JPH11229279A - Leatherlike sheet material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a leatherlike sheet material having excellent dyeing properties, deep-coloring properties and light-resistance fastness by forming an entangled nonwoven fabric containing specific copolymer polyester ultrafine fibers. SOLUTION: An entangled nonwoven fabric is produced by using an islands- in-a sea type conjugate fiber whose at least one component is a polyester obtained by copolymerizing a compound expressed by the formula [R1 to R10 are each an ester-forming functional group, H or an alkyl, and 1 or 2 of R1 to R10 are ester-forming functional groups; (x)=O, 1; (y) is an integer satisfying the equation: 1<=(x)f(y)] in an mount of 1-10 mol.% and a sulfonic group- containing compound in an amount of 1-5 mol.%. The obtained nonwoven fabric is impregnated with an elastic resin liquid, and then, the fabric is subjected to a coagulation treatment to form a dense foamed body. Subsequently, the nonwoven cloth is subjected to a treatment for removing the sea component to form ultrafine fiber bundles of single fineness of <=0.5 de, preferably <=0.3 de, more preferably <=0.1 de, and then,the cloth is dyed into a specific color tone with a disperse dye and a cationic dye to obtain the objective leatherlike sheet material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dyeing property, a deep color property,
And a leather-like sheet having excellent light resistance.

[0002]

2. Description of the Related Art Polyester artificial leather is widely used because of its many excellent properties.
Since it is made of ultrafine fibers of denier or less, there is room for improvement in terms of color clarity and depth, particularly the depth of black color, and coloring, as compared with regular products of 1 denier or more. This is because polyester artificial leather is dyed with a disperse dye having poor clarity, and the refractive index (refractive index in the direction perpendicular to the fiber axis) of the polyester ultrafine fiber is 1.7 and other fibers. And the reflectance of light on the fiber surface is higher, and as a result, the intensity of white reflection and scattering from the surface of artificial leather made of polyester fibers is higher.

[0003] As a solution to these problems, various modifications have been proposed in which a dyeing seat of a dye having excellent clarity such as a cationic dye or an acid dye is introduced into the ultrafine polyester fiber.
Although the sharpness of the color is improved, the light reflection scattering caused by the high refractive index of the polyester fiber is not reduced, and the effect of improving the color depth is essentially not exhibited.

On the other hand, by coating the polyester-based artificial leather surface with a compound having a low refractive index, darkening is improved,
It has also been proposed to increase the depth of color, and as compounds having a low refractive index, organofluorine compounds, organosilicon compounds and the like have been proposed. Also, a method has been proposed in which fine irregularities having a pitch smaller than the wavelength of light are formed on the surface of the polyester-based ultrafine fiber to suppress the reflection and scattering of light on the fiber surface.

However, fibers obtained by coating a polyester-based artificial leather surface with a compound having a low refractive index have poor durability of the coating against friction during use and dry cleaning, and have a sufficiently dark color. Even if the effect can be achieved, the feeling, the decrease in the color fastness of the dyed product,
Problems such as a decrease in light resistance occur. Furthermore, in the method of forming fine irregularities on the fiber surface, during the post-processing step, the irregularities are damaged and the effect of suppressing the reflection and scattering of light on the fiber surface is reduced, and the appearance is reduced due to wear and the like during use. Failure may occur.

Further, in order to improve the appearance and texture of artificial leather, it is necessary to increase the fuzz density. As a method of obtaining artificial leather having a high fluff density, there is a method of heat shrinking the original cloth before and after the raw cotton is entangled and fixed with the binder. As a method for obtaining a heat-shrinkable raw cotton, a method of leaving a large amount of an amorphous portion which is easily heat-shrinkable in a fiber without sufficient stretching of a spun yarn or a method of copolymerizing isophthalic acid as a polymerization component when polymerizing a polyester. In general, the acid component has been modified. However, with these methods,
Not enough strength can be obtained when made into artificial leather,
There is a problem that dye spots are easily formed.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and is not only excellent in dyeability and deep color, but also has sufficient strength and light resistance. ,
An object of the present invention is to provide a polyester-based artificial leather having extremely excellent color fastness.

