JPH01272886A - Production of fiber plush sheet - Google Patents

Abstract

PURPOSE:To obtain the title sheet excellent in discoloration resistance to light and heat, by treating, with an ion blocking agent, a fiber-interlaced nonwoven fabric plush sheet consisting of copper-contg. ultrafine polyamide fiber followed by dyeing with a metal complex salt dye and then treatment with a specific stabilizing agent. CONSTITUTION:Firstly, a fiber-interlaced aggregate composed of ultrafine polyamide fiber 5-100ppm in copper halide content and <=0.5de in single fiber fineness and/or bundled fiber thereof is impregnated with a polyurethane to prepare a substrate. Second, one surface of this substrate is put to raising treatment to produce a fiber plush sheet. Thence, this sheet is treated, in advance, with a metallic ion-blocking agent to block eluation of the copper halide followed by dyeing with a metal complex salt dye and then imparting said plush sheet surface with a hindered phenolic compound and a hindered amine compound, thus obtaining the objective suede fiber plush sheet excellent in resistance to light, heat and gas discoloration, which is suitable as an automobile sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a suede-like fiber nap sheet that has excellent resistance to light and heat and discoloration. The details relate to a suede-like fiber nap sheet suitable for automobile seats, interiors, etc.

[Conventional technology]

Conventionally, many proposals have been made to improve the light resistance, heat resistance, gas discoloration resistance, etc. of suede-like or silver-finished leather-like sheets. In particular, it is proposed in Japanese Patent Publication No. 57-5903 to use a polyurethane composition in which a compound represented by 3R411 is added to polyurethane to improve the polyurethane constituting the leather-like sheet. The use of a composite bottom has been proposed in Japanese Patent Publication No. 59-43590. As a precaution, a hindered amine compound is used as a stabilizer to improve the durability of polyurethane by adding it to some of the raw materials for polyurethane production and bonding it to the polyurethane chain or at the end of the polyurethane chain. The combination is disclosed in Japanese Patent Publication No. 57-58469, Japanese Patent Publication No. 59-51632, Japanese Patent Publication No. 59-51633, and Japanese Patent Publication No. 62-4.
It has been proposed in Japanese Patent No. 9883, etc. In addition, other compounds such as inorganic acids,
It has been reported in Japanese Patent Publication No. 61-6097 and Japanese Patent Application Laid-Open No. 59-9611 that attempts are made to increase the effect by incorporating four-carboxylic acids or their derivatives, polybasic acids, etc.
It has been proposed in Publication No. 8, etc.

In addition, it has been proposed in 1983 that polyurethane can be stabilized by blending specific phenolic compounds, hindered amine antioxidants, and specific hydrazine derivatives with polyurethane.
It is proposed in No. 61612.

In addition, copper compounds were also used as light stabilizers and heat aging resistance improvers for polyamide fibers.
In addition to the method proposed in Japanese Patent No. 46, the addition of all phenolic antioxidants has already been widely practiced.

[Problems that the invention helps solve]

To improve the light resistance, heat discoloration resistance, and gas discoloration resistance of conventional leather-like sheets, there are two methods: impregnating the 4R fiber sheet and adding a stabilizer to the polyurethane coating, and combining the stabilizer with the polyurethane. I hope that improvements have been made. However, many stabilizers have poor affinity with polyurethane,
Stabilizers blended with polyurethane may migrate to the surface and fall off, or chemical or physical effects may occur during the process of manufacturing sheet-like products, such as wet coagulation and solvent cleaning of polyurethane solutions, dyeing and finishing processes, etc. The effect of the stabilizer may be reduced due to deterioration or falling off of the stabilizer due to the deterioration of the stabilizer, or unfavorable conditions such as discoloration may occur due to the deterioration of the stabilizer. Furthermore, the fibers constituting the fiber sheet are polyamide fibers, which have a particularly large specific surface area, and in addition to the fact that the fibers are thickened and brittle, they also have improved light reflection properties, gas discoloration resistance, and the ability to dye dyes. There are limits to the suppression of discoloration and fading. Especially car seats,
There are many difficulties in developing materials that can withstand harsh usage conditions such as those used in automobile interiors.

