JPH0515831B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing artificial leather similar to natural suede-like leather, which has a soft and warm appearance, a soft and moist texture, and a three-dimensional pattern. . [Prior Art] Conventionally, methods for manufacturing suede-like fabrics include making woven, knitted or non-woven fabrics using ultrafine fibers such as nylon or polyester, dyeing them in a plain color and then raising them, or dyeing them in a plain color and then turning them into a plain color. A method is known in which the material is dyed, then impregnated with a polyurethane resin, hardened, and then subjected to surface finishing such as emery processing. However, with this method, it is not possible to obtain an appearance and feel that are close to those of natural suede-like leather. In order to eliminate these drawbacks, attempts have been made to make the appearance closer to natural suede-like leather using printing methods. That is, in Japanese Patent Application Laid-Open No. 59-22791,
Japanese Patent Laid-Open No. 54-55702 discloses a method of sublimation transfer printing on a raised fabric after plain dyeing, and a method of heat transfer printing on a raised fabric with a transfer sheet on which a pattern is formed. All of these methods use transfer sheet paper, and are unsatisfactory due to drawbacks such as complicated operations, inability to obtain deep color tone, and poor color fastness. [Problems to be Solved by the Present Invention] The present invention solves these problems by producing a natural product that has a plump and warm appearance, a soft and moist texture, and a three-dimensional pattern. The purpose of the present invention is to provide a manufacturing method that provides artificial leather similar to suede-like leather. [Means for Solving the Problems] The object of the present invention is to provide a knitted fabric containing fibrillated composite fibers made of polyester or polyester and polyamide, (a) a raising step, (b) (c) background dyeing and then partial direct printing, or partial direct printing and then solid pattern direct printing; however, in partial direct printing, a colored paste containing a carrier is used. Performing the three steps in any order;
The problem is solved by a method for manufacturing suede-like artificial leather, which includes the step of (d) applying and coagulating a polyurethane resin, and then raising the surface. The knitted fabric used in the present invention is composed entirely or mainly of fibrillated composite fibers in which one filament can be split into two or more. Fibrillated composite fibers are mixed yarns made of two or more types of polyester or composite fibers made of polyamide and polyester, and at least one component is not completely surrounded by other components in the cross section of the fiber. Each component is joined together. Such fibrillated composite fibers themselves are well known, and examples of their cross sections are shown in FIGS. 1 to 6. Figure 1 shows a composite fiber with a cross section in which two components are joined side-by-side. Figure 2 shows a composite fiber in which two components are joined side-by-side repeatedly. Figure 3 shows a composite fiber in which two components are joined side-by-side repeatedly. and a composite fiber having a cross section joined by forming a hollow part in the center, FIGS. 4 and 5
The figure shows a composite fiber having a cross section in which a radial-shaped component and another component with a shape that complements the radiating part are joined together. Figure 6 shows a radial-shaped component that complements the radiating part and extends toward the center. Composite fibers each having a cross section in which a component with a V-shaped recess facing toward the other side and a V-shaped component complementary to the recess and the same component as the radial-shaped component are joined. . The polyesters referred to in the present invention include, for example, polyethylene terephthalate, polytetramethylene terephthalate, polyethyleneoxybenzoate, poly-1,4-dimethylcycloxane terephthalate, polypivalolactone, copolyesters containing these as components, polybutylene terephthalate, Examples include so-called cationic dyeable polyesters into which sulfoisophthalic acid has been introduced. Examples of polyamide include nylon 4, nylon 6, nylon 7, nylon 11, nylon
12, nylon 66, nylon 6,10, polymethaxylene adipamide, polyparaxylylene decanamide, polybiscyclohexylmethanedecanamide, and copolyamides containing these as components. The fibrillated composite fiber in the present invention preferably has a single filament fineness of 1 to 10 deniers, particularly preferably 1 to 5 deniers, before opening. Single yarn fineness after opening is 1 denier or less, especially 0.5
It is desirable that it be less than denier, and this is what makes the surface feel similar to natural suede leather. More preferably, it is 0.1 to 0.3 denier. The knitted fabric used in the present invention can be obtained by knitting the fibrillated composite fibers described above by conventional warp knitting, circular knitting, or the like. In addition to knitted fabrics, there are other forms of fiber structures such as woven fabrics and non-woven fabrics, but compared to natural suede leather, these are harder, too thick, and have a ``tension'' in drapability.