[0008]

That is, the present invention provides a leather-like sheet comprising a base fabric containing a polyester fiber having a single fiber fineness of 0.5 denier or less impregnated with an elastic polymer, wherein the polyester fiber has the following properties: It is made of a polyester obtained by copolymerizing 1 to 10 mol% of a compound having the structural formula (1) and 1 to 5 mol% of a sulfonic acid group-containing compound, and the fibers are dyed with a disperse dye and a cationic dye. It is a leather-like sheet material characterized by the above.

[0009]

[Formula 2] (Wherein, R1 to R10 are groups selected from an ester-forming functional group, a hydrogen atom, and an alkyl group, and one or two of R1 to R10 are ester-forming functional groups.
x is 0 or 1, and y is an integer satisfying 1 ≦ x + y ≦ 3. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the main component of a polyester ultrafine fiber component must be 0.5 denier or less. It is preferably at most 0.3 denier, more preferably at most 0.1 denier. When the main component of the ultrafine fiber exceeds 0.5 denier, the appearance is poor when the suede tone is obtained, the softness is lowered, and the touch is also deteriorated.

The polyester which is a microfiber component in the present invention may be obtained by copolymerizing 1 to 10 mol% of the compound represented by the structural formula (1) and 1 to 5 mol% of a dicarboxylic acid having a sulfonic acid group. is important.

In the compound represented by the structural formula (1),
Examples of the ester-forming functional group include a hydroxy group, a hydroxyalkyl group, a carboxyl group, and ester-forming derivatives thereof. The alkyl constituting the hydroxyalkyl group is not limited, but is preferably an alkyl group having 1 to 4 carbon atoms, such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group or a hydroxybutyl group, and may be a branched alkyl. Further, the ester-forming derivative of the carboxyl group is a carboxymethyl group, a carboxyethyl group,
C1 such as carboxypropyl group, carboxybutyl group
Preferred are alkyl groups of 4 to 4.

It is necessary that the compound has one or two ester-forming functional groups, and if it is copolymerized in the polyester molecular chain, it exhibits high shrinkage characteristics as a polyester fiber and has high It is preferable in terms of dye exhaustion ability, polymerizability, etc., and the ester-forming functional groups may be the same type of group or different types of groups.

Further, in the compound, a hydrogen atom or an alkyl group is bonded to carbon other than the carbon to which the ester-forming functional group is bonded. It is desirable that a hydrogen atom is bonded to carbon other than the carbon atom. In addition, as an alkyl group, a C1-C5 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, is mentioned, and the said group may be branched.

As such a compound, norbornane 2,2
3-dimethanol, norbornane 2,3-diethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3-dicarboxylic acid dimethyl ester, norbornane 2,3-dicarboxylic acid diethyl ester, perhydrodimethanonaphthalenedimethanol, perhydro Dimethanonaphthalenediethanol, perhydrodimethanonaphthalenedicarboxylic acid, perhydrodimethanonaphthalenedicarboxylic acid dimethyl ester, tricyclodecanedimethanol, tricyclodecanediethanol, tricyclodecanedicarboxylic acid, tricyclodecanedicarboxylic acid dimethyl ester, tricyclo Examples thereof include decanedicarboxylic acid diethyl ester, and compounds in which an alkyl group is bonded to carbon other than the ester-forming functional group in these compounds.

Among the above compounds, norbornane 2,3-dimethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3 are preferred in terms of polymerizability, spinnability, strength of artificial leather, shrinkage performance, and dye exhaustion performance. -Dicarboxylic acid dimethyl ester, perhydrodimethanonaphthalenediethanol, perhydrodimethanonaphthalenedicarboxylic acid, perhydrodimethanonaphthalenedicarboxylic acid dimethyl ester, tricyclodecanedimethanol, tricyclodecanediethanol, tricyclodecanedicarboxylic acid, Tricyclodecanedicarboxylic acid dimethyl ester is preferred. Further, from the viewpoint of polymerizability, norbornane 2,
3-dimethanol, norbornane 2,3-dicarboxylic acid, norbornane 2,3-dicarboxylic acid dimethyl ester, perhydrodimethanonaphthalenediethanol, perhydrodimethanonaphthalenedicarboxylic acid, perhydrodimethanonaphthalenedicarboxylic acid dimethyl ester are 2 Preferably, two ester-forming functional groups are located in the trans position.