However, the copper chloride added during the production of fibers is eluted during various processing steps of the ultra-fine fiber-raised sheet, such as hot water treatment and finishing agent treatment, and adheres to the polyurethane, causing subsequent damage. Or, copper halide present on the surface of the ultrafine fibers is transferred to polyurethane during heat treatment. Copper rogenide that adheres to polyurethane may cause thermal discoloration or light intensity f depending on the type of polyurethane (difference in polyurethane molecular structure) if its amount is large. The suede-like fiber-raised sheet made of non-woven fabric and polyurethane has sufficient light resistance and gas discoloration resistance for use under harsh conditions such as car seats, and is also resistant to dyed NFT products. The object of this invention is to produce a nape-fiber sheet that has discoloration and fading properties and has excellent appearance and feel.

[Means to solve the problem]

The present invention consists mainly of ultra-fine polyamide fibers with an average single fiber size of 0.5 denier or less, containing 5 to 1100 pp of copper halide as copper content, and/i or bundled fibers thereof, and a nine-fiber entangled nonwoven fabric and polyurethane. When dyeing a fiber-napped sheet on the surface of which at least one surface of a substrate consisting of a polymer as a main component is mainly comprised of fiber-napped fibers formed by the fiber ends of the fibers constituting the substrate, after the fiber-napped sheet is treated with a metal ion sequestering agent. , dyeing with dyes mainly consisting of metal complex dyes, followed by hindered phenol compounds and hindered amine compounds? In other words, the present invention is characterized in that the copper halide is applied to at least the surface of the raised hair sheet.
Ultra-fine polyamide fibers containing 0 ppm and having an average strength of 0.5 denier or less and/or fiber-coordinated nonwoven fabrics composed entirely of bundled fibers thereof, and porous structures contained in the spaces of the nonwoven fabrics. is a base fibrous sheet consisting of a polymer consisting entirely of polyurethane with a non-porous structure, or at least one side of the base fibrous sheet is subjected to a napping treatment to mainly consist of fiber naps formed by the fiber ends of the base constituent fibers. After treating the surface of the fiber-raised sheetra with a metal ion sequestering agent, it is dyed with a dye mainly composed of metal complex dyes, and the fiber-raised sheetra is colored to the desired color tone, and then a hindered phenol compound and a hindered amine compound are added to the solvent. After dissolving, the dispersed stabilizer composition liquid is applied to at least the surface of the colored fiber-napped sheet, so that a concentrated stabilizer is adhered to the surface portion, or the stabilizer composition liquid is applied to the colored fiber-napped sheet. The stabilizer is completely coated inside the fiber napped sheet by coating and impregnating it from one side or by immersing the fiber napped sheet in a stabilizer composition solution.

The copper halide-containing ultrafine polyamide fibers of the present invention are produced by adding all the copper halide in the polyamide production process, and then forming polyamide pellets or spinning them into fibers. In addition, we attach or mix copper halide to polyamide pellets and re-shape them to make master pellets containing copper halide.The master pellets are then mixed with polyamide pellets in a predetermined amount and spun to make fibers. It can be made by attaching or mixing copper halide and spinning it into fibers.

Copper halides added during the production of polyamide fibers are copper iodide, copper chloride, copper bromide, and fC is a complex compound thereof. A particularly preferred copper compound is a complex compound thereof. The t of copper halide present in the polyamide fiber of the product is 5 to 1100 pp as a steel component,
Preferably, leaving it at a concentration of 10 to so ppm is most effective in suppressing thermal discoloration and thermal deterioration of polyamide.