It lacks so-called "flexibility" and is not desirable. The raising step (a) in the present invention can be carried out by any conventionally known raising method, such as cloth raising, emery, brushing, etc., either alone or in combination. The purpose of the opening step (b) in the present invention is to make the fibers extremely fine so that the feel of the product approaches that of soft and moist natural suede-like leather. That is, using fibrillated composite fibers and opening them is an important feature of the present invention. The opening process, that is, the separation (fibrillation) of different types of fibers is itself known, and is carried out by taking advantage of the difference in chemical resistance of different types of fibers. That is, in the case of polyester and polyamide, at least one of benzyl alcohol, phenylethyl alcohol and phenol
It contains or is coated with an aqueous solution or aqueous emulsion of the drug, and is then dehydrated using a mangle or a dehydrator. The temperature and pick-up amount of the impregnating agent are appropriately adjusted depending on the type of different fibers, their ratio, knitting structure, density, etc. After applying such a chemical, a steam treatment is performed at 70° C. or higher, preferably 90 to 120° C., to shrink the polyamide and release the bond with the polyester to form fibrils. In the case of composite fibers made of different types of polyester, opening is performed by utilizing the difference in solubility in alkali. For example, in the case of a cross section as shown in Fig. 5, a composite fiber in which part B is a polyester that is difficult to dissolve in alkali and part A is a polyester that has high solubility in alkali is treated with alkali to dissolve the part B and form a fibril. make changes. The alkali treatment conditions should be adjusted appropriately depending on the type of polyester used, the blending ratio of different polyesters, the structure and density of the knitted fabric, but as a general condition, it is 30-60 minutes at 95°C with 15% aqueous caustic soda solution. After opening, if necessary, heat setting at 180° C. for about 1 minute may be applied. (c) ground dyeing and then partial direct printing, or partial direct printing and then solid direct printing, where partial direct printing uses a colored paste containing a carrier; the purpose of the process is to: This two-step dyeing process provides a pattern with a three-dimensional effect, and the inclusion of a carrier in the color paste of the partial print shrinks the polyester and/or polyamide, thereby giving the pattern a deep three-dimensional effect. The purpose is to further enhance the texture and obtain a soft texture. Background dyeing can be performed by a known method.
For example, any method may be used, such as a batch method such as a liquid jet dyeing machine, Winx, Jitzger, etc. that uses ordinary disperse dyes, or a continuous dyeing method such as a thermosol method, high temperature steaming method, high pressure steaming method, etc. However, in the case of continuous dyeing method After padding and drying, you can print the next part without developing color. It is preferable that the density of the ground dyeing is slightly lighter than the density of the subsequent partial print, in order to create a three-dimensional effect. There are no particular restrictions on the pattern of the subsequent partial print, but if you want to emphasize the natural suede look, use a tataki pattern or a blurred pattern.
It is preferable that the dye is slightly darker than the ground dye. Also, if you want to emphasize the printed suede look, you can use prints with rich fashion properties such as tiger print, leopard print, floral print, geometric pattern, etc. without being particular about the pattern or color scheme. The above explanation of partial printing is also applicable to partial printing in which partial printing is first performed and then solid pattern printing is performed. After all, it is preferable for the color density of the partial print to be slightly darker than that of the solid pattern print in order to create a three-dimensional effect. Methods for printing solid patterns include screen printing,
Any method that prints a normal solid pattern, such as rotary screen printing or roller printing, may be used. In the present invention, printing is so-called direct printing, not transfer printing as in conventional methods. In transfer printing, the knitted fabric is pressed, so a serious drawback arises in that the product does not have a fluffy texture. In addition, deep color tones cannot be obtained,
And the color fastness is low. Two-step dyeing as described above and direct printing rather than transfer printing are some of the important features of the invention. The carrier in the partial print color paste, which is also an important feature of the invention, must be capable of shrinking the polyester and/or polyamide. Aromatic organic acids, esters, ethers, hydrocarbons, phenols, halides, and amines are known as substances having carrier ability. More specifically,
Phenylphenol-based, chlorobenzene-based, methylnaphthalene-based, and diphenyl-based compounds are known. In the present invention, phenylphenol carriers are preferred. A commercially available phenylphenol carrier is Tetrosin P from Yamakawa Pharmaceutical Co., Ltd.
