereby can effectively utilize coloured material according to the minimum coloured material amount of necessity.Be controlled on the constant owing to the amount that can adjust improvement solution artificially and with it in addition, so will never influence the feel and the roughness of leather.This carries out multi-color coloring and toning simply with regard to the energy freedom, and this is irrealizable for adopting usual way.When carrying out the ink-jet colored leather, stable in order to keep pattern quality, importantly painted of all-the-time stable and ink gun ink-jet between distance.As its means, realized at arranging process in the past, now can before colored leather, go.Therefore the leather that has been flattened can place on the leather coloring apparatus and enter the painted state of leather ink-jet that is very beneficial for.In addition, owing to regulate, drawing soft stretching drying to finish before colored leather, no longer is necessary so that tentatively leather is got the thin step of getting thin, that carry out at arranging process, therefore can prevent to be destroyed with the pattern of colored leather formation.

Simultaneously; so far the purpose of coating is to protect leathering; improve to handle and to finish having on the whole surf zone of pattern, also can only on a part of surface, finish, can easily control this ink-jet system according to the use of leather or the situation of colored pattern.Also change the kind of the various Treatment Solution that supply to each ink gun or the kind of the Treatment Solution that change is used for each nozzle easily, thereby can suitably adopt improvement solution.

In common interpolation process, usually adopting various sorted materials to carry out " wet to wet " (wet-on-wet) adds, so that obtain the arrangement leather of perfect condition, this also can improve step and carry out by many ink-jets of being arranged to delegation, and can carry out continuously, coloured material can also be included in according to the operating position of leather and fur products in the pattern improver, so that once finish its each step with simple continuous processing mode.

This shows that continuous colored leather step can be by adopting ink discharge device, that is, ink-jet system realizes, therefore can shorten the time that each step occupies and make its automation technolo.Yet, after China ink is sprayed onto on the leather and in this process before the enforcement of follow-up step, some Treatment Solution that are used to each step may make treatment surface not by good treatment not in this case, the step of one force drying effectively is provided between each step best, providing this step between colored leather step (comprising previous and final step) and improvement step is that effectively the effect that these steps played differs from one another.This step has also been strengthened combining between leather and tanning agent, emulsification oiling agent or the analog effectively as heat treated, and the leather protein hydrophily is reduced, thereby strengthen the combination between leather and the finishing agent, in such drying steps, thermal resistance according to leather is provided with suitable time and temperature, not special restriction.Yet and above situation can make it avoid the unnecessary of Treatment Solution to apply at an easy rate owing to handle by ink-jet system, these drying steps are not only simple but also can play satisfied effect.

Simultaneously, when usually leather being dyeed, consider as the protein adhesive source of leather Main Ingredients and Appearance and the combination between the dye molecule, with regard to this combination, coloring site is in leather inside, and this especially effect strengthens after the tanning, therefore we can say that leather is easy to be colored substantially, therefore no matter still be with regard to the muscle side with regard to the grain side of leather, the permeability that is considered to China ink is similarly, like this, and when implementing leather coloring process of the present invention, for sticking face side and muscle side, its technology can put on either side or both sides.

In the 4th embodiment, being used for being described in for example of the present invention is an equipment, its equipment is used to realize leather coloring process of the present invention, it comprises be used for carrying out painted ink discharge device on leather, make and on leather, form pattern, with a modifying device, be used for the pattern improver is applied to leather, can improve pattern by ink discharge device.This leather is one and forms the leather of pattern thereon by above-mentioned leather coloring process, and leather products is produced by this leather.

Then, be a leather coloring process, promptly by the painted pattern that forms on leather, its technology comprises:

One direct previous steps: be applied on the surface of leather regulating, be applied at least on the face by painted formation pattern with the ink penetration that black coloured material reacts;

One painted step: on leather surface, form colored pattern by ink discharge device, on the surface that applies the ink penetration conditioning agent, form above-mentioned pattern at least.