However, if the amount of copper halide added increases, the copper halide will be eluted during the hot water treatment, heat treatment, and chemical treatment that are carried out during the manufacturing process of fiber napping sheets, and will transfer to polyurethane, depending on the type of polyurethane. may have undesirable effects. Then, in order to prevent undesirable conditions such as elution or migration of copper halide, the metal ions are treated with a sequestering agent to sequester metal ions. Examples of metal ion sequestering agents include condensed phosphates such as sodium birophosphate, sodium tripolyphosphate, and sodium polyphosphate, ethylenediaminetetraacetic acid (or sodium salt), N-hydroxyethylethylenediaminetriacetic acid (or sodium salt), Aminopolycarboxylic acids or their salts such as diethylenetriaminepentaacetic acid (or sodium salt), iminodiacetic acid (ip is sodium salt), nitrilotriacetic acid (maku is sodium salt), hydroxycarboxylic acids such as triethanolamine, gluconic acid, citric acid, etc. It is at least one type of compound selected from acids and the like.

The metal ion sequestering agent is mainly water-based and is dissolved in a solvent to treat the fibrous sheet or fibrous napped sheet.

The fiber napping sheet of the present invention is made of ultrafine polyamide fibers made of polyamide containing copper halide and a polymer other than polyamide. A fiber web is made using generated multicomponent fibers of ultrafine polyamide fiber bundles, and fiber entanglement treatment is performed. to obtain a fiber-entangled nonwoven fabric, and then, before or after incorporating a polymer mainly composed of polyurethane into the fiber-entangled nonwoven fabric, the constituent fibers of the nonwoven fabric were treated to produce ultrafine polyamide fibers or ultrafine polyamide fiber bundles. A fiber-entangled nonwoven fabric containing a polymer mainly composed of polyurethane is obtained to obtain a differential fiber sheet. This base fiber sheet is sliced into a predetermined thickness or without slicing, and at least one surface of the product is subjected to a puffing treatment with sandpaper, a raising treatment with a raising machine, etc. to form a raised fiber surface, a brushing treatment, etc. After going through processes such as washing, it was made into a greige material for fiber-raised sheets. The average single fineness of the ultrafine polyamide fibers of this fiber-raised sheet has a texture of a leather-like sheet,
Affects appearance. Especially cowhide, sheepskin velour,
When a suede-like or nupak-like leather-like sheet is intended, the average single fineness is 0.5 denier or less, preferably in the range of 0.3 to 0.001 denier. Increasing the average single fineness to more than 0.5 denier is preferable in terms of performance such as depth of color, color fastness, and abrasion resistance of the dyed product, but it is preferable for the cowhide and elderly suede that are targeted in the present invention. When constructing a leather-like sheet with a textured or nubuck-like texture, even if various processing agents such as softeners and lubricants are applied, the texture, touch, and
Unfavorable in appearance.

The polyurethane contained in the fiber-entangled nonwoven fabric is
polyester diol with an average molecular weight of 700 to 3000,
polyether diol, polyester ether diol, polylactone diol, polycarbonate diol,
At least one kind of organic diisocyanate selected from polymer diols, aromatic diisocyanates, and/or ring group diisocyanates is selected from the group consisting of at least one kind of organic diisocyanate, and other organic diisocyanates or organic triisocyanates are blended as necessary. Active hydrogen atoms 2 such as organic diisocyanates, low molecular diols, low molecular diamines, hydrazine, hydroxyamines, etc.
These include polyester polyurethane, polyether polyurethane, polyester ether polyurethane, polylactone polyurethane, polycarbonate polyurethane, etc., which are obtained by polymerizing compounds that have Solution viscosity at 30°C [ma] = 0.5 to 1.3
A range of polyurethanes. A solution viscosity other than this is not preferable for forming cowhide, old velor, suede or nubuck leather-like materials, which are the object of the present invention. Furthermore, the polymer mainly composed of polyurethane used in the present invention has a dyeing amount of 50 to 50% with respect to metal complex dyes.
An easily dyeable polymer having a ratio of /2 or more can provide a surface product with less irritation. If the dyeing amount of the polyurethane contained in the fiber-entangled nonwoven fabric is 50 η/2 or more, it can be used as is, but if the dyeing rate of the polyurethane is 50 η/f without grooves, it can be used as an easily dyed polyurethane, such as polyurethane. Oxyethylene polyurethane or easily dyeable polymers such as polyvinylpyrrolidone, methoxylated nylon, etc. are blended with a suitable t't polyurethane to obtain the desired amount of dyeing. Preferably, rather than a single polyurethane that is easy to dye, a polyurethane composition containing an easily dyeable polymer gold to achieve the desired dyeing amount is preferable for dyeing fastness, gas resistance stability, polyurethane flexibility, and fiber napping. Preferably in terms of performance such as the texture of the sheet, the dye for dyeing the fiber-raised sheet may be either a 1:1 metal complex dye or a 1:2 metal complex dye, but the latter is preferred. The dyeing method uses a normal dyeing machine and dyes under normal conditions.

