CA1221882A - Artificial grained leather having different color spot groups - Google Patents
Artificial grained leather having different color spot groupsInfo
- Publication number
- CA1221882A CA1221882A CA000439873A CA439873A CA1221882A CA 1221882 A CA1221882 A CA 1221882A CA 000439873 A CA000439873 A CA 000439873A CA 439873 A CA439873 A CA 439873A CA 1221882 A CA1221882 A CA 1221882A
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- Prior art keywords
- fibers
- grain leather
- ultra fine
- artificial grain
- high molecular
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to an artificial grain leather having different color spot groups comprised of ultra fine fibers, in which at least one side of the fibrous substrate has two types of colors differing in hue and/or lightness value and being covered with transparent resin layers. The present invention produces a three-dimensional surface effect and a grain pattern effect, and is recognized as consisting of a mixture of ultra fine fibers each being quite different in color from the next, though providing the appearance of a single color from a distance, and producing a subdued and rich appearance as a result of the integration of colors by the color of a coating layer.
The present invention relates to an artificial grain leather having different color spot groups comprised of ultra fine fibers, in which at least one side of the fibrous substrate has two types of colors differing in hue and/or lightness value and being covered with transparent resin layers. The present invention produces a three-dimensional surface effect and a grain pattern effect, and is recognized as consisting of a mixture of ultra fine fibers each being quite different in color from the next, though providing the appearance of a single color from a distance, and producing a subdued and rich appearance as a result of the integration of colors by the color of a coating layer.
Description
~ ZX~38~' The present i.nvention relates to an artificial ~rain ic;~tller consisting of a fibrous substrate and a coating layer, said fibrous substratc composed of ultra fine fiber, having at least two kinds l;ith difrercnt color hues and/or lightness shades and being coated on at least one side thereof by transparent resins.
Recent development of an artificial gr~in le~th--r has progressed remarkably. !`~uch effort is being made to obtaill an artificial leathcr, the grained surface of which more closely resemhles that of the natural leather consisting of ultra fine fibers, and to correct the defects in natural leatiler.
However, there remain many requi.rements which have not yet been met. For instance~ a leather is needed which is ~ore agreeable to the touch than natural leather; or a leather having more sophisticated coloring WiliC}I has no~
been obtained by the conventional and artificial grain leather or natural leather which is single-tone colored; or a leather of higher quality and subdued color or a leather of coloring not achievable with print dyeing, in particular~ due to its pores; or an artificial leather whose feel is that of the natural grain leather which is obtained without embossing.
Further, the coated surface of conventional artificial grain leather has been shaded by applying a deep colored composition directly to the ~onochromatic coating using a print roll. Thus, conventional artificial grain leather has disadvantages, such as lack of impressiveness in colors, restricted color variety, lack of cubical appearance, and poor color fastness because it can easily become discolored by surface friction, heat, or solvents.
The present invention is directed to providing an artificial grain leather with a high grade appearance having superior grain pattern effect and a ~.~2~
three-dimensional surface effect. The term "three-dimensional surface effect" means a surface which has the appearance of depth and uneveness due to different color spot yroups.
The present invention also at-tempts to provide an artificial graln leather having different color spot groups, which looks like a single color at a distance but which, close up, can be discerned as a mixture of en-tirely differently colored ultra Eine fibers and which gives an impression of richness created by overlapping their colors on the surface.
Additionally, the present invention is directed to providing an artifical grain leather presenting an entirely new tint with quality appearance and having different color spotgroups, all of which cannot be attained by a natural leather and also an artificial grain leather having high strength and vivid color.
Thus, according to the present invention, there is now provided an artificial grain leather having different color spot groups comprising:
a fibrous substrate layer of ultra fine fibers, bundles of ultra fine fibers or mixtures of ultra fine fibers and bundles of ultra fine fibers, wherein said fibrous substrate layer contains a high molecular weight viscoelastic first polymer; said fibrous substrate has at least two types of colors selected from the group consisting of colors of different hues, colors of different light-ness values and mixtures thereof; and at least one side of said fibrous substrate layer is a coating layer of a transparent high ~ 2 , ~r ~
~X~ 3X
molecular weight second polymer and appears on the apparent face of the artific:ial grain leather.
The present invention will now be described in more detail by wav of example only, with reference to the accompany-ing drawing, in which:
Figure 1 illustrates in cross section a surface portion of an artificial grain leather having differen-t color spot yroups provided by the - 2a -present invcntion, Figure 2 is a cros, section of ultra fine composite fiber bundles provided by thc present inventiO;l, Figure 3 is a cross section of the ultra fine composite fihers with the core-sheath t~pe structure provided by the present inven~ioll, ~ igures 4 and 5 are cross sections of ultra fine composite ~ibers with the conjugating and the conjugated type structure, respectively, provided by the present invention, Figure 6 illustrates, in perspective view, ~ rais~d nap on the fibrous substrate which is made of a nappy matcrial.
The fibrous substrate of the present invention is composed of ultra fine fibers ~hich are not more than about 0.7 denier, preferably bet~een about 0.0001 and about 0.3 denier, or bundles comprising chiefly such ultra fine fibers. The fibrous substrate of the presen-t invention exhibits the unique and rich characteristics of high grade color and feel because of the synergistic effect of the composition provided by blending ultra fine fibers as mentioned above.
To produce the ultra fine fibers used in the present invention, a conventional process may be used. The method includes, for example, that of making the ultra fine fibers by a sui.table means from multicomponent fibers such as islands-in-a-sea type composite fibers, high molecular inter-arrangement fibers, stripped-off type (rice type, chrysanthemum type, ribbon type, etc.,) composite fibers, special polymer-blended type fibers, etc.
The making of such ultra fine fibers for the present invention generally includes, but is not limited to, chemical and physical means such as dis-solution or decomposition of one component, and decortication of components, etc. Other useful means include the use of super-draw ~ - 3 _ ~ .
~2~
spinning, strony blowing spinning with air, and star-cloud type.
Details are referred to in, for example, ~he "Chemical Fiber Monthly Bulletin" July issue, 1977.
The cross sectional shapes of the fiber to be used include round cross section which is the most common, as well as any other shapes such as fan-shaped triangles, fan-shaped frustums, rectangles, cross-shapes, T-shaped triangles, Japanese rice ball-shaped triangles, and other multi-lobar shapes, various kinds oE shapes with n-lobes and n-processes (n is an integer), hollow shapes, deformed hollow shapes and ellipses.
The phrase "comprising chiefly of" which may be used in the instant specification includes the cases where fibers of large denier above the defined limit are mixed or foreign sub-stances such as additives are applied to the fibers, to such an extent that there is no substantial influence on the functional effect of the present invention. The phrase implies, for example, that a very large amount of ultra fine fibers may contain small amounts of thicker fibers of not less than 0.7 denier. There are also some cases in which, in making ultra fine fibers by stripping off the stripped-off type multi-component fibers, another component lying between the ultra fine fiber components remains as thick deformed cross section yarn, or the multi-component type fiber itself being capable of producing ultra fine fibers remains as a larger fiber without being changed into ultra fine fibers. A further implication is that, even in the above case, if the portion of the unchanqed remaining larger fiber does not exceed -the greater part of the who]e fiber, the object of the present inven-tion can ade~uately be achieved. In any case, any variation within this limitation which does not cause a loss of the functional effect required by the present invention may be included in the present invention.
The fibrous substrate sheet used in the present invention may be composed of kni-tting (i.e., knitted fabric), unwoven fabric such as needle-punched felt, woven ~abric, a laminate of such materials or a sandwiched form of such materials.
At least one side of the substrate has the above-mentioned grained surface.
Methods for producing the fibrous substrate sheet are virtually limitless. When one side of the fibrous substrate is ~o have a nap, the substrate used is a nappy knit or fabric such as velveteen, corduroy, blanket, double velvet fabric, velvet, etc. After the sheet is formed, the nap is raised by methods used in the manufacture of similar fabrics, including abrasion with raising fillets or emery, buffing, loop-cut or electric placement of the nap.
The fibrous substrate of the present invention may contain various kinds of conventional high molecular viscoelastic substances such as polyurethane, polyurethane urea, acrylic resin, silicone rubber (which may be vulcanized) fluorine resin or a mixture thereof.
One feature of the fibrous substrate of the present invention is the multicolor dyeing of the substrate. The multi-color dyeing may be dyeing ultra fine fibers in a bundle with ~2 ~ 2 different colors or dyeing adjacent bundles with different colors.
~'he multicolor dyeing is achieved by using at least two types of ultra fine fiber material wi-th different dyeablilities and dyeing each of them with different types of dyestuff.
The ultra fine fibers are classified by the differences in dyeability into dyeable fibers wi~h desperse~ acidic, basic, direct and reactive dyestuff. A combina~ion of at least two types of fiber may be selected from the above-mentioned ~roup. The fibrous substrate is composed chiefly of the ultra fine fibers, a small amount of common fibers may be mixed with the ultra fine fibers as the other fiber having different dyeability provided that the desired mixed color ef~ect is achieved.
Examples of the dyeable fibers with disperse dyestuff include polyethylene terephthalate, polyoxyethylene benzoate, polybutylene terephthalate, or these substances whose copolymer-ization is modified to a greater or lesser extent or a blend formed by mixing with a modifying agent, and polyamides with a rigid structure.
Examples of the dyeable fibers with acidic dyestuff involve polyamides having amino end group such as the familiar nylon 6, 66, 610 12 PACM.
Examples of the dyeable fibers with basic dyestuff are substances having -SO3Me(Metal) group, especially -SO3Na group or combinations.
Typical polymers for fibers of the above group are polyacrylonitrile type copolymerization polymer, polyethylene ~218~3~
terephthalate or polybutylene terephthalate polymer copolymer-ized with sodium sulfoisophthalate, or mixed, etc.
As to the dyeable fibers with direct or reactive dye-stuff, which may be ones containing a reactive group, typical are the fibers having -OH group such as cellulose or polyvinvyl alcohol type. All the above fibers are of conven~ional ones, but substances other than the above may, of course, also be used.
A combination of at least two types of fiber selected from the above group is used to form the fibrous substrate. A
typical example of the methods of forming the fibrous substrate made of such combination fibers includes blending or mixspinning two types of multi-component type fibers, from which bundles of ultra fine fibers consisting of the island components can be produced by removing the sea components, the island components of said fibers having different dyeabilities from each other.
From the resultant mixed spun yarn, web or filament, the fibrous substrate is formed.