Tap into capable final step:, be applied at least by on the painted face that goes out pattern of ink discharge device being applied on the leather surface with the pattern color-fixing agent of leather China and Mexico coloured materials reaction always;

Change progressive rapid: improve the pattern that on leather, forms by its ink discharge device;

These steps are carried out substantially successively continuously.

The leather coloring process of its above-mentioned the 3rd embodiment can be finished by adopting such equipment.

For the above-mentioned the present invention of overall realization, when the colored leather step is finished with continuous substantially step by ink-jet system with the improvement step, leather is handled continuously, used ink gun is in certain period scanning, leather itself also moves simultaneously, thereby makes a treated side to the treated side continuous coloring that continues.Particularly, the previous steps and the final step of the described colored leather of first mode of third embodiment of the invention, can comprise these consecutive steps simultaneously, just, can be located at a kind of like this leather coloring process, wherein apply the ink penetration conditioning agent direct previous steps, colored leather step, apply the pattern color-fixing agent at direct final step with improve step and finish continuously successively substantially.

Embodiment 10

Figure 12 is a process chart, and its technology comprises carries out the prefabricated of leather and carry out colored leather and improvement on leather according to the present invention, to obtaining leather and fur products.Figure 13 shows the total at ink-jet coloring apparatus one embodiment of the present invention.

In Figure 12, preparatory process and tanning operation adopt the method for common usefulness to handle out the preparation leather from rawhide or skin, in this example, use sheepskin as rawhide, and bleach through chrome tanning with titanium oxide.Prefabricated like this sheep is through neutralizing with cylinder and sodium bicarbonate, and in cylinder emulsion oil-filling, promptly by mainly comprising the sulfurous acid cod

Emulsion oil-filling solution make its deliquescing.In common technology, dye liquor is added in the cylinder dyes simultaneously with emulsion oil-filling, then in this step, do not dye in the present invention.Then, adopt stretching machine, leather is through water squeezing and stretch step, infiltrates the excessive moisture of leather to extrude at neutralization and emulsion oil-filling, and extends to suitable size, hangs subsequently to do, regulate and draw soft so that get thin and deliquescing to leather.Then, sheepskin is toggled also deburring so that make it smooth, makes it to be fit to dried being placed on the ink-jet leather coloring apparatus, fixes its emulsion oil-filling agent simultaneously, thereby obtains being fit to the leather of water content.

After finishing to the step in this stage, leather is sent in each step that adopts the colored leather that ink-jet system carries out.Here, in order to implement these steps better, sheep is put to be done on the conveying supporting member 8 shown in Figure 9.This conveying supporting member 8 is one to comprise the part that the plain plate 81 made by stainless steel and the side on its whole surface have the adhesive 82 of quite little viscosity.

The sheepskin that has sticking face side outside can making thus is by firm attachment, and at first the ink penetration conditioning agent with the following stated is sprayed onto on its sticking face with spray gun, and its dry back coverage is 1g/m ², promptly pressing under room temperature and the standard humidity dry about 1 hour after the spraying.

Then, adopt the ink-jet leather coloring apparatus, on the grain of so handling, form pattern, sheepskin itself has goodish water imbibition, therefore, and in spraying, its component can be handled very fast infiltration leather well, need not anyly heat drying device especially.In addition, the ink penetration conditioning agent contains surfactant, can quicken the infiltration of all spray solutions in leather.Like this, after the drying, the component of ink penetration conditioning agent is not to form one deck in its surface under this state, but shown in Figure 14 A like that, infiltrate leather with this state.In Figure 14 A, label 7 expression leathers, 701 expressions be sprayed onto on the leather the ink penetration conditioning agent they infiltrate in the leather.Owing to can keep such state, make the surface state of painted areas can keep identical substantially with spraying ink penetration conditioning agent state before, therefore when advancing colored leather, the ink penetration conditioning agent neither can adhere on the surface by overslaugh Miboin body, and the feel that also can not influence whole leather changes.