The content of the compound represented by the structural formula (1) may be 1 to 1 with respect to the dicarboxylic acid component constituting the polyester.
It is in the range of 10 mol%, preferably 3 to 8 mol%. When the content is less than 1 mol%, the degree of crystallinity of the polyester is lowered and the rate of shrinkage of the fiber is insufficiently increased.
The intended artificial leather cannot be obtained. On the other hand, when the content is 1
If it exceeds 0 mol%, the polymerizability of the polyester will decrease, and it will be difficult to obtain a crystalline polyester. Even if it is obtained, the strength and melting point of the polyester will decrease, and the strength and heat resistance required for artificial leather will be reduced. I can't satisfy her. Further, as the content of the compound increases, the exhaustion ability of the dye increases and the crystallinity and melting point of the polyester decrease, but the shrinkage rate of the polyester artificial leather fabric tends to increase, so that the appearance, the fuzz density The content may be changed within the scope of the present invention in consideration of the feeling, the feeling, the dyeability, and the like.

Further, in the present invention, in order to color the ultrafine fibers into a color excellent in clarity and coloring, copolymerization is carried out by using a dicarboxylic acid having a sulfonic acid group in addition to the above-mentioned copolymerization components. is important. Examples of the dicarboxylic acid having such a sulfonic acid group include dimethyl sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, and isophthalic acid having a sulfonic acid metal base such as 5-lithium sulfoisophthalic acid; -Tetrabutylphosphonium sulfoisophthalic acid, 5-ethyltributylphosphonium sulfoisophthalic acid and the like can be mentioned, but it is preferable to use 5-sodium sulfoisophthalic acid from the viewpoint of versatility. The content of the dicarboxylic acid having such a sulfonic acid group must be 1 to 5 mol% of the dicarboxylic acid component constituting the polyester. If the amount is less than 1 mol%, sufficient dyeing performance cannot be obtained. On the other hand, if it exceeds 5 mol%, the fiber strength is reduced and it cannot be used as a leather-like sheet.

The polyester in the present invention is a polyester containing terephthalic acid as a main dicarboxylic acid component and at least one alkylene glycol selected from ethylene glycol, trimethylene glycol and tetramethylene glycol as a main glycol component.
Further, the third component other than the compound represented by the structural formula (1) and the dicarboxylic acid having a sulfonic acid group may be copolymerized within a range not to impair the object of the present invention.

As the third component, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid,
4,4'-diphenylmethanedicarboxylic acid, 4,4'-
Diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-diphenoxyethane-4 ', 4 "dicarboxylic acid, anthracene dicarboxylic acid, 2,5-pyridine dicarboxylic acid, diphenoxy ketone dicarboxylic acid, etc. Aromatic dicarboxylic acids; aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid; alicyclic dicarboxylic acids such as decalin dicarboxylic acid and cyclohexanedicarboxylic acid; β-
Hydroxycarboxylic acids such as hydroxyethoxybenzoic acid, p-oxybenzoic acid, hydroxypropionic acid and hydroxyacrylic acid; carboxylic acids derived from these ester-forming derivatives; aliphatic lactones such as ε-caprolactone; hexamethylene glycol; Aliphatic diols such as neopentyl glycol, diethylene glycol and polyethylene glycol; hydroquinone, catechol,
Naphthalene diol, resorcinol, bisphenol A,
Aromatic diols such as an ethylene oxide adduct of bisphenol A, bisphenol S, and an ethylene oxide adduct of bisphenol S; and aliphatic diols such as cyclohexanedimethanol can be given. One or more of these third components may be copolymerized.

Further, polycarboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, and tricarballylic acid; glycerin, trimethylolethane, trimethylolpropane, and the like, as long as the polyester is substantially linear.
A polyhydric alcohol such as pentaerythritol may be copolymerized.