Alternatively, instead of the multi-component type fiber, bundles of initially very fine fibers which can be obtained by the super draw process, may be blended or mix-spun. An example of fine fiber combinations useful in the latter method is a combination of a high molecular arrangement fiber of islands-in-a-sea type fiber dyeable with a disperse dyestuff and a high molecular arrangement fiber of an islands-in-a-sea type fiber dyeable with a basic dyestuff. An example of the former island polymer is polyethylene terephthalate, and an example of the latter island polymer is polyethylene terephthalate copolymerized ~ . ;
=, "
~x~
with sodium sulfoisophthalate.
A further example includes a mixture with the islands-in-a-sea type high molecular arrangement fiber whose island component is nylon 6 (the acid dyeable type containing many amino end groups).
The combining ratio (the ratio of each island component) may be selected optionally, and may range from about 1 to about 99% depending on the purpose to be achieved. The range of about 5 to about 95~ creates an outstanding effect. In ~eneral, a preferred effect often results from a choice of the proportion of not more than about 50% of the fiber that has the deepest color. Especially, when the deep-colored fiber is mixed in a low proportion, the mixed part produces pores effect, which further enhance, the effect of the present method. When the deep-colored is mixed in a high proportion, then a gradation effect results.
With the multi-component fiber used in the present invention, it is not necessary that the island component to be perfectly enclosed by the sea component. The so-called split or stripped-off multi-component fiber, in which both components adhere to each other in parallel, may be employed. In any case, the sea component is removed, and at least the island component or the component corresponding to the island component is principally utilized.
When the multi-component fiber is used, the forming of the ultra fine fiber is carried out at an appropriate stage either before or after the formation of the sheet. This is preferably conducted after the formation of the sheet in the present invention, for reasons of qood processahility and soft fibrous substrate.
When common fibers are mixed, it is necessary to control the proportion such that the common fibers never constitute the major part. Particularly, in the case of makinc3 a raised nap on one side of the fibrous substrate, the proportion of common fibers is preferably limited to less than about 20~, more preferably not more than about 10%, taking into consideration the feel, and the reversible lie of the nap, etc.
In any case, exceptional effects such as feel, luster, the combination with color of the grained surface coating, and additionally coloration of binder, which should not be defined merely as common multicolor mixing, are obtained due to the unique effect of the ultra fine fibers. A treatment for making ultra fine fibers, which may be selected from various method$, is necessary only when the multi-component fiber used has not yet been made ultra fine. With certain kinds of multi-component fibers, it is possible to simultaneously make the multi-component fibers into ultra fine fibers and dye the resulting ultra fine fibers. The dyeing may be carried out in the same way as for dyeing of staple, filament or fibrous sheet, and usually takes place after the fibers are formed into a sheet.
The ultra fine fibers are dyed by a single-bath method or a multi-bath dyeing method. The main feature of these methods and the actions which take place during the process are as follows:
. ~
,~, , .~
~2~2~8~
In the single-bath dyeing method, the period of which may be shor-t, it is necessary to select a proper dyestuff and to use a reserve printing agent and a suspending agent, because a problem may arise from the formation of precipitates produced by the interaction between the different types of dyestuff and the resulting contamination. ~lowever, imperfect removal of the contaminated dyes effects the lightness of color and fastness of the dye which restricts the quality of extremely deep and li~ht colors, and their vividness. In the multi-bath dyeing method, in which different types of dyestuffs can be used in each separate bath, there is no danger of precipitate formation from dyestuff reactions, and there is also an advantage that lightness shades and high fastness of dyeing colors can be obtained by employing the so-called intermediate cleaning process which cleans the fibers on the contamination side. The so-called single-bath, multi-step dyeing method, which is included in the single-bath dyeing method in the present invent-ion, produces an intermediate result between the single-bath and multi-bath dyeing methods. The methods mentioned above are conventional and dyeing in the present invention may be carried out by any such method. It is necessary, however, to select a combination of dyestuffs which cause dyeing in multi-colors as defined below. When two different fiber samples are removed from the base and they show a difference in dominant wave length of not shorter than about 5 m~, preferably not shorter than about 10 m~, measured by a color difference meter, the fiber is said ~L2~
to have a clear rnulticolor effect. Where a difference in dominant wave length is not greater than about 5 m~ and there is a remarkable difference in color concentration, these should also be included in the so-called multicolor of the present invention. The criterion is that two ~ypes of mixed colored fibers must be distinugished easily with the naked eye.
The transparent high molecular weight resins to be used in the coating layer of -the present invention include polyurethane, polyurethane urea, polyacrylic acid, polyacrylic ester, polyamino acid, polyamide, polyvinyl acetate, polyvinyl choride and these blends and copolymers, preferably polyurethane, polyurethane urea, polyacrylic ester and polyamino acid as main components.
In the said coating layer, it is important that visible light can pass through the coating layer and is reflected at the surface of the substrate layer to produce the different color spot effect. The coating layer must either be colorless and transparent or colored and transparent, and the thickness of the layer is preferably between the least thickness capable of forming continuous layers and about 100 microns, more pre-ferably between about 0.1 and about 100 microns.
The colored-transparent coating layer is made of a coating composition in which resins are mixed with pigments and/
or dyestuffs, and the proportion of the coating composition should be held to not more than about 30 parts for about 100 parts - lOa -., ,J
" .
~1 2Z1 882 of the resin solid, preferably between about 0.1 and about 10 parts. It is naturally possible to add to the coating compos-ition, ultraviolet absorbers, antioxidants, gas discoloration inhibitors, and delustering agents to the extent that these do not defeat the object of the present invention.
Uniting the coating layer with the substrate sheet is carried out as follows:
(1) A releasable substrate with a grain pattern or smooth is coated with the coating composition and allowed to dry completely. A second coat is applied and bonded to one side of the fibrous substrate before the coating loses its viscosity, and then is stripped off after drying, or later the resulting product is subjected to surface finishing with a gravure roll.
~ 2) A releasable substrate similar to (1) is coated with the - lOb -~;~2~88%
coating composition, and bonded to one side of the fibrous substrate hefore the coating loses its viscosi~y~ then is striyped off after drying, or later the resulting product is subjected to surface finishing with a gravure roll.
(3) One side o~ the fibrous substrate is directly coated by a combination of knife, reverse roll coater, gravure coater, etc., and allowed to dry.
(4~ One side of tile non-dyeing raw fibrous substrate receives the coating in the same manner as (1) to (3) and is dyed, or later the resulting product is finished by a gravure roll.
Eurthermore, this coating may be ~one in a single step or multistep and variation of the degree of coloring at each step makes it possible to produce colors with different hues and/or lightnesses on the same fibrous substrate. In this case, the compounding proportion of the pigment is preferably decreased in successive upper layers. In the multistep coating, different resins may be used when the adhesive strength between the layers is not lower than about 0.5 kg/cm, preferably not lower than about 1.0 kg/cm.
Figure 1 shows the surface cross section of the artificial grain leather having different color spot groups of the present invention, where A
indicates the colored ultra fine composite fiber, B indicates the other colored fiber, C indicates colored or uncolored binderJ D indicates the colored-transparent coating layer, E indicates the non-unifornl grain pattern surface produced by embossing, crumpling, or grain pattern of release paper, the arrows A+D(+E~, C+D(~E) and B+D(+E) show that incidental and reflected angles of light and coloration varles from portion to portion.
The method to enhance the effect of the present invention and to obtain a strong artificial grain leather having high vividness of color, is described as follows:
~Z~2~8~3Z
A tri-component type composite fiber, composed of the island component consisting of ~he surrounding component and the other component, which is unified by the sea component, is used as shown in Figures 3 to 5.
Figure 2 sho~Ys the islands-in-a-sea type composite fiber of the core-sheath type. In this case, X which is the core of the island is polyethylene terephthalate with an extremely high degree of polymerizatioll, polyoutylene terephthalate or its copolymer. ilowever, the X oontai~s no ora very little 5-sodium sulfoisopht}lalate, the amount being less than Y. Usually, polyethylene terephthalate or polybutylene terephthalate homopolylller is preferred On the other hand, Y is polyester containing 5-sodium sulfoiso-phthalate unit. In particular, Y is preferably a copolymer with X component.
The copolymerizing proportion of 5 sodium sulfoisophthalate is preferably between about 1.5 mol percent and about 4.0 mol percent, more preferably between about 2 mol percent and about 2.8 mol percent. The proportion is represented by amount with respect to the total amount of the acid component.
The Y component is allocated to the sheath of the island component, and surrounds the greater part of the side of the core component, preferably not less than about 80%, and more preferably about 100%.
The less the core is covered by the sheath, the poorer is the coloration.
The copolymer component of the above-mentioned sheath componen~
shows a remarkably high apparent viscosity on melting as compared with the intrinsic viscosity.
On the other hand, it is preferred that core component X have as high an intrinsic viscosity as possible by industrial spinning, in order to produce a sufficient strength. It is required that at least the relation X > Y
~2~8~3~
be held at the intrinsic viscosity, since departure from the said relation prevents the object of the present invention from being achieved. Preferably, X should be larger than Y by about 0.1, especially by not less than about 0.15.
Tlle strength is enhanced especially when fiber is drawn enough to obtain an elongation of not more than about 100~, preferably between about 65% and about 10~.
The Z component in Figure 2 indicates the so-called sea component, which is removed as necessary and the fiber for the present invention is formed as shown in Figure 3. The present invention does not relate to fibers but to an artificial grain leather consisting of a fibrous substrate layer which contains fiber and elastic substances and coating layer.
Ultra fine composite fiber XY preferably has a denier of not more than about 0.5, especially between about 0.25 and about 0.05. The above value, which influences color fastness, dyeability, and feel in relation to the dyestuff, makes the present invention most effective. The ultra fine composite fiber XY need not have a round cross section; the various cross sections may be used as necessary. The intrinsic viscosity is measured, for example, in orthochlorophenol at 25C. The fiber strength of the ultra fine composite fiber XY used in the present invention is not less than about 3 grams/denier, preferably not less than about 4 grams/denier. In the present invention in which the strength is retained in the core component, the proportion of X in XY
is between about 90 and 10% by weight, preferably between about 70 and 30%
by weight.
Figure 6 is a perspective view showing a raised nap on the fibrous substrate which is made of a nappy material. In the figure, Q represents the surface of the fibrous substrate without raised nap and P polyurethane elastic 3L2~
substance. It seems that the effect is producea by b~th the adhesion between ~ and fiber XY and the coagulation property of P around the fiber, and thus the feel is further improved.
The process following the construction of the fibrous substrate in the above manner is the same as described earlier. Thus the obtained artificial grain leather has a multicolor effect as well as high strength ~ h an excellent vividness in color.