Then, on the leather of handling like this 7, adopt ink-jet leather coloring apparatus as shown in Figure 5 forming pattern by ink-jet is painted.When being undertaken by the operation of ink-jet coloring apparatus when painted, the state that ink droplets infiltrates leather 7 as shown in Figure 14B.Be sprayed onto like this on the leather 7 and infiltrate wherein each ink droplet and can be held, represent the lip-deep diffusion of infiltrating the degree of depth of leather and having infiltrated ink penetration conditioning agent zone with label 706.Like this, when ink-jet is painted, can obtain uniform pattern form.On the other hand, when the ink-jet leather coloring apparatus that adopts as Fig. 5, the sheep shown in Figure 15 A is carried out ink-jet when painted, its mode is identical but do not apply any ink penetration conditioning agent, and it is such that the infiltration state of its ink droplet becomes Figure 15 B.Thus, the ink droplet state of representing with label 707, on same leather its to infiltrate the degree of depth of leather be different with from the teeth outwards diffusion, thereby cause uneven pattern form.

After such colored leather is finished, pattern color-fixing agent as described below is sprayed onto on the sticking face of the sheep that has formed pattern continuously according to the mode that adopts spray gun spraying ink penetration conditioning agent, its coverage of dry back is 2g/m ², then to being coated with sprayed coating drying under the room temperature normal temperature about 1 hour.In this stage, for coloured material and the more macromolecular gathering of formation that bonding participation pattern constitutes, the molecular weight of the polyene propyl group sulfone of ionic reaction is bigger than the molecular weight of the ink penetration conditioning agent that applies in advance.The result who sprays its pattern color-fixing agent is shown in Figure 14 C, and its solution promptly infiltrates leather from sticking face side gradually from forming a side of pattern.In process of osmosis, have big relatively infiltrative benzalkonium chloride at first be present in the coloured material ions binding that forms pattern part, then it is in conjunction with beginning to influence polyene propyl group sulfone and coloured material, dissolving and combination together.By such reaction, it is big that the molecule of coloured material obviously becomes, thereby prevent that the ion of coloured material in leather from moving, and constitutes to stablize its color, makes coloured material water insoluble simultaneously.In other words, pattern can be stabilized and present WATER RESISTANCE.

The ink penetration conditioning agent:

Benzalkonium?chloride 3％

Polyene propyl group sulfone (weight average molecular weight is 10,000) 3%

Water 94%

The image fixative

benzalkonium?chloride 1％

Polyene propyl group sulfone (weight average molecular weight is 50,000) 5%

Water 94%

By above-mentioned technology the pattern that sheep carries out the painted formation of leather ink-jet is made up of the ink dot with uniform shapes, and is to have highdensity stable pattern.Pattern also helps the improvement to durability such as WATER RESISTANCE, is suitable for very much the arrangement coating that next step carries out.

Pattern form on the sheep these steps till by this stage are finished, and then, the sheep with such formation pattern is sent to the improvement step, puts coating in order.

Figure 13 shows sheepskin is improved the consecutive steps that adopts when handling, as shown in figure 13, improve step and be provided with three phases, promptly, they are to be coated with by the company by ink-jet systems eject pattern improver to add arrangement to be used for descending being coated with of coating, inter coat and last coating to add arrangement, and they are by being realized by the consecutive steps of ink-jet systems eject pattern improver.The spray coating liquor that uses in these steps, promptly the coating solution that uses in common spraying process can be used as the coating solution that these steps are used, and for example can use material polyurethane-type, propylene or the cruel type of breast with suitable compound mode.The step of improving sheep is described below with reference to Figure 13.In description, respectively first, second and the 3rd improve step be coated with under being called add, the centre be coated with add, on be coated with and add.

