JP3137908B2 - Artificial leather substrate for dyeing and method for producing artificial leather substrate for dyeing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a monofilament having a thickness of 0.1 mm.
The present invention relates to an artificial leather base material for dyeing comprising a polyamide ultrafine fiber of 2 denier or less and polyurethane, and more particularly to provide a soft and supple artificial leather base material for dyeing without applying a softening agent after dyeing. Things. Dyed artificial leather base material, as it is on the surface, or after resin processing, embossing or embossing or applying it to the field for labels or clothing accessories, or providing a coating layer on the surface by lamination It has been used in various fields such as artificial leather with silver, for use in bags for casual shoes and handbags, and for use in shoes, bags and clothing accessories by raising the base material. The dyeing resistance of such artificial leather has been advanced to a level comparable to that of natural leather by improvement and modification, and demand has been increasing in terms of ease of care and uniformity.

[0002]

2. Description of the Related Art Hitherto, many methods have been proposed for dyeing an artificial leather substrate to obtain a soft and flexible artificial leather.

For example, Japanese Patent Publication No. 3-40155 describes a method of dyeing a sheet having a coating layer of an elastic polymer or a sheet having naps. In this method, the dyeing base material is cut into parts, and the cut surface is dyed in a deep color to improve the appearance of the product.To obtain a flexible and flexible dyeing base material, the dyeing base before dyeing is obtained. There is no description of the properties required for the material.

In Japanese Patent Publication No. Hei 6-74548, a dyeing base material is subjected to a water-repellent treatment before dyeing, and a water-repellent degree of 55 to 70 is obtained at 80 ° C.
It is described that the dyeing can be performed in a deep color by dyeing. This method involves distributing the dye to the substrate surface and the inside of the substrate, stopping the dye at a high concentration on the surface side, and dyeing it in a deep color. be able to. Water repellents used include fluorine water repellants, silicone water repellants, R-CO
NH— or R—NHCO— (R is a carbon number of 11 to 25)
Water-repellents having a skeleton of (alkyl group) have been proposed. However, these water repellents have little effect as softeners and are rather hard. Since silicone-based water repellents have low water repellency, they must be crosslinked.
When crosslinked, the softening effect is reduced, and if there is no affinity for the fiber, it is dropped off by dyeing. For this reason, even if it can be dyed in a deep color, the effect as a softening agent is small, so that rubbing or softening treatment after dyeing is required.

Further, as a method for producing a nap-up cloth, Japanese Patent Publication No. 57-42749 discloses a method of impregnating a fiber-entangled sheet with a binder by adding a substance having a releasing effect such as paraffin or silicone to the binder. There has been proposed a method of preventing adhesion between fibers and a binder and obtaining a uniform and stable nap length during polishing. However, in the method of impregnating the ultrafine-thinning fiber with a binder and then extracting the parent fiber with toluene or the like, silicone and the like are extracted together with the extraction, and the nap length is stabilized, but the softness and flexibility of the nap are unchanged. Therefore, it is necessary to perform a softening agent or a kneading treatment later. In other words, if the softener is impregnated into the ultrafine fiber bundle, and if each one does not have flexibility, the softness and suppleness as artificial leather, and the slimy feeling and the shark mark property in the case of suede can be obtained. There is no.

[0006] Finally, Japanese Patent Publication No. 55-32828 discloses a method for producing a suede-like sheet comprising ultrafine fibers and polyurethane, in which a polyorganosilicone is applied before and during buffing, and this silicone adheres to the surface of the elastic polymer. There has been proposed a method of buffing in a state of being buffed. However, this method aims at an effect as an auxiliary when bristles are raised. The silicone used here is mainly composed of dimethyl silicone or polyether silicone, and the base material to which these are adhered is
Standing hair is elegant and has good chalk mark properties, but the silicone easily comes off by dyeing, and as it is, it is inferior in flexibility and suppleness, slimy and chalk mark properties, and requires drawdown processing and softener treatment There is.