It is not enough for the artif:icial grain leather of the present invention to be rearded merely as one having colored fine spot groups resulting from the ultra fine fibers and single multicolored spots due to the grouping.
From the synergistic effect of the colored surface layer and additional coloration of thè high polymer elastic substance inside the fibrous substrate, the artificial grain leather of the present invention is uni~ue offering the following features: a three-dimensional surface effect; a grain pattern effect caused by fine spots; the same high grade effect as pores resulting from fine spots; a good pores effect, good feel effect caused by blending staples. The multicolor spots mentioned above consist mainly of spots having sizes not larger than about 3 mm, preferably not larger than about 1.5 mm, and more preferably not larger than about 0.8 mm.
The present invention makes it possible to obtain an artificial grain leather having different color spot groups with a three-dimensional surface effect, pores and grain pattern effect, which constitutes an entirely new type of product not found in known conventional artificial and natural grain leather.
The artificial grain leather having the different color spot groups of ~2~8~2 tilC present inventioll can be used in fields such as clothing, industry, furnisil-ings, wall decorations~ interiors, bags and purses, etc. and finds especially effective use in fields where emphasis is on color tint.
Examples relating to the present invention are desc~ibed below~
but the present invention is not limited or restricted by their examples.
Example 1 Two types of high molecular arrangement ~iber of the island~ -a-sea type were prepared as follows:
(I) Staple A of 51 mm, comprising the multi-component type fiber in which the island component (the number of islands is 16 pieces): the sea component = 60 : 40, and the island component COIlsiStS of polyethylene terephthalate containing as copolymer 2.4 mol percent of sodium sulfoisophthalate and the sea component consists of polystyrene copolymerized with 22% by weight of ethylhexyl acrylate, and having 3.8 denier after being spun, drawn and crimped to about 12 crimps/inch.
Recent development of an artificial gr~in le~th--r has progressed remarkably. !`~uch effort is being made to obtaill an artificial leathcr, the grained surface of which more closely resemhles that of the natural leather consisting of ultra fine fibers, and to correct the defects in natural leatiler.
However, there remain many requi.rements which have not yet been met. For instance~ a leather is needed which is ~ore agreeable to the touch than natural leather; or a leather having more sophisticated coloring WiliC}I has no~
been obtained by the conventional and artificial grain leather or natural leather which is single-tone colored; or a leather of higher quality and subdued color or a leather of coloring not achievable with print dyeing, in particular~ due to its pores; or an artificial leather whose feel is that of the natural grain leather which is obtained without embossing.
Further, the coated surface of conventional artificial grain leather has been shaded by applying a deep colored composition directly to the ~onochromatic coating using a print roll. Thus, conventional artificial grain leather has disadvantages, such as lack of impressiveness in colors, restricted color variety, lack of cubical appearance, and poor color fastness because it can easily become discolored by surface friction, heat, or solvents.
The present invention is directed to providing an artificial grain leather with a high grade appearance having superior grain pattern effect and a ~.~2~
three-dimensional surface effect. The term "three-dimensional surface effect" means a surface which has the appearance of depth and uneveness due to different color spot yroups.
The present invention also at-tempts to provide an artificial graln leather having different color spot groups, which looks like a single color at a distance but which, close up, can be discerned as a mixture of en-tirely differently colored ultra Eine fibers and which gives an impression of richness created by overlapping their colors on the surface.
Additionally, the present invention is directed to providing an artifical grain leather presenting an entirely new tint with quality appearance and having different color spotgroups, all of which cannot be attained by a natural leather and also an artificial grain leather having high strength and vivid color.
Thus, according to the present invention, there is now provided an artificial grain leather having different color spot groups comprising:
a fibrous substrate layer of ultra fine fibers, bundles of ultra fine fibers or mixtures of ultra fine fibers and bundles of ultra fine fibers, wherein said fibrous substrate layer contains a high molecular weight viscoelastic first polymer; said fibrous substrate has at least two types of colors selected from the group consisting of colors of different hues, colors of different light-ness values and mixtures thereof; and at least one side of said fibrous substrate layer is a coating layer of a transparent high ~ 2 , ~r ~
~X~ 3X
molecular weight second polymer and appears on the apparent face of the artific:ial grain leather.
The present invention will now be described in more detail by wav of example only, with reference to the accompany-ing drawing, in which:
Figure 1 illustrates in cross section a surface portion of an artificial grain leather having differen-t color spot yroups provided by the - 2a -present invcntion, Figure 2 is a cros, section of ultra fine composite fiber bundles provided by thc present inventiO;l, Figure 3 is a cross section of the ultra fine composite fihers with the core-sheath t~pe structure provided by the present inven~ioll, ~ igures 4 and 5 are cross sections of ultra fine composite ~ibers with the conjugating and the conjugated type structure, respectively, provided by the present invention, Figure 6 illustrates, in perspective view, ~ rais~d nap on the fibrous substrate which is made of a nappy matcrial.
The fibrous substrate of the present invention is composed of ultra fine fibers ~hich are not more than about 0.7 denier, preferably bet~een about 0.0001 and about 0.3 denier, or bundles comprising chiefly such ultra fine fibers. The fibrous substrate of the presen-t invention exhibits the unique and rich characteristics of high grade color and feel because of the synergistic effect of the composition provided by blending ultra fine fibers as mentioned above.
To produce the ultra fine fibers used in the present invention, a conventional process may be used. The method includes, for example, that of making the ultra fine fibers by a sui.table means from multicomponent fibers such as islands-in-a-sea type composite fibers, high molecular inter-arrangement fibers, stripped-off type (rice type, chrysanthemum type, ribbon type, etc.,) composite fibers, special polymer-blended type fibers, etc.
The making of such ultra fine fibers for the present invention generally includes, but is not limited to, chemical and physical means such as dis-solution or decomposition of one component, and decortication of components, etc. Other useful means include the use of super-draw ~ - 3 _ ~ .
~2~
spinning, strony blowing spinning with air, and star-cloud type.
Details are referred to in, for example, ~he "Chemical Fiber Monthly Bulletin" July issue, 1977.
The cross sectional shapes of the fiber to be used include round cross section which is the most common, as well as any other shapes such as fan-shaped triangles, fan-shaped frustums, rectangles, cross-shapes, T-shaped triangles, Japanese rice ball-shaped triangles, and other multi-lobar shapes, various kinds oE shapes with n-lobes and n-processes (n is an integer), hollow shapes, deformed hollow shapes and ellipses.
The phrase "comprising chiefly of" which may be used in the instant specification includes the cases where fibers of large denier above the defined limit are mixed or foreign sub-stances such as additives are applied to the fibers, to such an extent that there is no substantial influence on the functional effect of the present invention. The phrase implies, for example, that a very large amount of ultra fine fibers may contain small amounts of thicker fibers of not less than 0.7 denier. There are also some cases in which, in making ultra fine fibers by stripping off the stripped-off type multi-component fibers, another component lying between the ultra fine fiber components remains as thick deformed cross section yarn, or the multi-component type fiber itself being capable of producing ultra fine fibers remains as a larger fiber without being changed into ultra fine fibers. A further implication is that, even in the above case, if the portion of the unchanqed remaining larger fiber does not exceed -the greater part of the who]e fiber, the object of the present inven-tion can ade~uately be achieved. In any case, any variation within this limitation which does not cause a loss of the functional effect required by the present invention may be included in the present invention.
The fibrous substrate sheet used in the present invention may be composed of kni-tting (i.e., knitted fabric), unwoven fabric such as needle-punched felt, woven ~abric, a laminate of such materials or a sandwiched form of such materials.
At least one side of the substrate has the above-mentioned grained surface.
Methods for producing the fibrous substrate sheet are virtually limitless. When one side of the fibrous substrate is ~o have a nap, the substrate used is a nappy knit or fabric such as velveteen, corduroy, blanket, double velvet fabric, velvet, etc. After the sheet is formed, the nap is raised by methods used in the manufacture of similar fabrics, including abrasion with raising fillets or emery, buffing, loop-cut or electric placement of the nap.
The fibrous substrate of the present invention may contain various kinds of conventional high molecular viscoelastic substances such as polyurethane, polyurethane urea, acrylic resin, silicone rubber (which may be vulcanized) fluorine resin or a mixture thereof.
One feature of the fibrous substrate of the present invention is the multicolor dyeing of the substrate. The multi-color dyeing may be dyeing ultra fine fibers in a bundle with ~2 ~ 2 different colors or dyeing adjacent bundles with different colors.
~'he multicolor dyeing is achieved by using at least two types of ultra fine fiber material wi-th different dyeablilities and dyeing each of them with different types of dyestuff.
The ultra fine fibers are classified by the differences in dyeability into dyeable fibers wi~h desperse~ acidic, basic, direct and reactive dyestuff. A combina~ion of at least two types of fiber may be selected from the above-mentioned ~roup. The fibrous substrate is composed chiefly of the ultra fine fibers, a small amount of common fibers may be mixed with the ultra fine fibers as the other fiber having different dyeability provided that the desired mixed color ef~ect is achieved.
Examples of the dyeable fibers with disperse dyestuff include polyethylene terephthalate, polyoxyethylene benzoate, polybutylene terephthalate, or these substances whose copolymer-ization is modified to a greater or lesser extent or a blend formed by mixing with a modifying agent, and polyamides with a rigid structure.
Examples of the dyeable fibers with acidic dyestuff involve polyamides having amino end group such as the familiar nylon 6, 66, 610 12 PACM.
Examples of the dyeable fibers with basic dyestuff are substances having -SO3Me(Metal) group, especially -SO3Na group or combinations.
Typical polymers for fibers of the above group are polyacrylonitrile type copolymerization polymer, polyethylene ~218~3~
terephthalate or polybutylene terephthalate polymer copolymer-ized with sodium sulfoisophthalate, or mixed, etc.
As to the dyeable fibers with direct or reactive dye-stuff, which may be ones containing a reactive group, typical are the fibers having -OH group such as cellulose or polyvinvyl alcohol type. All the above fibers are of conven~ional ones, but substances other than the above may, of course, also be used.
A combination of at least two types of fiber selected from the above group is used to form the fibrous substrate. A
typical example of the methods of forming the fibrous substrate made of such combination fibers includes blending or mixspinning two types of multi-component type fibers, from which bundles of ultra fine fibers consisting of the island components can be produced by removing the sea components, the island components of said fibers having different dyeabilities from each other.
From the resultant mixed spun yarn, web or filament, the fibrous substrate is formed.