At first a conveying supporting member 13 of being made by corrosion resistant plate is placed on the conveyer 2011, so that transmit left in the drawings, secure adhesion and is formed figuratum leather 7 on described conveying supporting member.Then conveyer 2011 is carrying supporting member 13 to be sent to the lower end (in the drawings) of sub-scanning leather 2003, and belt 2003 improves zone 2001 by the drive source (not shown) towards first and extends.When carrying supporting member 13 to arrive the lower end of sub-scanning belt 2003, carrying 90 ° of supporting member 13 continuous rotations to be the back side vertical, corrosion resistant plate is attached on the surface of sub-scanning belt 2003, here, carry supporting member 13 to be designed to and to combine with sub-scanning belt 2003, distinguish so that leather 7 can move the first following coating solution spraying that improves zone 2001.Subsequently, sub-scanning belt 2003 is driven with the direction of balancing speed along arrow U, carries supporting member 13 to move upward (as seeing among Figure 13) simultaneously, and leather 7 is sent to down coating solution spraying district.When leather during by such conveying, coating solution under the ejection of spraying district, and the following coating on the leather begins to be positioned at an end of leather 7, and leather is then held by the back side skin of plate 2002, and this back side is towards sub-scanning belt 2003.After finishing the following coating on the whole surface of leather, its sub-scanning belt 2003 is driven again, leather arrives the flat part (as shown in the figure) of the sub-scanning belt 2003 among the figure, up to carrying supporting member 13 near leather lifting platform 2021, then will carry supporting member 13 to unload from the sub-scanning belt, and move on on the leather lifting platform 2021, accepted and carried the leather lifting platform 2021 of supporting member 13 to be driven decline automatically, carrying supporting member 13 to move on on the conveyer 2012 along support column 2031.

Leather 7 through coating processing down carries out the inter coat processing continuously at second improvement part 2004, it handles identical with the modes of first improvement zone 2001 operations, promptly, carry supporting member 13 to be fixed on the sub-scanning belt 2006, it moves along arrow V direction with balancing speed, and when improving the coating solution spraying district in zone 2004 near second, spraying inter coat solution, then be placed on the leather lifting platform 2022, descend along support column 2032, thereby move to conveyer 2013 places.Repeat similar operation again, improve zone 2007 the 3rd and finish the top coat processing.At last, carry supporting member 13 to be sent to the front end of conveyer 2014, like this, leather improves, and promptly top finish ends.

In these a series of operations, improve the various processing that improve the 2004 and the 3rd improvement zone 2007, zone in zone 2001, the second first and all realize mechanism in these zones and operation by ink-jet system, identical with ink-jet coloring apparatus shown in Figure 5, therefore here do not describe.Direction B correspondence among Fig. 5 and all directions U among Figure 13, V and W, under the situation that this improvement is handled, the black feeding device 61 of the leather ink-jet coloring apparatus of Fig. 5 can be made into a chamber, and being full of coating liquid used in the variety of processes, the operation of its equipment is identical with colored leather.

In the present embodiment, leather is moving between the supreme coating step of coating step down, because these steps are a series of operations, leather does not shift out or be sent to the outside, even also be so when coating solution changes, does not therefore use manual operation.Therefore leather passes through these steps automatically, compares with normal conditions to reach purpose of energy saving.In the motion between above-mentioned steps, main is the time that will determine to transmit the conveying supporting member 13 that has leather, but will to help what carried out before be effective enforcement that dry coating is handled such time.

Described these operations have been finished, and will form the pattern of high-resolution on leather, obtain the pattern that can not degenerate in top finish, and have shortened the time of handling.In consecutive steps, leather has the required characteristics of making various leather and fur productss, and leather can be filled out heavily, carries out various stitchings, makes leather products such as suitcase.

Embodiment 11

Figure 16 shows the general structure of the leather coloring apparatus of another pattern of third embodiment of the invention, Figure 17 shows the major part of Figure 16 ink-jet color applicator, this pattern is compared with example 10 patterns, its China ink quilt ejection vertically downward, and leather carries along a direction, therefore can simplify the operation.In this leather coloring apparatus, to finish by ink discharge device 15 with the painted step of China ink, the previous and final step of colored leather is finished by ink discharge device 14 and 16, is finished by ink discharge device 17 and improve step.The all devices structure is identical.How to operate in order to describe leather coloring apparatus, at first describe the main operation of ink-jet system with reference to Figure 17.