[0007]

Therefore, the present inventors have developed an artificial leather base for dyeing which can provide a soft and supple dyed artificial leather without requiring a softening treatment or a kneading treatment after dyeing. It is an object of the present invention to provide a material and a method for producing the base material.

[0008]

That is, the present invention provides:
An artificial leather substrate for dyeing comprising an ultrafine fiber of polyamide of 0.2 denier or less and polyurethane, wherein 0.2 to 10% of an amide-modified silicone is added to the substrate. It is a base material and its manufacturing method.

Hereinafter, the present invention will be described in detail. The artificial leather substrate for dyeing of the present invention can be obtained by impregnating a nonwoven fabric of polyamide fibers with polyurethane.

The polyamide used in the present invention includes:
Nylon 6, nylon 6/6, nylon 6/10, nylon 12, and the like. Preferably, nylon 6 is used.

As a method for converting the above polyamide into ultrafine fibers, for example, a polyamide and polyolefin are mixed and spun to form an ultrafine fiber bundle by extracting polyisocyanate with a sea-island structure fiber using polyamide as a dispersion phase and polyolefin as a dispersion medium. And a method of extracting polyolefin with toluene as a bonded type composite fiber composed of polyamide and polyolefin, and alkali-eluting polyester from a polyamide-polyester sea-island structure fiber or bonded type composite fiber to form an ultrafine fiber bundle. There is a method to do.

[0012] The fineness (fineness) of the fibers must be 0.2 denier or less. When a material having a denier of more than 0.2 denier is used, the quality of the obtained suede-like surface becomes inferior when the substrate is raised. Preferably,
It is 0.001 to 0.05 denier, and the fine dyeing property is inferior to 0.001 denier. If it exceeds 0.05 denier, the dyeing property is good, but the flexibility, sliminess and chalk mark property are inferior.

As a method for producing the nonwoven fabric, a conventionally known method is used. When ultra-fine using a composite fiber, as a raw cotton in the state of the composite fiber before ultra-fine, as card, a needle punch and the like to perform a non-woven fabric, impregnated with polyurethane, dried, coagulated, and then, A method of making finer by hot toluene or alkali treatment is preferable. By using this method, it is possible to obtain a soft and supple artificial leather having flexibility in the fibers.

Examples of the polyol component of the polyurethane impregnated in the nonwoven fabric include a polyether type, a polyester type, and a polycarbonate type. Examples of the isocyanate component include diphenylmethane diisocyanate, tolylene diisocyanate, and isophorone diisocyanate. As the polyurethane used in the present invention, all of these combinations can be selected and used depending on the application. For example, in view of physical properties and toluene resistance, it is preferable to use diphenylmethane diisocyanate polyurethane. Further, a polyurethane not containing a polyoxyethylene ether component and a polyurethane containing a polyoxyethylene ether can be appropriately mixed and used. By containing the polyoxyethylene ether component in an amount of 1 to 30% based on the weight of the polymer, the obtained base material has good dyeability and can be dyed in a dark color.

As the amide-modified silicone used in the present invention, those represented by the following formula (1) are used.

[0016]

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Wherein R ¹ is a divalent hydrocarbon, R ² is a monovalent organic group, X is an integer of 1 to 100, and Y is an integer of 1 to 10. . Examples of the divalent hydrocarbon represented by R ¹ include an alkylene group, and specifically, an alkylene group having 1 to 5 carbon atoms such as methylene, ethylene, and propylene is preferably used.

Examples of the monovalent organic group represented by R ² include an alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl and propyl; and a C ⁶ to C 6 group such as phenyl and naphthyl. Twelve aromatic groups are preferably used. X
Is preferably 5 to 10, and Y is preferably 2 to 7.

The amide-modified silicone of the present invention must have an amide bond and a silicone skeleton. By having an amide bond, the affinity with the polyamide fiber is increased, and the state where the silicone is bonded to the polyamide fiber can be maintained even after the base material is dyed.

On the other hand, by having a silicone skeleton, the coefficient of friction of the fiber surface can be reduced, and flexibility can be imparted to the substrate even after the dyeing treatment.