Alternatively, instead of the multi-component type fiber, bundles of initially very fine fibers which can be obtained by the super draw process, may be blended or mix-spun. An example of fine fiber combinations useful in the latter method is a combination of a high molecular arrangement fiber of islands-in-a-sea type fiber dyeable with a disperse dyestuff and a high molecular arrangement fiber of an islands-in-a-sea type fiber dyeable with a basic dyestuff. An example of the former island polymer is polyethylene terephthalate, and an example of the latter island polymer is polyethylene terephthalate copolymerized ~ . ;
=, "
~x~
with sodium sulfoisophthalate.
A further example includes a mixture with the islands-in-a-sea type high molecular arrangement fiber whose island component is nylon 6 (the acid dyeable type containing many amino end groups).
The combining ratio (the ratio of each island component) may be selected optionally, and may range from about 1 to about 99% depending on the purpose to be achieved. The range of about 5 to about 95~ creates an outstanding effect. In ~eneral, a preferred effect often results from a choice of the proportion of not more than about 50% of the fiber that has the deepest color. Especially, when the deep-colored fiber is mixed in a low proportion, the mixed part produces pores effect, which further enhance, the effect of the present method. When the deep-colored is mixed in a high proportion, then a gradation effect results.
With the multi-component fiber used in the present invention, it is not necessary that the island component to be perfectly enclosed by the sea component. The so-called split or stripped-off multi-component fiber, in which both components adhere to each other in parallel, may be employed. In any case, the sea component is removed, and at least the island component or the component corresponding to the island component is principally utilized.
When the multi-component fiber is used, the forming of the ultra fine fiber is carried out at an appropriate stage either before or after the formation of the sheet. This is preferably conducted after the formation of the sheet in the present invention, for reasons of qood processahility and soft fibrous substrate.
When common fibers are mixed, it is necessary to control the proportion such that the common fibers never constitute the major part. Particularly, in the case of makinc3 a raised nap on one side of the fibrous substrate, the proportion of common fibers is preferably limited to less than about 20~, more preferably not more than about 10%, taking into consideration the feel, and the reversible lie of the nap, etc.
In any case, exceptional effects such as feel, luster, the combination with color of the grained surface coating, and additionally coloration of binder, which should not be defined merely as common multicolor mixing, are obtained due to the unique effect of the ultra fine fibers. A treatment for making ultra fine fibers, which may be selected from various method$, is necessary only when the multi-component fiber used has not yet been made ultra fine. With certain kinds of multi-component fibers, it is possible to simultaneously make the multi-component fibers into ultra fine fibers and dye the resulting ultra fine fibers. The dyeing may be carried out in the same way as for dyeing of staple, filament or fibrous sheet, and usually takes place after the fibers are formed into a sheet.
The ultra fine fibers are dyed by a single-bath method or a multi-bath dyeing method. The main feature of these methods and the actions which take place during the process are as follows:
. ~
,~, , .~
~2~2~8~
In the single-bath dyeing method, the period of which may be shor-t, it is necessary to select a proper dyestuff and to use a reserve printing agent and a suspending agent, because a problem may arise from the formation of precipitates produced by the interaction between the different types of dyestuff and the resulting contamination. ~lowever, imperfect removal of the contaminated dyes effects the lightness of color and fastness of the dye which restricts the quality of extremely deep and li~ht colors, and their vividness. In the multi-bath dyeing method, in which different types of dyestuffs can be used in each separate bath, there is no danger of precipitate formation from dyestuff reactions, and there is also an advantage that lightness shades and high fastness of dyeing colors can be obtained by employing the so-called intermediate cleaning process which cleans the fibers on the contamination side. The so-called single-bath, multi-step dyeing method, which is included in the single-bath dyeing method in the present invent-ion, produces an intermediate result between the single-bath and multi-bath dyeing methods. The methods mentioned above are conventional and dyeing in the present invention may be carried out by any such method. It is necessary, however, to select a combination of dyestuffs which cause dyeing in multi-colors as defined below. When two different fiber samples are removed from the base and they show a difference in dominant wave length of not shorter than about 5 m~, preferably not shorter than about 10 m~, measured by a color difference meter, the fiber is said ~L2~
to have a clear rnulticolor effect. Where a difference in dominant wave length is not greater than about 5 m~ and there is a remarkable difference in color concentration, these should also be included in the so-called multicolor of the present invention. The criterion is that two ~ypes of mixed colored fibers must be distinugished easily with the naked eye.
The transparent high molecular weight resins to be used in the coating layer of -the present invention include polyurethane, polyurethane urea, polyacrylic acid, polyacrylic ester, polyamino acid, polyamide, polyvinyl acetate, polyvinyl choride and these blends and copolymers, preferably polyurethane, polyurethane urea, polyacrylic ester and polyamino acid as main components.
In the said coating layer, it is important that visible light can pass through the coating layer and is reflected at the surface of the substrate layer to produce the different color spot effect. The coating layer must either be colorless and transparent or colored and transparent, and the thickness of the layer is preferably between the least thickness capable of forming continuous layers and about 100 microns, more pre-ferably between about 0.1 and about 100 microns.
The colored-transparent coating layer is made of a coating composition in which resins are mixed with pigments and/
or dyestuffs, and the proportion of the coating composition should be held to not more than about 30 parts for about 100 parts - lOa -., ,J
" .
~1 2Z1 882 of the resin solid, preferably between about 0.1 and about 10 parts. It is naturally possible to add to the coating compos-ition, ultraviolet absorbers, antioxidants, gas discoloration inhibitors, and delustering agents to the extent that these do not defeat the object of the present invention.
Uniting the coating layer with the substrate sheet is carried out as follows:
(1) A releasable substrate with a grain pattern or smooth is coated with the coating composition and allowed to dry completely. A second coat is applied and bonded to one side of the fibrous substrate before the coating loses its viscosity, and then is stripped off after drying, or later the resulting product is subjected to surface finishing with a gravure roll.
~ 2) A releasable substrate similar to (1) is coated with the - lOb -~;~2~88%
coating composition, and bonded to one side of the fibrous substrate hefore the coating loses its viscosi~y~ then is striyped off after drying, or later the resulting product is subjected to surface finishing with a gravure roll.
(3) One side o~ the fibrous substrate is directly coated by a combination of knife, reverse roll coater, gravure coater, etc., and allowed to dry.
(4~ One side of tile non-dyeing raw fibrous substrate receives the coating in the same manner as (1) to (3) and is dyed, or later the resulting product is finished by a gravure roll.
Eurthermore, this coating may be ~one in a single step or multistep and variation of the degree of coloring at each step makes it possible to produce colors with different hues and/or lightnesses on the same fibrous substrate. In this case, the compounding proportion of the pigment is preferably decreased in successive upper layers. In the multistep coating, different resins may be used when the adhesive strength between the layers is not lower than about 0.5 kg/cm, preferably not lower than about 1.0 kg/cm.
Figure 1 shows the surface cross section of the artificial grain leather having different color spot groups of the present invention, where A
indicates the colored ultra fine composite fiber, B indicates the other colored fiber, C indicates colored or uncolored binderJ D indicates the colored-transparent coating layer, E indicates the non-unifornl grain pattern surface produced by embossing, crumpling, or grain pattern of release paper, the arrows A+D(+E~, C+D(~E) and B+D(+E) show that incidental and reflected angles of light and coloration varles from portion to portion.
The method to enhance the effect of the present invention and to obtain a strong artificial grain leather having high vividness of color, is described as follows:
~Z~2~8~3Z
A tri-component type composite fiber, composed of the island component consisting of ~he surrounding component and the other component, which is unified by the sea component, is used as shown in Figures 3 to 5.
Figure 2 sho~Ys the islands-in-a-sea type composite fiber of the core-sheath type. In this case, X which is the core of the island is polyethylene terephthalate with an extremely high degree of polymerizatioll, polyoutylene terephthalate or its copolymer. ilowever, the X oontai~s no ora very little 5-sodium sulfoisopht}lalate, the amount being less than Y. Usually, polyethylene terephthalate or polybutylene terephthalate homopolylller is preferred On the other hand, Y is polyester containing 5-sodium sulfoiso-phthalate unit. In particular, Y is preferably a copolymer with X component.
The copolymerizing proportion of 5 sodium sulfoisophthalate is preferably between about 1.5 mol percent and about 4.0 mol percent, more preferably between about 2 mol percent and about 2.8 mol percent. The proportion is represented by amount with respect to the total amount of the acid component.
The Y component is allocated to the sheath of the island component, and surrounds the greater part of the side of the core component, preferably not less than about 80%, and more preferably about 100%.
The less the core is covered by the sheath, the poorer is the coloration.
The copolymer component of the above-mentioned sheath componen~
shows a remarkably high apparent viscosity on melting as compared with the intrinsic viscosity.
On the other hand, it is preferred that core component X have as high an intrinsic viscosity as possible by industrial spinning, in order to produce a sufficient strength. It is required that at least the relation X > Y
~2~8~3~
be held at the intrinsic viscosity, since departure from the said relation prevents the object of the present invention from being achieved. Preferably, X should be larger than Y by about 0.1, especially by not less than about 0.15.
Tlle strength is enhanced especially when fiber is drawn enough to obtain an elongation of not more than about 100~, preferably between about 65% and about 10~.
The Z component in Figure 2 indicates the so-called sea component, which is removed as necessary and the fiber for the present invention is formed as shown in Figure 3. The present invention does not relate to fibers but to an artificial grain leather consisting of a fibrous substrate layer which contains fiber and elastic substances and coating layer.
Ultra fine composite fiber XY preferably has a denier of not more than about 0.5, especially between about 0.25 and about 0.05. The above value, which influences color fastness, dyeability, and feel in relation to the dyestuff, makes the present invention most effective. The ultra fine composite fiber XY need not have a round cross section; the various cross sections may be used as necessary. The intrinsic viscosity is measured, for example, in orthochlorophenol at 25C. The fiber strength of the ultra fine composite fiber XY used in the present invention is not less than about 3 grams/denier, preferably not less than about 4 grams/denier. In the present invention in which the strength is retained in the core component, the proportion of X in XY
is between about 90 and 10% by weight, preferably between about 70 and 30%
by weight.
Figure 6 is a perspective view showing a raised nap on the fibrous substrate which is made of a nappy material. In the figure, Q represents the surface of the fibrous substrate without raised nap and P polyurethane elastic 3L2~
substance. It seems that the effect is producea by b~th the adhesion between ~ and fiber XY and the coagulation property of P around the fiber, and thus the feel is further improved.
The process following the construction of the fibrous substrate in the above manner is the same as described earlier. Thus the obtained artificial grain leather has a multicolor effect as well as high strength ~ h an excellent vividness in color.
It is not enough for the artif:icial grain leather of the present invention to be rearded merely as one having colored fine spot groups resulting from the ultra fine fibers and single multicolored spots due to the grouping.