-300, PE-C, ME Neoton C, Katsumata Kasei Co., Ltd.'s Katulon DK-P, DK-C (all trademarks), etc., and the amount used is 10% to 30% by weight,
Preferably it is 15% to 25% by weight. If the amount is less than 10% by weight, the shrinkage of the fibers will be insufficient, and a three-dimensional effect and soft feel will not be obtained. 30% by weight
If it exceeds this value, there is a drawback that the shrinkage becomes too large and the surface of the product becomes disordered and embrittlement occurs. The effects of the present invention using carriers other than phenylphenol, such as chlorobenzene or methylnaphthalene, are small. Next, after partial printing, it is preferable to perform a heat treatment which also serves as a dye coloring step. For the purpose of creating prints with a three-dimensional effect, steaming is best because it can achieve large shrinkage, and high-temperature steaming with as little tension as possible is preferable.The best conditions are 170-180℃ for 5-10 minutes. . In dry heat treatment, the temperature is 1 to 200℃ to 210℃ to develop the color of the dye.
2 minutes are required, and for shrinkage, 170 to 180°C and 1 to 2 minutes are preferable in view of the embrittlement of the fibers. Therefore, it is difficult to obtain optimal conditions for both color development and shrinkage. The three-dimensional effect obtained according to the invention is durable and is not lost by dry cleaning or washing in a washing machine. After processing in a high-temperature steamer as described above, it is preferable to wash by ordinary reduction washing. The steps of (a) raising, (b) opening, and (c) dyeing described above can be performed in any order. for example,
It is possible to open the fibers after raising the fibers, or to do the reverse order. Dyeing after napping or vice versa is possible. Although dyeing can be carried out in any order, it is preferable to carry out the dyeing after opening. The easiest and most natural order in terms of quality control is the order of raising, opening, and dyeing. The order of opening, raising, and dyeing is also preferred. Now, the knitted fabric treated in this way is then (d)
After applying and coagulating the polyurethane resin, the surface is subjected to a raising step. This process itself is also known in the artificial leather manufacturing process, and any known method can be used. As the polyurethane resin, polyurethane elastomers are preferred. Add crosslinking agents, colorants, fillers, light stabilizers, etc. as necessary. Polyurethane itself or a solution, emulsion or paste resin containing polyurethane is applied to and impregnated into the knitted fabric by a conventional method such as coating, spraying or padding. The amount of polyurethane applied is 3 to 50% by weight, preferably 5 to 40% by weight, based on the weight of the knitted fabric. If it is less than 3% by weight, the elasticity of the leather will be poor and the texture will be cloth-like. 50
If it exceeds % by weight, it lacks flexibility and has a rubber-like texture, which is undesirable. Polyurethane coagulation methods include direct evaporation of the solvent (dry coagulation method),
A method of immersing the material in a coagulating liquid and coagulating it (wet coagulation method) can be used. A wet coagulation method is preferable in order to leave micropores in the coagulated resin layer and give it flexibility. Examples of the coagulating liquid include water, a mixture of dimethylformamide and water, inorganic salts (salt,
Examples include aqueous solutions of glauber's salt and ammonium sulfate. After wet coagulation, the solvent is removed by washing with water and then dried. A method of raising polyurethane after coagulating is known, and for example, a method called buffing or sanding can be performed. [Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
"Parts" in the description of Examples are parts by weight. The test method is as follows. Tear strength (g): JIS L1096-D method Shrinkage and three-dimensional impression of print: Visual judgment Example 1 The cross section is as shown in Figure 5, and the A component is nylon 6 and the B component is polyethylene terephthalate. Using a certain 50 denier/25 filament fibrillated composite fiber as the front yarn,
A tricot satin was knitted using 30 denier/12 filament polyethylene terephthalate yarn as the back yarn. However, a 28-gauge tricot knitting machine was used, and the number of courses was 90 courses/inch. Both the front and back sides of the obtained tricot gray fabric were raised using a needle cloth raising machine. Next, the raised tricot was subjected to a fibrillated composite fiber opening treatment in the following manner. First, the sample was impregnated with an emulsified aqueous solution containing 8% by weight of benzyl alcohol and 2% by weight of an anionic activator at 30°C and squeezed. The pick-up ratio of the emulsified aqueous solution was 75% by weight/raised fabric. Next, it was treated with saturated steam at 95°C for 10 seconds, then washed with water to remove benzyl alcohol, and then dried. Then, after heat setting at 180℃ for 60 seconds,
Tataki pattern (brown) on the entire surface using the printing paste below
The overprint was done by screen printing (30-80% by weight). The tataki pattern used is shown in Figure 7. The black part indicates the printed part.