As the amide-modified silicone, those commercially available from silicone manufacturers such as Toray Dow Corning Silicone, Shin-Etsu Chemical and Toshiba Silicone can be used.

The amide-modified silicone may have an organic group such as an amino group or an epoxy group in the compound. Moreover, you may use together with another organically modified silicone.

It is necessary that the amide-modified silicone is provided in a solid content of 0.2 to 10% based on the weight of the base material.

If the applied amount is less than 0.2%, the flexibility is insufficient, and if it is more than 10%, the flexibility is high, but there is a disadvantage that the fibers fall off the surface. Preferably,
0.5 to 5%.

In the case where a nonwoven fabric is prepared using the conjugate fiber before the ultrafine processing, the amide-modified silicone is added to the artificial leather base material for dyeing after the polyamide fiber is finely reduced to 0.2 denier or less. Treated as an amide-modified silicone solution containing 0.01-1.0%.

By adding acetic acid to the amide-modified silicone solution, the polyamide fibers swell and the affinity between the amide-modified silicone and the amide group is increased. If the amount of acetic acid is less than 0.01%, the swelling of the polyamide fiber is insufficient, and if it is more than 1.0%, there is no effect corresponding to this.

The acetic acid added to the amide-modified silicone solution and treated on the base material is evaporated by drying, and does not remain in the artificial leather base material for dyeing finally obtained.

The method for treating the amide-modified silicone solution is not particularly limited, but specific examples include a dip nip method, an impregnation method, a coating method, and a spray method. Especially, it is preferable to process by a dip nip method.

The treatment time of the amide-modified silicone solution is preferably after the composite fibers constituting the non-woven fabric have been made extremely fine by extraction or the like. This is because the fibers that make up the nonwoven fabric
This is because, by making the fibers extremely fine, the surface area of the fibers is increased, and the amide-modified silicone is easily applied to each fiber.

Thereafter, the substrate treated with the amide-modified silicone solution is dried, the leveling of the silicone on the fiber surface is uniformly performed, and the affinity between the polyamide fiber and the amide-modified silicone is increased.

As the drying conditions, for example, it is preferable to keep at 140 ° C. for 2 minutes or more, preferably for 5 minutes or more.

The amide-modified silicone-treated substrate thus obtained usually has a water repellency of 50 or less. Therefore,
When the dyeing treatment is performed on the base material, the dye can be uniformly dyed without delaying the penetration of the dye into the base material and without dyeing the inside of the base material.

Further, the substrate can be dyed as it is, but it can also be dyed after the surface of the substrate is fixed by applying a polyurethane solvent or a resin solution to the surface of the substrate.

The base material thus obtained is uniformly dyed and has a high degree of flexibility even after dyeing, and has sufficient flexibility without using a kneading treatment or a softening agent. Things.

Further, by laminating the surface of the substrate after dyeing, a silver surface layer is formed on the surface of the substrate, and a very supple and soft artificial leather with silver can be obtained. In this artificial leather with silver, an easily dyeable polyurethane may be laminated on the base material before dyeing, and then the artificial leather with dyed silver whose surface color and base material layer color match by dyeing. The artificial leather with dyed silver is a very natural texture when casual shoes and sandals are used.
Appearance.

Before the amide-modified silicone is applied, the base material is made into a napped base by buffing and the like, and then the amide-modified silicone is applied and dyed to improve flexibility, sliminess and surface chalk mark property. Excellent suede-like artificial leather can also be used. Since the amide-modified silicone does not fall off even by dyeing, it has high flexibility, has no sticking of fibers, and has good sliminess and chalk mark properties. In particular, it can be preferably used for shoes, bags, etc. without rubbing or softening.

As described above, since the amide-modified silicone has a high affinity for the polyamide fiber, the artificial leather substrate provided with the amide-modified silicone is
It is possible to maintain a state in which the amide-modified silicone is bonded to the base material even when subjected to a treatment such as dyeing, and to impart flexibility without performing a flexible process even after the dyeing treatment is performed. Becomes possible.

[0038]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
The percentages used herein are based on the weight of the substrate unless otherwise specified.