From the synergistic effect of the colored surface layer and additional coloration of thè high polymer elastic substance inside the fibrous substrate, the artificial grain leather of the present invention is uni~ue offering the following features: a three-dimensional surface effect; a grain pattern effect caused by fine spots; the same high grade effect as pores resulting from fine spots; a good pores effect, good feel effect caused by blending staples. The multicolor spots mentioned above consist mainly of spots having sizes not larger than about 3 mm, preferably not larger than about 1.5 mm, and more preferably not larger than about 0.8 mm.
The present invention makes it possible to obtain an artificial grain leather having different color spot groups with a three-dimensional surface effect, pores and grain pattern effect, which constitutes an entirely new type of product not found in known conventional artificial and natural grain leather.
The artificial grain leather having the different color spot groups of ~2~8~2 tilC present inventioll can be used in fields such as clothing, industry, furnisil-ings, wall decorations~ interiors, bags and purses, etc. and finds especially effective use in fields where emphasis is on color tint.
Examples relating to the present invention are desc~ibed below~
but the present invention is not limited or restricted by their examples.
Example 1 Two types of high molecular arrangement ~iber of the island~ -a-sea type were prepared as follows:
(I) Staple A of 51 mm, comprising the multi-component type fiber in which the island component (the number of islands is 16 pieces): the sea component = 60 : 40, and the island component COIlsiStS of polyethylene terephthalate containing as copolymer 2.4 mol percent of sodium sulfoisophthalate and the sea component consists of polystyrene copolymerized with 22% by weight of ethylhexyl acrylate, and having 3.8 denier after being spun, drawn and crimped to about 12 crimps/inch.
(2) Staple B of about 51 mm, comprising the multi-component type fiber in which the island component (the number of islands is 16 pieces) :
the sea component = 80 : 20, the island component consists of polyepsilon caproamide having amino end group, and the sea component consists of polystyrene copolymerized with 22% by ~Jeight of 2-ethylllexyl acrylate styrene, and having 4.5 denier after being drawn and crimped to about 9 to 12 crimps/inch.
A needle-punched felt with nonwoven fabric of abow~ 530 g/m2 was obtained by subjecting these types of staple to the following treatments;
staple mixing, sufficient opening, carding, cross-lapping, and ultra-high density needle punching of 3500/cm . The resulting product was placed in a hot bath of 12% partially saponified polyvinyl alcohol, and simultaneously Z~8~3~
shrunk and sized. Then, the product was placed in hot air and dried. Ihe hardened sheet like a plastic~ e plate was f~rther passed through a trichloroethylene cleaning unit, and was agaill dried after the sea component of both A and B fibers had been almost completely removed. The resulting product was impregnated with 12~, polyurethane dimethyl formamide solution (to which 0.5~ of carbon was added), and was coagulated in a dimethyl formamide a~ueous coagulatillg solution. The product was further thoroughly cleaned in hot water, which removed the previously applied sizing agent and dimethyl formamide solvent, followed by drying and then slicing into two. The original surface ~as further subjected to buffing by a belt sander. As a result, the non-dyeing raw fibrous substrate for the artificial leather having a good suede-like appearance was obtained.
The above-mentioned product was dyed as follows:
~ 1) Single bath dyeing condition (A/B = 50/Su on the basis of fiber from which the sea component had been removed).
By using cationic dyestuff and acidic dyestuff in the same bath, the dyeing treatment ~as carried out on the following conditions:
Cathilon Red CD -RLII ~ 3%
Kayanol Milling Blue Gl~ 3%
Ospin KB-30F ~ 4%
(manufactured by Tokai Seiyu) Acetic Acid (90%) 0.5 cc/Q
Anhydrous Glaubers salt 4.0 g/Q
Bath ratio l : 50 Dyeing Temperature and Time 120C x 60 min ~zz~z .-~fter dyeing, the cont~minated dye was subjected to soaping in the follol~ing conditions:
Sandet G-29 ~ g/
~manufacture~l by Sanyo Kasei) Acetic Acid (90%) 0.5 cc/~
Bath Ratio 1 : 5Q
Treatment Ternperature and Time 70C x 20 min In or~er to improve the color fastness of the ~cid dye, the fixing treatment was carried out in the following conditions:
Nylon Fix T~ manufactured by Nippon Senka Kogyo) 4~6 Formic Acid 1%
Bath Ratio 1 : 50 Treatment Temperature and Time 80C x 20 min The suede like substrate obtained on the single bath dyeing condition consists of a mixture of red/blue nap and carbon ~black) contained in the impregnated polyurethane present among the red/blue nap. It has three colors different in hues and lightness and a violet and subdued color tone overall.
One side of the above-mentioned fibrous substrate was coated as follol~s:
A release paper with the basic grain pattern of sheep was coated with a D~lF solution of linear type polyurethane in which 2 parts of a prepared pigment consisting of 50% of blue pigment and 50% of polyurethane vehicle had been compounded with 100 parts of solid o polyurethane. After hot air drying the above paper, a coating of about 4.5 microns was produced.
~ . - 17 -~2Z~8~32 e r0sulting coating was further coated with a DMF/~EK/ethyl acetate solution of reac~ive type polyurethane in which 4 parts of the foregoing prepared pigmeilt had been compounded with 100 parts of polyurethane solid, so that the thickness of the coating be about 20 microns. Thus obtained product in a semi-~ried state was bonded to thc sliced surface of the substrate, passed through rollers with a gap of 0.15 mm to weld the surface and then dried with hot air. After aging at 30C for 24 hours, the release paper was stripped off. The obtained coated product was an artificial grain leather having the deep different color spot groups, into which light penetrates through the transparent colored resin layer wllich differs in lightness from the blue color of the substrate and is refracted in different ways from the red, blue and black portions of the fibrous substrate. It was found that the above-mentioned artificial grain leather consisted of spot group colored deeply not larger than 3 mm in size.
When the product was subjected to crumpling, the grain pattern is produced by the different color spot groups, the crumpling grain pattern, and basic grain pattern of sheep mixed with one another~ and the resulting uneveness of the surface further enhanced the feature of the present invention.
For determination of the durability of the different color spot groups, the surface abrasion resistance was measured. In a conventional coating on a coating layer applied by a print roll~ the printed portion is removed easily but the coating of the present invention showed a high durability which it reta:ined until the coating layer was broken.
Example 2 The non-dyeing raw fibrous substance in Example l was dyed as follows:
~22~8~
~ 2) Double bath dyeillg condition (A/B = l0/90 on the basis of fiber from l~hich t}le sea component hacl been removed~
The so~ium sulfoisophthalate-copolymerizing polyethylerle terephthalate side ~as dyed using cation dyestuff in the following conditions:
Cathilon Blac~ CD - BL~I ~ 18~
Ospin KB -30 F ~ 4%
Acetic Acid 0.5 cc/
Anhy~rous Glauber's Salt 4.0 g/~
Bath P~atio l : 50 Dyeing Temperature and Time120C x 60 min After dyeing of ~he sodium sulfoisophthalate-coyolymerizing polyethylene terephthalate side, for the purpose of removing the contaminated cationic dyestuff on the polyepsilon capramide side, cleaning was done on the following conditions:
I-lydrosulfite 2.0 g/Q
Soda Ash 1.0 8/Q
Sandet G - 29 ~ l.0 g/Q
Bath Ratio 1 : 50 Treatment Temperature and Time 70C x 20 min Next, the polyepsilon capramide was dyed using acid dye in the following conditions:
Mitsui Nylon Black GL ~ 2%
Ospin KB - 30 F ~ 4%
Ammonium Sulfate 4 g/Q
Bath ~atio l : 50 Dyeing Temperature and Time98C x 60 min ~2Z~2 After dyeing, soaping was carried out in the following conditions:
Sandet G - 29 ~ 1.0 g/Q
Acetic Aci~ 0.5 cc/
Bath Ratio 1 : 50 Treatment Temperature ar.d Time 70~C x 20 min The suede-like fibrous substrate obtained in the double bath dyeing shown in (2) was a mixture of light grey colored nap and black colored nap, with two degrees of color lightness, and presented a grey and subdued color tone overall.
One side of the fibrous substrate was then coated as follows:
Smooth release paper wlth no grain pattern was coated with a IPA/DMF solution of linear type non-yellowing polyurethane, and a coating of 7 microns was prepared in the same manner as in Example 1. Thus obtained coating was further coated with a D~F/~lEK/toluene solution of reactive type non-yellowing polyurethane to a thickness making the coating 15 microns thick. As in E~ample 1, the resulting paper was bonded to the fibrous substrate, welded on, dried in hot air, aged, and stripped off. ~le coated product obtained was an artificial grain leather having deep different color spot groups with different degrees of lightness, into which light-rays penetrated through the transparent colorless resin layer, and refracted in different directions from tht light grey and black portions of the fibrous substrate; the grey portion had the appearance of natural grain leather. It 'was found that no spot was larger than 3 mm.
When subjected to crumpling, the artificial grain leather had a fresh appearance, and a multicolor effect resulting from a combination of crumpling grain pattern with grain pattern produced by the different color spot groups not larger than 3 mm in size.
~ ~ - 20 -~2~88~:
Example 3 Two types of high molecular inter-arrangement fiber having an islands-in-a-sca t~pe cross section was prepared as follows:
(1) Island component: Polyethylene terephthalate Sea co~ponent: Polystyrene mixed with 5% of PEG
Number of island components: 16 Denier of high molecular inter-arrangement fiber: 3.8 Length of fiber: 51 mm Number of crimps: About 12 nodes/25 mm Ratio of island/sea: 38/42 (2) Island component: Polyethylene tarephthalate copolymerized with 2.4 mol percent of 5-sodium sulfoisophthalate Sea component: Polystyrene Number of island components: 16 Denier of high molecular inter-arrangement fiber 3.8 Length of fiber: 51 mm Number of crimps About 12 nodes/25 mm Ratio of island/sea 79/21 The above-mentioned components were subjected to staple mixing in the ratio of 70 to 30, carding, cross lapping, and needle punching, to produce a needle-punched felt with a texture of 530 g/m2. The resulting product was passed through boiling water, and after drying was passed through a 6% aqueous solution of polyvinyl alcohol mixed with 4% polyurethane emulsion, squeezed through a mangle, and dried. Subsequently, thus product was 122~8~
cleaned with trichloroethylene aftcr drying bcing inassed through a 12Qo pol)~inyl alcohol a(~ueous solutionJ squeezed throllgil a mangle and dried.