The polyester according to the present invention can be polymerized by a usual method. For example, terephthalic acid is directly esterified with alkylene glycol, terephthalic acid is reacted with a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and alkylene glycol, or transesterified with terephthalic acid and alkylene oxide. The reaction in the first step for producing an alkylene glycol ester of an acid and / or a low polymer thereof, and the reaction product obtained in the first step are subjected to the reaction using a polymerization catalyst such as antimony trioxide, germanium oxide, or tetraalkoxyethane. 230-300 ° C under reduced pressure
To a polycondensation reaction until the desired degree of polymerization is reached. At this time, a desired amount of the compound represented by the structural formula (1) and the dicarboxylic acid component having a sulfonic acid group is added to an arbitrary stage until the polycondensation reaction is completed, for example, the starting material of the polyester is added or the transesterification It can be added later before the polycondensation reaction. Further, in order to increase the degree of polymerization of the polyester, it is also possible to carry out solid phase polymerization after conducting polymerization in a liquid phase.

The polyester used in the present invention has an intrinsic viscosity [phenol / tetrachloroethane (50/5 by weight).
0) measured at 30 ° C. using the mixed solvent of 0.4) to 0.4-1.
It is preferably in the range of 5. When the intrinsic viscosity of the polyester is less than 0.4, the strength of the artificial leather becomes insufficient, and the intended purpose is hardly achieved. On the other hand, if the intrinsic viscosity of the polyester exceeds 1.5, the melt viscosity of the polyester becomes too high, and the production state of raw cotton such as spinning and drawing deteriorates, which is not preferable.

The polyester used in the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, a fluorescent brightener, a matting agent, an antistatic agent, a flame retardant, and a flame retardant as long as the present invention is not impaired. Additives such as agents, lubricants, coloring agents, plasticizers, and inorganic fillers may be blended. Also, if necessary, fine particles having an average particle size of 100 μm or less are about 0.1 to 5 wt%,
It can be added during or after the polycondensation reaction. The material of the fine particles is not particularly limited. For example, silica gel (colloidal silica), dry silica, dry silica containing aluminum oxide, an alkyl group on the particle surface, and a silanol group on the particle surface are blocked. Inactive particles such as dry silica, alumina sol (colloidal alumina), fine particle alumina, fine particle titanium oxide, and calcium carbonate sol (colloidal calcium carbonate), and a phosphorus compound and a metal compound are reacted and precipitated inside the polyester reaction system. Precipitated fine particles are preferably used. In particular, silica fine particles having an average particle size of 15 to 70 nm are preferable, and the spinnability and stretchability are improved, and irregularities are obtained on the fiber surface, and the color of the leather-like sheet after dyeing becomes deeper. The sharpness is also improved.

The method for producing a leather-like sheet according to the present invention will be described below. The leather-like sheet material of the present invention can be obtained, for example, by combining the following steps as a typical production method. That is, (1) at least one
A step of producing a sea-island structural fiber whose component is the copolymerized polyester specified in the present invention, (2) a step of producing an entangled nonwoven fabric made of the fiber, (3) a step of temporarily fixing the nonwoven fabric as necessary, (4) a step of impregnating the entangled nonwoven fabric with an elastic resin liquid and coagulating to form a dense foam; (5) a step of removing a sea component polymer from the fibers to modify them into ultrafine fiber bundles; ) It can be obtained by sequentially performing a step of dyeing with a disperse dye and a cationic dye.

First, the production of fibers will be described. In the above (1), an example of producing sea-island structural fibers is mentioned. The ultrafine fibers constituting the leather-like sheet of the present invention are as follows.
The above-mentioned copolymer polyester is melt-spun alone to produce fibers having a single fiber fineness of 0.5 denier or less, or composite spinning using the above-mentioned copolymer polyester for the island component of the sea-island structure fiber, and thereafter removing the sea component By using the above-mentioned copolyester as one component of various splittable conjugate fibers such as ultrafine fibers having a single fiber fineness of 0.5 denier or less or a cross-sectional structure in which different polymers are alternately laminated in multiple layers, composite melt spinning Then, it can be obtained by various methods such as splitting and dissolving afterwards, but 0.5
If ultrafine fibers of denier or less are used, the processability, handleability, and fiber damage up to the creation of a leather-like sheet afterwards tend to be problems. In addition, it is desirable to use a sea-island structural fiber or a split-type composite fiber having a cross-sectional structure other than that to obtain an ultrafine fiber. Furthermore, in order to realize an excellent suede touch suitable for clothing, it is preferable to form ultrafine fibers via sea-island structural fibers capable of obtaining ultrafine fibers of 0.1 denier or less.