In the measurement of flexibility according to the present invention, a bending resistance (RB) value is measured and used as a substitute property of flexibility.

Measurement method of bending resistance (RB) A test piece having a width of 2.5 cm and a length of 9 cm is gripped at one end at 2 cm, and a radius of curvature is about 2 cm 4 at a position 2 cm from the other end.
/ 1 Measure the repulsive force when bent into a semicircle and measure 1cm in width.
It is shown by converting to the value of If the RB value is 3.0 or less, the flexibility is good, and if the RB value exceeds 3.0, the resin becomes hard.

Example 1 Nylon 6 and low-density polyethylene chips were melt-mixed and spun at a ratio of 50:50, stretched, crimped, and cut into 8 denier (de), cut length 5
1 mm raw cotton was made. The layers were laminated with a card and a cross layer, and were needle-punched with a needle of 3 barbs at a needle density of 1400 needles / cm ² to prepare a nonwoven fabric having a basis weight of 574 g / m ² and a thickness of 2.5 mm. 150 ° C
Was heated with a drier, and was cooled and nip-fixed with a metal roll at 90 ° C. to be fixed. The basis weight of this product was 570 g / m ² and the thickness was 1.9 mm. Next, 1050 g / m ^{2 of} a polyurethane DMF solution containing a 20% polyoxyethylene ether and a coagulation modifier added to a 15% concentration of polyurethane was impregnated, and the surface was wiped to remove the polyurethane resin.
The mixture was coagulated in a 10% DMF water bath and dried at 150 ° C. Thereafter, polyethylene was extracted with a triene at 80 ° C. The average single yarn denier after this extraction was 0.005 denier. Its basis weight was 450 g / m ² . This substrate was coated with two rolls of DMF at 200 mesh, dried and polished with 320 mesh sandpaper,
Furthermore, it was polished from the opposite direction with a 180-mesh sandpaper to create a suede-like base material having fine nylon fibers raised on the surface. 3% amide-modified silicone (Toray Dow Corning Silicone BY-22-860) solution represented by the following formula (2)

[0042]

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Was impregnated, squeezed with a mangle to adhere 70%, and dried with a dryer at 150 ° C. This is 1.6mx
It was cut to 1.35 m, dyed with a gold-containing dye at 80 ° C. for 2 hours, washed and dried to obtain a suede-like artificial leather dyed in dark brown. This product was flexible as it was, had good chalk mark properties, and was optimal for casual shoes. The bending resistance value of this was RB = 2.0.

Example 2 A non-woven fabric was prepared in the same manner as in Example 1, a polyurethane impregnated with toluene and extracted with toluene at 445 g / m ² , and the same amide silicone as in Example 1 was added. A 2% solution was dipped, squeezed with a mangle to adhere 70%, and dried at 150 ° C. to obtain an artificial leather base material for dyeing. From the surface of the artificial leather substrate, 20 DMF
Two rolls coated with a 0 mesh gravure roll were dyed with a gold-containing dye at 95 ° C. for 6 hours and dyed beige. The dyed substrate is very flexible, supple after drying,
When pressed with a mold at 230 ° C., a very clear burn mark entered. It looked very good as a label. The bending resistance value of this was RB = 2.5.

Comparative Example 1 Instead of the amide-modified silicone in Example 1, a 2% solution of polyether-modified silicone (SH8410, manufactured by Dow Corning Toray Silicone Co., Ltd.) was prepared, dipped, squeezed by a mangle, and adhered by 80%. After drying, the dyed product was dyed in the same manner as in Example 1 because the silicone was water-soluble and dropped off during dyeing. After dyeing, the texture was hard and a softening treatment was required. Its bending resistance value was RB = 4.5.

Comparative Example 2 In Example 2, dimethyl silicone (manufactured by Toray Dow Corning Silicone Co., Ltd.) was used as the silicone.
SH-8710), except that SH-8710) was used. The base material after dyeing had a hard feel and required rubbing and softener treatment. The bending resistance value of this is RB
= 4.3.