The resulting product was further impregnated in ~ 12o DMF solution of polyurethane coagulated in DMF-watcr and washed ~ith hot ~ater. tfrer drying the resulting product was sliced in two buffed and dyed in the following conditions:
Dyeing Machine: Small-sized fluid dyeing machine (1) Baci.c dyestuff Cathilon Blue CD - RL~ Hodogaya Kagaku) 3.3% owf Cathilon Yellow RL~(Hodogaya Kagaku) 2.~o owf Diacryl Red GL - N~(Mitsubishi Kasei) 1.4% owf (2) Disperse Dyestuff Resolin Blue FBL~(Bayer) 0.5O owf Kayalon Polyester Rubine BLS ~ 0.2% owf (Nippon Kayaku) Terasil Orange 5RL~(Ciba-Geigy) 0.6% owf Assistant Agent:
Mignol~(Ipposha Yushi) 0.5% g/Q
Acetic Acid 0.6% g/Q
Sodium Acetate 0.3% g/Q
Bath Ratio 1 : 30 Time 2 hr Temperature 120C
After dyeing reduction cleaning was carried out on the following conditions:
Hydrosulfite 5% owf Caustic Soda 8% owf - Bath Ratio 1 : 30 I ~, ~L22~38~
Subsequently~ drying was done at ~0C.
Ihe resulting suede-like fibrous substrate presented colors with different lightness values resulting from ,:L mixture of greyish brown colored nap and bro~l colored nap3 and had a soft touch and hand.
The above ibrous substrate was coated as follows:
The linear type non-yellowing polyurethane solution used in Example 2 was mixed in the following proportions with prcpared pigments per lO0 parts of polyurethane solid.
Black pigment (Channel Type Carbon Black/Polyurethane vehicle: 25/75) 0.05 parts White Pigment (Titanium/Polyurethane vehicle: 75/25) 0.1~5 parts Yellow Pigment (Insoluble Azo/Polyurethane vehicle:
50/50) 0.02 parts Brown Pigment (Disazo Condensation Pigment/Polyurethane vehicle: 50/50) 0.0;5 parts The polyurethane terephthalate film was coated with the resulting compound as in Example 1, and further coated with a reactive type non-yellowing polyurethane solution in said manner. The resulting product was bonded to the other side to the sliced surface. The coated product was an artificial grain leather having different color spot groups in which the lightness values differed from Example 2 and were slightly different between the front and back. A clothing in which the front and back of the above-mentioned product werc combined entirely showed a color effect resulting from a combination of the different color spot groups, which was unpreceden~ed.
Example 4 The undyed raw fibrous substrate of Example 1 was coated and dyed ~.~2~8B2 as follows:
~ elease paper was coa~ed with acid dye accepting polyurethane so that the thickness of the coating was 30 microns, bonded to the non-dyeing raw fibrous substrate in a semi-dried s~ate and coa~ed as in Example 1.
The resulting yroduct was dyed in the same conditions as in Exal~le 1.
The product obtained was an artificial grain leather having the same transparent different color spot groups as in Example 1, in which the fibrous substrate surface layer consisted of a mixture of blue and red colored nap with carbon (black) contained in the impregnated polyurethane lying beneath the blue colored film.
Example 5 By means of gravure roll ~50 mesh), the sliced surface of the fibrous substrate of Example 3 was coated with linear type non-yellowing polyurethane solution, used in Example 3, mixed with a similar pigment, and dried. Subsequently, the resulting product was coated with a coating made from 70% of the above-mentioned pigment by means of gravure roll (80 mesh), and dried. The above product was further coated again with one mixed with 30% of the above-mentioned pigment by means of gravure roll (150 mesh), followed by drying, and an artificial grain leather having the different color spot groups of the present invention was obtained.
Example 6 Two types of high molecular inter-arrangement fibers having the islands-in-a-sea type cross section was prepared as follows:
(1) Staple A of tri-component type fiber, having the following composition and property:
X Component: 32 par~s by weight of polyethylene terephthalate 12;;~ 2' Y Component: 25 parts by weight of polyethylene terephthalate containing 5-sodium sulfoisophthalate unit of 2.43 mol/total amount of the acid component Component: 43 parts by weight of polystyrene copolymerized with 22 wt percent of 2-ethylhexyl acrylate.
Length and Fineness of Fiber: about 51 mm x 3.8 d ~umber of Crimps: about 16 crimps/2.54 AB ~omposite ~iber Strength: about 4.5 g/d (2) Staple B havillg the following comyosition:
Island Component: polyethylene terephthalate Sea Component: polystyrene mixed with S% PEG
Number of island components: 16 Denier of high molecular inter-arrangement fiber: 3.8 Length of fiber: 51 mm Number of crimps: about 12 crimps/2S mm Ratio of island/sea: 38/42 The above-mentioned staples were subjected to staple mixing in a ratio of 30 to 70 (Staple A ~o Staple B~, carding, cross-lapping, and needle punching; a needle-punched felt with a weight of 500 g/m2 was obtained.
This felt was passed through boiling water, dried, and then passed through an aqueous solution of 6% polyvinyl alcohol mixed with 4% emulsion polyurethane, squee~ed through a mangle, and dried again. Subsequently, the resulting product was cleaned with trichloroethylene, passed through a 12%
polyvinyl alcohol aqueous solution after being dried, squeezed through a mangle, and dried again. The resulting product was impregnated in a 12% DMF
solution of polyurethane, coagulated in DMF - water, and washed with hot water. The obtained product was sliced into two, then buffed, and subjected ~2~L8~32 to dyeing in the following conditions:
Dyeing ~lachine. Small-si7ed ~luid Dyeing ~achine (l) Basic Dyestuff Cathilon Blue CD - RL~ Hodogaya Kagaku) 2.3% owf Cathilon Ycllow RL~llodogaya Kagaku) 2.8% owf Diacry1 Red GL - ~ ~litsubishi ~Yasei) 1.4% owf (2) Disperse Dyestuff Resolin blue FB ~ Bayer) 0.5", ow Kayalon Polyester Rubine BLS ~ 0.2% owf (Nippon Kaya~u) Terasil Orange 5 RL~(Ciba Geigy) 0.6% owf Assistant Agent;
~lignol~Ipposha Yushi) 0.5% g/Q
Acetic Acid 0.6% g/Q
Sodium Acetate 0.3% g/Q
Bath Ratio 1 : 30 Time 2 hr Temperature 120C
After dyeing, reduction cleaning was carried out in the following 20 conditions:
Hydrosulfite 5% owf Caustic Soda 8% owf Bath Ratio 1 : 30 Subsequently, drying was done at 90'~C.
The obtained suede-like fibrous substrate displayed colors having various ligl-tness values which resulted from a combination of greyish-brown colored nap and the brown-colored nap, and also had a soft touch and hand.
~'''~ .
~2Z~8~2 One side of the above-mentioned fibrous substrate was coated as follows:
Linear type non-yellowing polyurethane solution used in Example was compounded with the following proportlons of prepared pi~lents for 100 par~s of polyurethane solid:
Black Pigment ~channel type carbon black/polyurethane vehicle: 25/75~ 0.0~ parts White Pigment (titanium/po1yurethane vehicle: 75/25) 0.195 parts Yellow Pigment (insoluble azo/polyurethane vehicle:
50/50) 0.02 parts Brown Pigment ~disazo condensation pigment/polyurethane vehicle: 50/50 0.03 parts The polyethylene terephthalate film was coated with the above compound in the same manner as in Example 1, and further coated with reactive type non-yellowing polyurethane solution in the same way as in Example 2. The resulting product was bonded to the opposite side to the sliced surface. The obtained coated product was an artificial grain leather having the different color spot groups in which the lightness values differed from those of Example 2 and was slightly different from front to back.
When the above-mentioned grained surface was viewed through a microscope at a magnification of 80, the fiber forming the different color spot groups was visible through the coating layer. Clothing in which the front and back was of this artificial grain leather displayed a color effect caused by the combination of different color spot groups which was unprecedented.
the sea component = 80 : 20, the island component consists of polyepsilon caproamide having amino end group, and the sea component consists of polystyrene copolymerized with 22% by ~Jeight of 2-ethylllexyl acrylate styrene, and having 4.5 denier after being drawn and crimped to about 9 to 12 crimps/inch.
A needle-punched felt with nonwoven fabric of abow~ 530 g/m2 was obtained by subjecting these types of staple to the following treatments;
staple mixing, sufficient opening, carding, cross-lapping, and ultra-high density needle punching of 3500/cm . The resulting product was placed in a hot bath of 12% partially saponified polyvinyl alcohol, and simultaneously Z~8~3~
shrunk and sized. Then, the product was placed in hot air and dried. Ihe hardened sheet like a plastic~ e plate was f~rther passed through a trichloroethylene cleaning unit, and was agaill dried after the sea component of both A and B fibers had been almost completely removed. The resulting product was impregnated with 12~, polyurethane dimethyl formamide solution (to which 0.5~ of carbon was added), and was coagulated in a dimethyl formamide a~ueous coagulatillg solution. The product was further thoroughly cleaned in hot water, which removed the previously applied sizing agent and dimethyl formamide solvent, followed by drying and then slicing into two. The original surface ~as further subjected to buffing by a belt sander. As a result, the non-dyeing raw fibrous substrate for the artificial leather having a good suede-like appearance was obtained.
The above-mentioned product was dyed as follows:
~ 1) Single bath dyeing condition (A/B = 50/Su on the basis of fiber from which the sea component had been removed).
By using cationic dyestuff and acidic dyestuff in the same bath, the dyeing treatment ~as carried out on the following conditions:
Cathilon Red CD -RLII ~ 3%
Kayanol Milling Blue Gl~ 3%
Ospin KB-30F ~ 4%
(manufactured by Tokai Seiyu) Acetic Acid (90%) 0.5 cc/Q
Anhydrous Glaubers salt 4.0 g/Q
Bath ratio l : 50 Dyeing Temperature and Time 120C x 60 min ~zz~z .-~fter dyeing, the cont~minated dye was subjected to soaping in the follol~ing conditions:
Sandet G-29 ~ g/
~manufacture~l by Sanyo Kasei) Acetic Acid (90%) 0.5 cc/~
Bath Ratio 1 : 5Q
Treatment Ternperature and Time 70C x 20 min In or~er to improve the color fastness of the ~cid dye, the fixing treatment was carried out in the following conditions:
Nylon Fix T~ manufactured by Nippon Senka Kogyo) 4~6 Formic Acid 1%
Bath Ratio 1 : 50 Treatment Temperature and Time 80C x 20 min The suede like substrate obtained on the single bath dyeing condition consists of a mixture of red/blue nap and carbon ~black) contained in the impregnated polyurethane present among the red/blue nap. It has three colors different in hues and lightness and a violet and subdued color tone overall.