Figure 17 shows in the above-mentioned leather coloring apparatus general structure part corresponding to ink discharge device 15 and 16, and they have finished colored leather step and its final step.The operation of these ink discharge devices mode of operation basic and in the example 11 is identical.In set ink discharge device 15, the ink gun 1500 that sprays painted China ink comprises the ink gun assembly of being arranged to four groups, and all multiinjectors set gradually, and ink gun 1500 also is connected with the auxiliary black case 1501 that temporarily holds China ink, and its black case has been loaded onto China ink.The inside of auxiliary black case 1501 is divided into the chambers of the China inks that mass colour, cyan, four kinds of looks magenta and yellow are housed respectively, so that with China ink being fed on painted assembly of four ink-jets of (color-by-color) side by side.China ink of all kinds is delivered to each chamber that so is divided into from separating the ink-feeding device that is provided with by the pipe (not shown).Mark K, C, M, Y on the auxiliary black case 1501 represent black, cyan, magenta and yellow respectively.These ink guns 1500 and auxiliary black case 1501 all are arranged on the slide 1502, slide 1502 along the arrow C direction shown in the figure along guide rail 1503 and 1504 shuttle-scannings move, begin downward ink-jet according to figure signal from ink gun 1500 simultaneously, thus painted on leather 18.When slide moved back and forth one time, leather 18 was transferred along the arrow E direction continuously, and is painted up to forming on whole surface.

When the place, part of above-mentioned ink discharge device 15 carried out colored leather to leather, in the reciprocating motion process each time of slide 1502, the zone of being sprayed may change, and this is because the leather size was just nonstandard originally.As a kind of countermeasure, can on leather 18, make territory, a maximum spout ink-covered area to the ink-jet zone of ink gun in advance, yet, adopting this mode, the part of China ink still can be sprayed onto the outside of leather 18, causes the waste of China ink.In order to prevent the waste of this China ink, in ink discharge device shown in Figure 17, near ink gun 1500, be provided with the leather checkout gear 1505 that is used to detect the leather situation, it is synchronous detecting output and ink-jet head driving signal, in case ink gun 1500 scans the part in leather 18 outsides, ink-jet is promptly ended.The leather checkout gear 1505 here adopts the reverberation relay.This leather checkout gear 1505 need not be provided with any specific mechanism.Except this device, can adopt the method that various types of optical pickup apparatus and light emitting devices are used in combination, can also adopt such method, promptly survey the end of leather, thereby discern the scope that exists of leather 18 by the contact of energy pin under a kind of low-force.

Equally, with reference to Figure 16, be used for the step that the painted back of leather ink-jet is carried out, the ink discharge device 16 that promptly is used for spray pattern color-fixing agent solution be arranged in parallel with the vibration-direction of above-mentioned slide 1502 and is arranged on the upstream side of leather 18 throughput directions.Refer again to Figure 17, in ink discharge device 16, the ink gun 1600 of ejection pattern color-fixing agent comprises an ink gun assembly, and it has all a plurality of nozzles that set in a row.This ink gun 1600 is connected with the auxiliary processing liquid case 1601 that temporarily holds the pattern color-fixing agent and the pattern color-fixing agent has been housed, its auxiliary black case 1601 is designs like this, by a pipe (not shown) its pattern colouring agent is fed in this case from separate the supply treatment fluid device that is provided with.Operate its ink discharge device 16, carry out final step and handle, the pattern color-fixing agent is coated with is added on the leather 18, on this leather, carried out colored leather by above-mentioned ink discharge device 15.Ink gun 1600 and auxiliary processing liquid case 1601 all are arranged on the slide 1602, according to the signal that passes to ink gun 1600 from the conveyer (not shown), slide 1602 moves back and forth scanning along the arrow D direction among the figure and along guide rail 1603 and 1604, from all nozzles of ink gun 1600, spray the pattern color-fixing agent simultaneously downwards, after just carrying out colored leather, promptly leather 18 is carried out direct final step and handle.So slide whenever moves back and forth once, leather 18 is just carried continuously along the arrow E direction, handles up to its whole surface having been carried out direct final step.In order to detect the zone that leather 18 exists, by reverberation interrupt the 10 leather checkout gears 1605 that constitute also be arranged on ink gun 1600 near.Control its pattern color-fixing agent thus and only be sprayed onto the part that leather exists.