Further, the hindered phenol compound and hindered amine compound applied to the dyed leather fiber nap sheet of the present invention prevent discoloration and fading of the dyed product, which is also affected by the quantification phenomenon of polyamide fibers and polyurethane. In particular, it is necessary to have sufficient light resistance and gas resistance for a long period of time even under severe usage conditions such as those used in automobile seats. Hindered aluminum, R3dH%CH3, -C)b-C)h, -CH・(
It is a compound having at least two groups represented by CH3)2(Choose A9). For example. Also, hindered phenol compound -CH
3, -〇) A group selected from I・(CH3)2, -C(C'')3, ゐ is H, -CH3, -CH2CH3, -CH,
It is a compound having at least two groups represented by (CHs)2, -C (C), and (C). for example%
L3. ! 5-to! Js(4-t-butyl-3-hydroxy-2,6-dimethylpenzyl)isocyanuric acid, 1,
3.5-t+)su(3゜5-t-butyl-4-hydroxybenzyl)isocyanurm,)'J ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-
human mixiphenyl) propionate]. At least one compound selected from these solid compounds is attached to at least the surface. Compounds other than those listed above may not exhibit significant effects as stabilizers, or may cause unfavorable results such as causing discoloration or fading of dyed products or contributing to the deterioration of polyurethane due to interaction with dyes. be.

In addition, the blending ratio of the stabilizer is in the range of 1:1 to 4 of the hindered amine compound to the hindered phenol compound, but especially on the fiber nap surface, the amount of the hindered phenol compound is at least 10% greater than the hindered amine compound. Attaching it has a great effect. The amount of the blend of the hindered phenol compound and the hindered amine compound attached to the 4'II napped sheet is 0.5 to 15 weight. Preferably, the surface layer portion is mainly attached and the nine portions are attached. i is 2~15i
It is tchi. If the amount of adhesion is small, the stabilizing effect will be small, but
Even if the applied amount is increased, a remarkable effect proportional to the applied amount cannot be obtained. Moreover, if a large amount exceeding the appropriate amount is deposited, fogging properties, heat discoloration resistance, and gas discoloration resistance will be deteriorated. The preferable adhesion state of the stabilizer composition is to apply the stabilizer composition mainly to the surface of the fiber nap sheet.The application method is -f'J L Id Ri-yHyarol coater method, reverse roll coater method, spray coater method. It is applied by a curtain 70-coater method, etc., and the solvent is removed to make it adhere to the surface in a large amount.In addition, the stabilizer composition liquid contains a material that does not impair the nap state, texture, and various surface properties of the fiber nap sheet. A polymer that does not discolor or fade the surface, such as polycarbonate polyurethane or non-yellowing polyurethane, may be added as a stabilizer spreading agent.

It is also preferable for commercialization of the treated fiber-raised sheet to be subjected to a rolling process to modify the texture and appearance, or a surface brushing process, as necessary.

〔Example〕

Next, embodiments of the present invention will be explained with specific examples.

Note that parts and parts in the examples refer to weight unless otherwise specified.