One side of the above-mentioned fibrous substrate was coated as follol~s:
A release paper with the basic grain pattern of sheep was coated with a D~lF solution of linear type polyurethane in which 2 parts of a prepared pigment consisting of 50% of blue pigment and 50% of polyurethane vehicle had been compounded with 100 parts of solid o polyurethane. After hot air drying the above paper, a coating of about 4.5 microns was produced.
~ . - 17 -~2Z~8~32 e r0sulting coating was further coated with a DMF/~EK/ethyl acetate solution of reac~ive type polyurethane in which 4 parts of the foregoing prepared pigmeilt had been compounded with 100 parts of polyurethane solid, so that the thickness of the coating be about 20 microns. Thus obtained product in a semi-~ried state was bonded to thc sliced surface of the substrate, passed through rollers with a gap of 0.15 mm to weld the surface and then dried with hot air. After aging at 30C for 24 hours, the release paper was stripped off. The obtained coated product was an artificial grain leather having the deep different color spot groups, into which light penetrates through the transparent colored resin layer wllich differs in lightness from the blue color of the substrate and is refracted in different ways from the red, blue and black portions of the fibrous substrate. It was found that the above-mentioned artificial grain leather consisted of spot group colored deeply not larger than 3 mm in size.
When the product was subjected to crumpling, the grain pattern is produced by the different color spot groups, the crumpling grain pattern, and basic grain pattern of sheep mixed with one another~ and the resulting uneveness of the surface further enhanced the feature of the present invention.
For determination of the durability of the different color spot groups, the surface abrasion resistance was measured. In a conventional coating on a coating layer applied by a print roll~ the printed portion is removed easily but the coating of the present invention showed a high durability which it reta:ined until the coating layer was broken.
Example 2 The non-dyeing raw fibrous substance in Example l was dyed as follows:
~22~8~
~ 2) Double bath dyeillg condition (A/B = l0/90 on the basis of fiber from l~hich t}le sea component hacl been removed~
The so~ium sulfoisophthalate-copolymerizing polyethylerle terephthalate side ~as dyed using cation dyestuff in the following conditions:
Cathilon Blac~ CD - BL~I ~ 18~
Ospin KB -30 F ~ 4%
Acetic Acid 0.5 cc/
Anhy~rous Glauber's Salt 4.0 g/~
Bath P~atio l : 50 Dyeing Temperature and Time120C x 60 min After dyeing of ~he sodium sulfoisophthalate-coyolymerizing polyethylene terephthalate side, for the purpose of removing the contaminated cationic dyestuff on the polyepsilon capramide side, cleaning was done on the following conditions:
I-lydrosulfite 2.0 g/Q
Soda Ash 1.0 8/Q
Sandet G - 29 ~ l.0 g/Q
Bath Ratio 1 : 50 Treatment Temperature and Time 70C x 20 min Next, the polyepsilon capramide was dyed using acid dye in the following conditions:
Mitsui Nylon Black GL ~ 2%
Ospin KB - 30 F ~ 4%
Ammonium Sulfate 4 g/Q
Bath ~atio l : 50 Dyeing Temperature and Time98C x 60 min ~2Z~2 After dyeing, soaping was carried out in the following conditions:
Sandet G - 29 ~ 1.0 g/Q
Acetic Aci~ 0.5 cc/
Bath Ratio 1 : 50 Treatment Temperature ar.d Time 70~C x 20 min The suede-like fibrous substrate obtained in the double bath dyeing shown in (2) was a mixture of light grey colored nap and black colored nap, with two degrees of color lightness, and presented a grey and subdued color tone overall.
One side of the fibrous substrate was then coated as follows:
Smooth release paper wlth no grain pattern was coated with a IPA/DMF solution of linear type non-yellowing polyurethane, and a coating of 7 microns was prepared in the same manner as in Example 1. Thus obtained coating was further coated with a D~F/~lEK/toluene solution of reactive type non-yellowing polyurethane to a thickness making the coating 15 microns thick. As in E~ample 1, the resulting paper was bonded to the fibrous substrate, welded on, dried in hot air, aged, and stripped off. ~le coated product obtained was an artificial grain leather having deep different color spot groups with different degrees of lightness, into which light-rays penetrated through the transparent colorless resin layer, and refracted in different directions from tht light grey and black portions of the fibrous substrate; the grey portion had the appearance of natural grain leather. It 'was found that no spot was larger than 3 mm.
When subjected to crumpling, the artificial grain leather had a fresh appearance, and a multicolor effect resulting from a combination of crumpling grain pattern with grain pattern produced by the different color spot groups not larger than 3 mm in size.
~ ~ - 20 -~2~88~:
Example 3 Two types of high molecular inter-arrangement fiber having an islands-in-a-sca t~pe cross section was prepared as follows:
(1) Island component: Polyethylene terephthalate Sea co~ponent: Polystyrene mixed with 5% of PEG
Number of island components: 16 Denier of high molecular inter-arrangement fiber: 3.8 Length of fiber: 51 mm Number of crimps: About 12 nodes/25 mm Ratio of island/sea: 38/42 (2) Island component: Polyethylene tarephthalate copolymerized with 2.4 mol percent of 5-sodium sulfoisophthalate Sea component: Polystyrene Number of island components: 16 Denier of high molecular inter-arrangement fiber 3.8 Length of fiber: 51 mm Number of crimps About 12 nodes/25 mm Ratio of island/sea 79/21 The above-mentioned components were subjected to staple mixing in the ratio of 70 to 30, carding, cross lapping, and needle punching, to produce a needle-punched felt with a texture of 530 g/m2. The resulting product was passed through boiling water, and after drying was passed through a 6% aqueous solution of polyvinyl alcohol mixed with 4% polyurethane emulsion, squeezed through a mangle, and dried. Subsequently, thus product was 122~8~
cleaned with trichloroethylene aftcr drying bcing inassed through a 12Qo pol)~inyl alcohol a(~ueous solutionJ squeezed throllgil a mangle and dried.
The resulting product was further impregnated in ~ 12o DMF solution of polyurethane coagulated in DMF-watcr and washed ~ith hot ~ater. tfrer drying the resulting product was sliced in two buffed and dyed in the following conditions:
Dyeing Machine: Small-sized fluid dyeing machine (1) Baci.c dyestuff Cathilon Blue CD - RL~ Hodogaya Kagaku) 3.3% owf Cathilon Yellow RL~(Hodogaya Kagaku) 2.~o owf Diacryl Red GL - N~(Mitsubishi Kasei) 1.4% owf (2) Disperse Dyestuff Resolin Blue FBL~(Bayer) 0.5O owf Kayalon Polyester Rubine BLS ~ 0.2% owf (Nippon Kayaku) Terasil Orange 5RL~(Ciba-Geigy) 0.6% owf Assistant Agent:
Mignol~(Ipposha Yushi) 0.5% g/Q
Acetic Acid 0.6% g/Q
Sodium Acetate 0.3% g/Q
Bath Ratio 1 : 30 Time 2 hr Temperature 120C
After dyeing reduction cleaning was carried out on the following conditions:
Hydrosulfite 5% owf Caustic Soda 8% owf - Bath Ratio 1 : 30 I ~, ~L22~38~
Subsequently~ drying was done at ~0C.
Ihe resulting suede-like fibrous substrate presented colors with different lightness values resulting from ,:L mixture of greyish brown colored nap and bro~l colored nap3 and had a soft touch and hand.
The above ibrous substrate was coated as follows:
The linear type non-yellowing polyurethane solution used in Example 2 was mixed in the following proportions with prcpared pigments per lO0 parts of polyurethane solid.
Black pigment (Channel Type Carbon Black/Polyurethane vehicle: 25/75) 0.05 parts White Pigment (Titanium/Polyurethane vehicle: 75/25) 0.1~5 parts Yellow Pigment (Insoluble Azo/Polyurethane vehicle:
50/50) 0.02 parts Brown Pigment (Disazo Condensation Pigment/Polyurethane vehicle: 50/50) 0.0;5 parts The polyurethane terephthalate film was coated with the resulting compound as in Example 1, and further coated with a reactive type non-yellowing polyurethane solution in said manner. The resulting product was bonded to the other side to the sliced surface. The coated product was an artificial grain leather having different color spot groups in which the lightness values differed from Example 2 and were slightly different between the front and back. A clothing in which the front and back of the above-mentioned product werc combined entirely showed a color effect resulting from a combination of the different color spot groups, which was unpreceden~ed.
Example 4 The undyed raw fibrous substrate of Example 1 was coated and dyed ~.~2~8B2 as follows:
~ elease paper was coa~ed with acid dye accepting polyurethane so that the thickness of the coating was 30 microns, bonded to the non-dyeing raw fibrous substrate in a semi-dried s~ate and coa~ed as in Example 1.
The resulting yroduct was dyed in the same conditions as in Exal~le 1.
The product obtained was an artificial grain leather having the same transparent different color spot groups as in Example 1, in which the fibrous substrate surface layer consisted of a mixture of blue and red colored nap with carbon (black) contained in the impregnated polyurethane lying beneath the blue colored film.
Example 5 By means of gravure roll ~50 mesh), the sliced surface of the fibrous substrate of Example 3 was coated with linear type non-yellowing polyurethane solution, used in Example 3, mixed with a similar pigment, and dried. Subsequently, the resulting product was coated with a coating made from 70% of the above-mentioned pigment by means of gravure roll (80 mesh), and dried. The above product was further coated again with one mixed with 30% of the above-mentioned pigment by means of gravure roll (150 mesh), followed by drying, and an artificial grain leather having the different color spot groups of the present invention was obtained.
Example 6 Two types of high molecular inter-arrangement fibers having the islands-in-a-sea type cross section was prepared as follows:
(1) Staple A of tri-component type fiber, having the following composition and property:
X Component: 32 par~s by weight of polyethylene terephthalate 12;;~ 2' Y Component: 25 parts by weight of polyethylene terephthalate containing 5-sodium sulfoisophthalate unit of 2.43 mol/total amount of the acid component Component: 43 parts by weight of polystyrene copolymerized with 22 wt percent of 2-ethylhexyl acrylate.
Length and Fineness of Fiber: about 51 mm x 3.8 d ~umber of Crimps: about 16 crimps/2.54 AB ~omposite ~iber Strength: about 4.5 g/d (2) Staple B havillg the following comyosition:
Island Component: polyethylene terephthalate Sea Component: polystyrene mixed with S% PEG
Number of island components: 16 Denier of high molecular inter-arrangement fiber: 3.8 Length of fiber: 51 mm Number of crimps: about 12 crimps/2S mm Ratio of island/sea: 38/42 The above-mentioned staples were subjected to staple mixing in a ratio of 30 to 70 (Staple A ~o Staple B~, carding, cross-lapping, and needle punching; a needle-punched felt with a weight of 500 g/m2 was obtained.