【table】

[Table] After the print was dried, a solid pattern was printed on brown using a screen printing machine using the following printing paste (100 to 120% by weight). (Solid pattern color glue prescription) Holon Brown S-3RL (manufactured by Sandoz Co., Ltd., disperse dye) 5 parts Paste 30 parts Tartaric acid 0.2 parts Sodium chlorate 0.2 parts Warm water 64.6 parts Total 100 parts Viscosity 2,800 cps Print After drying, it was treated in a high-temperature steamer at 180° C. for 8 minutes, and then washed with hot water, reduction washing, hot water, and water using a winch, and dried in a shot loop dryer. Next, it was impregnated with a 10% polyurethane N,N' dimethylformamide solution to give a solid content of 10%, wet-coagulated in water, thoroughly washed with water, and dried. Next, the raised surface was polished using a sanding machine equipped with No. 120 sandpaper to obtain artificial suedes No. 1 to No. 6 as shown in Table 1. 15 to 25 phenyl phenol carriers
In the case of adding %, an artificial suede with a firm feel, a smooth surface touch, and a three-dimensional color was obtained. These had a plump appearance and a soft texture.

[Table] Example 2 A fibrillated composite fiber of 50 denier/25 filament having a cross section as shown in Fig. 4 and having component A as nylon 6 and component B as polyethylene terephthalate was used as the front yarn. normal
A tricot satin was knitted using 30 denier/12 filament polyethylene terephthalate yarn as the back yarn. However, a 28-gauge tricot knitting machine was used, and the number of courses was 90 courses/inch.
Both the front and back sides of the obtained tricot gray fabric were raised using a needle cloth raising machine. Next, the raised tricot was subjected to fiber opening treatment in the same manner as in Example 1, then heat set at 180°C for 60 seconds, and then ground dyed brown using a jet dyeing machine under the following dyeing conditions. . Diamondx Orange U-SE (Mitsubishi Kasei Corporation, disperse dye) 1.56% owf Diamondx Red U-SE (Mitsubishi Kasei Corporation, disperse dye) 0.46%owf Diamondx Blue U-SE (Mitsubishi Chemical Corporation, disperse dye) Co., Ltd., disperse dye) 0.51% owf Nitsuka Sunsalt #7000 (Nichika Chemical Co., Ltd., dispersant) 0.5g/ adjusted to PH=5 with acetic acid and sodium acetate Bath ratio 1:30 Dyeing temperature, Time: 130℃ x 60 minutes After dyeing, wash with hot water at 60℃ for 10 minutes, then use Noigen ET135 (soaping agent manufactured by Daiichi Kogyo Co., Ltd.) 2g/
After soaping at 60℃ for 20 minutes, washing with water, and drying, a tataki pattern (2 shades of brown) was applied to the entire surface under the printing conditions below.
The overprint (color) was done using screen printing. The print patterns shown in FIGS. 7 and 8 were used for the dark and light color prints, respectively.

[Table] After the prints were dried, they were treated in a high-temperature steamer at 180°C for 8 minutes, then washed with hot water, reduced cleaning, hot water, and water using a winch, and dried in a shot loop dryer. Next, polyurethane application, sanding, and finishing treatments were performed to obtain artificial leather. We have obtained a suede-like artificial leather with a deep, calm brown color, a surface texture very similar to natural suede, a plump appearance, and a flexible texture. [Effects of the Invention] The present invention provides artificial leather that resembles natural suede-like leather and has a soft and warm appearance, a soft and moist texture, and a three-dimensional pattern. . Suede-like artificial leather with such an appearance and feel could not be obtained by conventional methods.

[Brief explanation of the drawing]

1 to 6 are enlarged views showing examples of cross sections of fibrillated composite fibers used in the present invention. FIGS. 7 and 8 show the tataki pattern used in the partial print of the present invention. The black part is the part that will be printed.

Claims (1)

[Scope of Claims] 1 A knitted fabric containing a fibrillated composite fiber made of polyester or polyester and polyamide is subjected to (a) a raising process, (b) a fiber opening process, and (c) a background dyeing process. Then perform partial direct printing, or perform partial direct printing and then solid pattern direct printing, with the exception that in partial direct printing, a color paste containing a carrier is used, and the following three steps are performed in any order. A method for producing suede-like artificial leather, which includes the following steps: (d) applying and coagulating a polyurethane resin, and then raising the surface. 2. A claim in which the single fiber fineness of the polyester and polyamide constituting the knitted fabric after opening is 1 denier or less, and the fabric weight of the fiber structure is 200 to 400 g/cm ² and the thickness is 0.5 to 1.0 mm. The method described in paragraph 1. 3. The method according to claim 1 or 2, wherein the carrier is a phenylphenol compound. 4. The method according to any one of claims 1 to 3, wherein the steps (a), (b), (c), and (d) are performed in the order.