Example 1 35 parts of low-density polyethylene with a melt index (MI) of 70 and go ppm of copper iodide were added to give the following relative viscosity (
17rel) 2.65 Noro - A multi-component fiber with a fineness of 4.5 denier made of 65 parts (island component) of nylon (island component) has an average basis weight of 730? Polymer glycol of 85 parts of polytetramethylene ether glycol and 15 parts of polyethylene ether glycol,
A polyurethane obtained by reacting an organic diisocyanate and a chain extender is dissolved in dimethylformamide, a coagulation regulator is added to the polyurethane solution, the polyurethane composition is impregnated, coagulated in a non-solvent coagulating liquid, and then the fiber is dissolved. The polyethylene gold was dissolved and removed in hot toluene to form a 6-nylon fiber bundle containing copper iodide (single fiber average fineness 0.
A fibrous sheet 1 containing polyurethane in the entangled nonwoven fabric (1 denier) and having a fabric weight of 7081♀ was obtained.

Next, the fibrous sheet I was immersed in a 1/100 molar aqueous solution of ethylenediaminetetraacetic acid disodium salt and heated to 90°C.
The sheet was treated with water for 30 minutes, washed with water, and dried to obtain a fibrous sheet ■.

The fibrous sheets 1 and 2 were divided into two parts in the middle of the thickness, and the surface during coagulation was treated with an emery puff machine, and the raised fiber surface was released to form fibrous raised sheets IA and 1 with an average thickness of 0.7 m.
[I got an A. The fiber napping sheets IA and [A is a blue metal acetate dye combination sole material, dyed at 95°C for 60 minutes, soaped, washed, and dried to obtain blue suede-like sheets) IB and ■B. Next.

The brushed surface of IB and IIB contains 33 parts of pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl) flobionate) and dimethyl-1-(2-hydroxy succinate). ethyl)−
A composition solution of 3 parts of 4-hydroxy-2,2,6゜6-titramethylpiveridine condensate and 94 parts of ethyl acetate was mixed with a gravure roll for about 25 mm. /After applying the amount of Go and drying,
Massage treatment, brushing treatment, suede preparation I
C and ■C were obtained. These were subjected to a light resistance test using a xenon tester and a heat discoloration test in which they were treated in dry air at 160° C. for 10 hours. The results are shown in Table 1.

The amount of tomo copper remaining in the product was about 23 ppm.

In other words, as the amount of metal ions increases, the light resistance and thermal discoloration resistance of the suede-like sheet tend to decrease slightly, but by treating it with a metal ion sequestering agent, the stability of the suede-like sheet increases and the problem of fogging is reduced. It was also suitable as an automobile seat.

Example 2 The fibrous sheet 1 of Example 1 was treated with an aqueous solution of various metal ion sequestrants at 90°C for 30 minutes, washed with water, dried, and then dyed and finished in the same manner as in Example 1 to obtain a suede finish. Table 2 shows the results of the light resistance test and thermal fading test conducted on the product.

In other words, by sealing off metal ions, a suede-like sheet with excellent heat discoloration and fading properties can be obtained. It is a fiber-raised sheet based on a polymer mainly composed of , and has excellent light resistance, heat resistance, discoloration resistance, and gas discoloration resistance, and has a suede-like appearance, feel, stain resistance, and fogging resistance. It is a fiber nap sheet.

Patent applicant RiRashi Co., Ltd.

Claims (1)

[Claims] (1) Mainly composed of polyurethane and fiber-entangled nonwoven fabric mainly composed of ultrafine polyamide fibers with an average single fiber size of 0.5 denier or less and/or bundled fibers thereof containing 5 to 100 ppm of copper halide as copper content When dyeing a fiber napped sheet on the surface of which at least one surface of a substrate consisting of a polymer is mainly composed of fiber napped formed by the fiber ends of the fibers constituting the substrate, after the fiber napped sheet is treated with a sequestering agent. 1. A method for producing a fiber napped sheet, which comprises dyeing with a dye mainly consisting of a metal complex dye, and then applying a hindered phenol compound and a hindered amine compound to at least the surface of the fiber napped sheet.