The ink discharge device 14 that is used to spray the ink penetration conditioning agent is identical with ink discharge device 16 with the operation of the ink discharge device 17 that is used to spray the top finish material, and it is described in this and saves.

Refer again to Figure 16, be used to carry the device of leather 18 to have a following described structure, that is, its conveyer has an adsorbent equipment 19 that is used to adsorb leather 18, and it adsorbs not colored surface side of leather by suction.This adsorbent equipment 19 has one in mechanism that the direction upper edge of Figure 17 direction E rail 1901 moves, in order to begin the colored leather operation, at first leather 18 is positioned on the adsorbent equipment 19, produce suction within a certain period of time by a drive source (not shown) then, catch leather to make it smooth simultaneously securely by suction, then, adsorbent equipment 19 advances along the arrow E direction, near ink gun 1400, begin the colored leather operation up to the front end of leather 18 at this.After this, slide 1502 makes a round trip again, places leather 18 on the adsorbent equipment 19 just along the arrow E direction, and move forward continuously once according to the first painted width of ink-jet, the same speed of leather 18 is pushed into again, and near ink gun 1500, then carries out above-mentioned being coated with continuously and add.To being coated with on the leather 18 add finish after, discharge absorption, end operation to leather 18.

The equipment that employing has this spline structure has just constituted leather coloring apparatus, and this equipment comprises previous steps, painted step, final step and improvement step, and all these steps are all carried out continuously.Previous steps and final step have only occupied the very short time between these steps and the painted step, therefore can be regarded as the direct previous steps and the direct final step of painted step.And in this leather coloring apparatus, leather can easily be provided with and transport path in a straight line, therefore simplified the structure that is used to carry.Therefore painted on the leather more is of value to automation.Its equipment is except these advantages, and the distance that is provided with between each ink discharge device can change arbitrarily, therefore be used to comprise before claiming and the colored leather of last treatment step or improve carry out the dry time after the operation can be according to the setting arbitrarily of this distance.This has just more enlarged range of application and the component of each Treatment Solution or the scope of emitted dose of used China ink.

Embodiment 12

Figure 18 shows a more advanced example of example 11 patterns, and illustrates the total of leather ink-jet coloring apparatus. Ink discharge device 14,15,16 in ink discharge device of She Zhiing and the example 11 is identical with 17 in this example.In this example, the ink discharge device that linearly is provided with is respectively equipped with drying device 300 and 310 at its outlet side.At the also similar drying device that is provided with of each outlet side of ink discharge device 16 and 17, economize among Figure 18 and got this device.If such drying device is set, after comprising that painted step previous and final step or improvement step is implemented, leather 18 directly enters each drying device, and the solvent component of each Treatment Solution of being sprayed is compelled to evaporation, thereby has shortened the time before the subsequent treatment.The size that this just can shorten each time of handling and reduce whole leather ink-jet coloring apparatus.

The common non-refractory of leather, it depends on kind or the process for tanning of animal.Therefore the temperature in the drying device is unnecessary too high, its temperature is preferably 60 ℃ or lower, this temperature also is the temperature of setting in common emulsion oil-filling, under such temperature value, impossible dry leather at once, therefore leather ink-jet coloring apparatus shown in Figure 180 is of value to realization control, so that the motion of adsorbent equipment 19 is stopped, thereby leather 18 is stayed in drying device 300 or 310 in official hour, dry better leather, in this case, controllable device makes it also to end the operation of ink discharge device in above-mentioned stopping.Example 13

Figure 19 shows another pattern of third embodiment of the invention, and wherein, in the leather ink-jet coloring apparatus of Figure 16, only before improving step and afterwards this section is provided with drying device.In having the colored leather step of previous steps and final step, its Treatment Solution can not be added in the leather 18 too much, therefore each step is not too needed drying.Similarly, the top finish material that improves in the step does not need excessive use yet, just can keep the key property of feel and leather, therefore not too needs drying in improving step yet.