Comparative Example 3 In place of the silicone used in Example 1, a quaternary ammonium salt of a higher fatty amide (Eleganol MK manufactured by Meisei Chemical Co., Ltd.) was adhered by the same treatment. This was dyed in the same manner, however, it was not supple and the nap was not sufficiently felt in a glued state. Compounds having an amide bond and having no silicone skeleton were subject to flexibility. Its bending resistance value was RB = 4.5.

Comparative Example 4 Amino-modified silicone (Silcoat FZS manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
An artificial leather substrate was prepared and dyed in the same manner as in Example 1, except that a 5% solution was adhered to 70% by a dip nip. In this case, the aminosilicone fell off during the dyeing, giving rise to flexibility. Its bending resistance value was RB = 4.0.

Example 3, Comparative Example 5 Nylon 6 and low-density polyethylene chips were melt-mixed and spun at a ratio of 50:50, stretched, crimped, and cut to produce raw cotton having a cut length of 51 mm. It is laminated with a card and a cross layer, and is needle-punched with a 3-barb needle at a needle density of 1400 needles / cm ² , and has a basis weight of 650 g / m ² and a thickness of 3.5 mm.
Was prepared. The non-woven fabric was heated by a dryer at 150 ° C., and cooled and nip with a metal roll at 90 ° C. to be fixed. This product has a basis weight of 655 g / m ² and a thickness of 2.30 m.
m. Next, polyurethane 1 containing 7% of 100% Md = 110 kg / cm ² of polyoxyethylene ether
Impregnated with 1300 g / m ^{2 of} a polyurethane DMF solution having a coagulation modifier added to a concentration of 5%, and set the surface to 80% of the substrate thickness.
After squeezing and removing the polyurethane resin, 10% DMF
Coagulated in a water bath of concentration and dried at 140 ° C. After this 8
The dip and nip were repeated with a triene at 0 ° C. to extract polyethylene. The basis weight was 520 g / m ² .
The thickness was 1.5 mm. The average single yarn de of this was 0.007 de. This was sliced to half the thickness.

Next, a release paper having a handle is coated with a one-pack type polyurethane elastomer, dried, and further coated on the release paper.
A liquid type polyurethane elastomer was coated, dried, and then laminated on the slice surface of the substrate. After aging, the substrate and release paper were peeled off. The thus obtained artificial leather having a coating layer was dyed in dark brown using a gold-containing dye. This base material was soft, had a dark surface, a light cross section, was dyed and had a good appearance, and had a good fit when worn. Its RB was 2.0.

For comparison, RB = 3.0 was obtained in the same manner as in Example 3 except that the polyether-modified silicone used in Comparative Example 1 was used.

[0052]

According to the present invention, by applying a silicone having an amide group having a strong affinity for polyamide fibers to an artificial leather base material composed of ultrafine polyamide fibers and polyurethane, the silicone does not fall off even after the dyeing treatment. A soft and supple dyed artificial leather can be obtained without a softening treatment after dyeing.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06N 3/14

Claims (5)

(57) [Claims] 1. An artificial leather base material for dyeing comprising a polyamide ultrafine fiber having a single fiber thickness of 0.2 denier or less and a polyurethane, wherein an amide-modified silicone is added to the base material based on the weight of the base material. An artificial leather base material for dyeing, which is provided in an amount of 2 to 10% by weight. 2. The artificial leather base material for dyeing according to claim 1, wherein the artificial leather base material for dyeing has nap on at least one surface. 3. The artificial leather substrate for dyeing according to claim 1, wherein a polyurethane coating layer is provided on at least one surface of the artificial leather substrate for dyeing. 4. The artificial leather base material for dyeing according to claim 1, wherein the polyurethane is a polyurethane containing 1 to 30% of a polyoxyethylene ether component. 5. An amide-modified silicone solution containing 0.01 to 1.0% of acetic acid is added to an artificial leather base material for dyeing comprising a polyurethane ultrafine fiber having a single fiber thickness of 0.2 denier or less and polyurethane. A method for producing an artificial leather substrate for dyeing, characterized in that the amide-modified silicone is applied so as to be attached in an amount of 0.2 to 10% by weight based on the weight of the substrate.