This felt was passed through boiling water, dried, and then passed through an aqueous solution of 6% polyvinyl alcohol mixed with 4% emulsion polyurethane, squee~ed through a mangle, and dried again. Subsequently, the resulting product was cleaned with trichloroethylene, passed through a 12%
polyvinyl alcohol aqueous solution after being dried, squeezed through a mangle, and dried again. The resulting product was impregnated in a 12% DMF
solution of polyurethane, coagulated in DMF - water, and washed with hot water. The obtained product was sliced into two, then buffed, and subjected ~2~L8~32 to dyeing in the following conditions:
Dyeing ~lachine. Small-si7ed ~luid Dyeing ~achine (l) Basic Dyestuff Cathilon Blue CD - RL~ Hodogaya Kagaku) 2.3% owf Cathilon Ycllow RL~llodogaya Kagaku) 2.8% owf Diacry1 Red GL - ~ ~litsubishi ~Yasei) 1.4% owf (2) Disperse Dyestuff Resolin blue FB ~ Bayer) 0.5", ow Kayalon Polyester Rubine BLS ~ 0.2% owf (Nippon Kaya~u) Terasil Orange 5 RL~(Ciba Geigy) 0.6% owf Assistant Agent;
~lignol~Ipposha Yushi) 0.5% g/Q
Acetic Acid 0.6% g/Q
Sodium Acetate 0.3% g/Q
Bath Ratio 1 : 30 Time 2 hr Temperature 120C
After dyeing, reduction cleaning was carried out in the following 20 conditions:
Hydrosulfite 5% owf Caustic Soda 8% owf Bath Ratio 1 : 30 Subsequently, drying was done at 90'~C.
The obtained suede-like fibrous substrate displayed colors having various ligl-tness values which resulted from a combination of greyish-brown colored nap and the brown-colored nap, and also had a soft touch and hand.
~'''~ .
~2Z~8~2 One side of the above-mentioned fibrous substrate was coated as follows:
Linear type non-yellowing polyurethane solution used in Example was compounded with the following proportlons of prepared pi~lents for 100 par~s of polyurethane solid:
Black Pigment ~channel type carbon black/polyurethane vehicle: 25/75~ 0.0~ parts White Pigment (titanium/po1yurethane vehicle: 75/25) 0.195 parts Yellow Pigment (insoluble azo/polyurethane vehicle:
50/50) 0.02 parts Brown Pigment ~disazo condensation pigment/polyurethane vehicle: 50/50 0.03 parts The polyethylene terephthalate film was coated with the above compound in the same manner as in Example 1, and further coated with reactive type non-yellowing polyurethane solution in the same way as in Example 2. The resulting product was bonded to the opposite side to the sliced surface. The obtained coated product was an artificial grain leather having the different color spot groups in which the lightness values differed from those of Example 2 and was slightly different from front to back.
When the above-mentioned grained surface was viewed through a microscope at a magnification of 80, the fiber forming the different color spot groups was visible through the coating layer. Clothing in which the front and back was of this artificial grain leather displayed a color effect caused by the combination of different color spot groups which was unprecedented.
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An artificial grain leather having different color spot groups comprising:
a fibrous substrate layer of ultra fine fibers, bundles of ultra fine fibers or mixtures of ultra fine fibers and bundles of ultra fine fibrers, wherein said fibrous substrate layer contains a high molecular weight viscoelastic first polymer; said fibrous substrate has at least two types of colors selected from the group consiting of colors of different hues, colors of different lightness values and mixtures thereof; and at least one side of said fibrous substrate layer is a coating layer of a transparent high molecular weight second polymer and appears on the apparent face of the artificial grain leather.
a fibrous substrate layer of ultra fine fibers, bundles of ultra fine fibers or mixtures of ultra fine fibers and bundles of ultra fine fibrers, wherein said fibrous substrate layer contains a high molecular weight viscoelastic first polymer; said fibrous substrate has at least two types of colors selected from the group consiting of colors of different hues, colors of different lightness values and mixtures thereof; and at least one side of said fibrous substrate layer is a coating layer of a transparent high molecular weight second polymer and appears on the apparent face of the artificial grain leather.
2. An artificial grain leather as claimed in claim 1, wherein said ultra fine fibers consist of at least two types of ultra fine fiber materials having different dyeabilities and are dyed with different types of dyestuff.
3. An artifical grain leather as claimed in claim 1, wherein said high molecular weight second polymer layer is colored and transparent.
4. An artificial grain leather as claimed in claim 2, wherein said high molecular weight second polymer layer is colored and transparent.
5. An artificial grain leather as claimed in claim 1, 2 or 3, wherein the high molecular weight first polymer contained in said substrate layer is colored.
6. An artificial grain leather as claimed in claim 1, 2 or 3, wherein said substrate layer consists mainly of ultra fine fibers or bundles of such ultra fine fibers, the fibers being not larger than about 0.7 denier.
7. An artificial grain leather as claimed in claim 1 or 3, wherein the fiber constituting said substrate layer consists of a combination of at least two types of fibers of different dyeabilities.
8. An artificial grain leather as claimed in claim 1, 2 or 3, wherein the fiber constituting said substrate layer is selected from the group consisting of islands-in-a-sea type composite fibers, high molecular inter-arrangement fibers, stripped-off type composite fibers, special polymer blend type fibers and mixtures thereof.
9. An artificial grain leather as claimed in claim l, 2 or 3, wherein the shape of the cross section of the fiber constituting said substrate layer is selected from the group consisting of round, fan, ellipse, frustrums, cross, hollow, deformed hollow, and fan-like triangular.
10. An artificial grain leather as claimed in claim 1, 2 or 3, wherein said substrate is selected from the group consist-ing of such materials as woven fabric, knitted fabric, nonwoven fabric, laminates of said materials, and sandwiched forms of said materials.
11. An artificial grain leather as claimed in claim 1, 2 or 3, wherein said high molecular first and second polymers are selected from the group consisting of polyurethane, polyurethane urea, acrylic resin, silicone rubber, fluorine resin, and mixtures of said substances.
12. An artificial grain leather as claimed in claim l, 2 or 3, wherein said high molecular second polymer layer with a transparent surface is selected from the group consisting of a single layer and multilayers made up of successive coatings.
13. An artificial grain leather as claimed in claim l, 2 or 3, wherein the thickness of said high molecular second polymer layer is not larger than about 100 microns.
14. An artificial grain leather as claimed in claim 1, 2 or 3,wherein the ultra fine fibers constituting said substrate layer comprise a surrounding component and another component, said surrounding component covering the greater part of the side of said other component, said surrounding component being a polyester containing 5-sodium sulfoisophthalate units, said other component selected from the group consisting of a component containing no 5-sodium sulfoisophthalate unit and a component containing only a smaller quantity of 5-sodium sulfoisophthalate than said surrounding component, said other component being a polyester selected from the group consisting mainly of ethylene terephthalate units and butylene terephthalate units, and said other component having a larger intrinsic viscosity than said surrounding component.
15. An artificial grain leather having different color spot groups, comprising:
a fibrous substrate sheet consisting chiefly of ultra fine fibers, bundles of such ultra fine fibers or mixtures of ultra fine fibers and bundles thereof, a high molecular weight viscoelastic first polymer contained in said fibrous substrate sheet, and a coating layer of a high molecular weight second polymer forming at least one side of said fibrous substrate layer on the apparent face of the artificial grain leather, wherein said ultra fine fibers consists of at least two types of ultra fine fiber materials having different dyeabilities and are dyed with different types of dyestuffs such that said fibrous substrate has at least two types of colors distinguishable to naked eyes selected from the group consisting of colors of different hues, colors of different lightness and mixtures thereof, and said polymer coating layer is transparent and thin enough to allow visible light to pass therethrough and to be reflected at the surface of said fibrous substrate layer.
a fibrous substrate sheet consisting chiefly of ultra fine fibers, bundles of such ultra fine fibers or mixtures of ultra fine fibers and bundles thereof, a high molecular weight viscoelastic first polymer contained in said fibrous substrate sheet, and a coating layer of a high molecular weight second polymer forming at least one side of said fibrous substrate layer on the apparent face of the artificial grain leather, wherein said ultra fine fibers consists of at least two types of ultra fine fiber materials having different dyeabilities and are dyed with different types of dyestuffs such that said fibrous substrate has at least two types of colors distinguishable to naked eyes selected from the group consisting of colors of different hues, colors of different lightness and mixtures thereof, and said polymer coating layer is transparent and thin enough to allow visible light to pass therethrough and to be reflected at the surface of said fibrous substrate layer.
16. An artificial grain leather as claimed in claim 15, wherein the fiber constituting said substrate layer is derived from a composite fiber selected from the group consisting of islands-in-a-sea type composite fibers, high molecular inter-arrangement fibers, stripped-off type composite fibers, special polymer blend type fibers and mixtures thereof.
17. An artificial grain leather as claimed in claim 16, wherein said substrate is selected from the group consisting of such materials as woven fabric, knitted fabric, nonwoven fabric, laminates of said materials, and sandwiched forms of said materials.
18. An artificial grain leather as claimed in claim 15, 16 or 17, wherein said high molecular first and second polymers are selected from the group consisting of polyurethane, polyurethane urea, acrylic resin, silicone rubber, fluorine resin, and mixtures of said substances.
19. An artificial grain leather as claimed in claim 15, 16 or 17, wherein said high molecular weight second polymer layer is colored and transparent.
20. An artificial grain leather according to claim 15, 16 or 17, wherein the ultra fine fibers having different dye-abilities are dyed with different dyestuffs, the difference of dominant wave lengths of which is not shorter than 10 mµ.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP84198/83 | 1983-05-16 | ||
| JP8419883A JPS59211685A (en) | 1983-05-16 | 1983-05-16 | Artificial leather with silver |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221882A true CA1221882A (en) | 1987-05-19 |
Family
ID=13823773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000439873A Expired CA1221882A (en) | 1983-05-16 | 1983-10-27 | Artificial grained leather having different color spot groups |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS59211685A (en) |
| CA (1) | CA1221882A (en) |
-
1983
- 1983-05-16 JP JP8419883A patent/JPS59211685A/en active Granted
- 1983-10-27 CA CA000439873A patent/CA1221882A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59211685A (en) | 1984-11-30 |
| JPS618192B2 (en) | 1986-03-12 |
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