On the other hand, if this stage is provided with drying device 300 after the step of the front and back of colored leather and before improving step, heat effect rather than desiccation are applied to this part of leather, and this has just more strengthened coloured material in the colored leather 18 and the combination between the leather itself.And after improving step, drying device 310 is set, then can further improve the fixed performance between top finish material and the leather 18.Because such structure can prevent the degeneration of colored pattern.

Adopt above-mentioned structure having the stable pattern of formation on the leather that quite lacks coloring site, and obtain more firm pattern.And easily when colored leather the operation leather, and very fast on leather, carry out painted.

Above-mentioned example all is described its method, wherein, leather is being carried out when painted, and each step process is all carried out whole leather surface.In leather coloring process of the present invention, these methods never only limit to this, can adopt the above-mentioned steps order at least the regional area of leather to be handled.In other words, for the zone of arbitrary needs on the leather, can carry out in the following order, promptly adopt the previous steps of ink penetration conditioning agent, the painted step of leather ink-jet adopts the final step of pattern color-fixing agent and improves a kind of like this order of step.Like this, the present invention can also comprise such formation, and when with ink discharge device a leather being scanned, the ink discharge device that sprays each treatment fluid continuously is row and is provided with, and the treatment fluid in each step is applied continuously, thereby finishes the painted of the whole surface of leather.

As mentioned above, according to third embodiment of the invention, thereby by ink discharge device painted when on leather, forming pattern on the leather, the ink penetration conditioning agent applies as its previous steps, and the pattern color-fixing agent applies as its final step, therefore, it is fabulous that the pattern that forms on leather has higher definition and better coloring and fastness.

In addition, mode to the processing leather of common employing, the inventor has noticed a kind of processing mode, it is not only the processing that the physical property to leather itself changes, that is, dyeing and top finish have been re-recognized the processing procedure that begins to handle from rawhide or skin, find to adopt ink discharge device to carry out top finish, can produce leather and fur products effectively.The result can carry out with the colored leather step is a kind of continuously as the improvement step of typical top finish.

By these treatment steps, can make that the pattern on the leather has good performance, and make the step automation till arrangement.This method has also been brought many advantages, promptly can obtain the realization of pattern of processing, polychrome and the high-resolution of many and class in a small amount, and the handling problem of unnecessary Treatment Solution is also solved in addition.

Like this, do not limit common leather use, do not increase under the situation of product cost and time very much, can obtain to have the leather and fur products of first-rate quality pattern and high quality of products.

Claims (8)

1. leather coloring apparatus, it comprises:

A device that when carrying out ink-jet, changes the China ink amount according to the type that will carry out the natural leather of colored leather according to chrominance signal;

An ink discharge device; With

One is used for natural leather with under the ink discharge device state of contact be not sent to the conveyer of the colour attaching area of ink discharge device.

2. leather coloring apparatus according to claim 1, it is characterized in that, described ink discharge device is a polychrome ink discharge device, and described leather coloring apparatus comprises that also an output is used for carrying out the master computer of the necessary polychrome information of colored leather on natural leather.

3. leather coloring apparatus according to claim 1 is characterized in that, carry out painted natural leather and be arrived low lipid level or partly degreasing of quilt by degreasing.

4. leather coloring apparatus according to claim 2 is characterized in that, carry out painted natural leather and be applied in one deck China ink receiving layer.

5. leather coloring apparatus according to claim 4 is characterized in that, described ink discharge device is configured to China ink is applied on the subregion of described black receiving layer.

6. be a kind of application of acquisition according to each described leather coloring apparatus among the claim 1-5 to the painted leather of small part.

7. a utilization is according to painted leather or the leather and fur products of each described leather coloring apparatus part among the claim 1-5.

8. leather according to claim 7 or leather and fur products is characterized in that also comprising the protective layer of one deck on coloured part.

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