For example, in the case of a sea-island structure fiber, the copolyester obtained as described above and one or more thermoplastic polymers incompatible with the copolyester are subjected to composite spinning or mixing. Although it can be obtained by spinning, the sea component polymer is preferably a polymer having a lower melt viscosity and a higher surface tension than the copolymerized polyester under spinning conditions.

The other thermoplastic polymer which is composite-spun or mixed-spinned with the copolyester is different from the copolyester in solubility or degradability in a solvent or a decomposer (more soluble or degradable than the copolyester). Is large) and a polymer having low compatibility with the copolyester, and is, for example, at least one polymer selected from polymers such as polyethylene, polystyrene, copolyethylene copolymer, and alkali-soluble polyester. For example, polystyrene can be easily extracted with toluene, and polyethylene can be easily extracted with tricrene.
Modified polyesters such as sodium sulfoisophthalate copolymerized polyethylene terephthalate can be decomposed and removed with alkali. However, since the sulfoisophthalic acid is copolymerized in the copolyester forming the ultrafine fibers, the alkali solubility is relatively high.Therefore, when the polyester is selected as another thermoplastic polymer, the alkali of the copolyester is selected. It is desirable to use a modified polyester whose alkali dissolution rate is sufficiently higher than the dissolution rate (for example, 25 times or more).

By extracting or decomposing and removing the easily removable polymer from the conjugate fiber, it is possible to obtain a copolyester ultrafine fiber bundle having a desired single fiber fineness. In the present invention, the copolyester fiber bundle may be endlessly connected in the fiber length direction, or may be in a discontinuous state.

After the composite spun yarn is once wound,
Or it is subjected to stretching without being wound up, and the stretching is 50 to
In a water bath at a temperature of about 100 ° C., the cut stretch ratio
The stretching is performed at a stretching ratio of at least 0.70, preferably at least 0.70. If the stretching ratio is less than 0.55 times the cutting stretching ratio,
An artificial leather having sufficient strength cannot be obtained.

Next, in the sheet-like material of the present invention, for example, the above-mentioned sea-island structure fiber is opened with a card, a web is formed through a webber, and the obtained fiber web is laminated to a desired basis weight and thickness. Then, entanglement is performed by a known method, for example, a needle punching method or a high-pressure water entanglement method, to form a nonwoven fabric, or the staple is entangled with a knitted woven fabric using a water current or the like, and the fabric is woven. And If the woven or knitted fabric used for reinforcing the nonwoven fabric has the same composition as the main microfiber, not only does it not easily wrinkle when performing the shrinking treatment, but also the woven or knitted fabric has a high shrinkage and has a high fluff density, appearance and feel. It is particularly preferable because it is excellent. In addition, if necessary, a polyvinyl alcohol-based sizing agent is applied to the nonwoven fabric manufactured by the above method, or the surface of the constituent fibers is melted to bond the nonwoven fabric constituent fibers together, thereby temporarily fixing the nonwoven fabric. May be performed. By performing this treatment, it is possible to prevent the nonwoven fabric from being structurally destroyed by tension or the like in the subsequent step of impregnating the elastic polymer solution or the like.

The compound represented by the structural formula (1) is contained in the molecular chain of the polyester so that the aliphatic cyclic skeleton of the compound is positioned as a side chain with respect to the molecular chain. Therefore, even if the content of the compound is low, the non-crystallinity increases and the exhaustion ability of the dye increases. In addition, the lowering of the secondary transition point temperature is suppressed, and when the fiber shrinks due to heat, the stress at the time of relaxation inside the fiber accumulates, so that the original fabric is highly shrunk, and the appearance is improved by increasing the fuzz density I do. Moreover, it becomes an artificial leather having excellent strength, color fastness and light fastness.

Next, the cloth is impregnated with an elastic polymer liquid,
Gel is formed by heating and drying, or immersed in a liquid containing a non-solvent of the elastic polymer and wet-solidified to form a dense foamed sponge of the elastic polymer. As the elastic polymer to be impregnated here, for example, an average molecular weight of 500 to 30
00 polyester diol, polyether diol,
At least one polymer diol selected from diols such as polycarbonate diols or complex diols such as polyester polyether diol;
At least one diisocyanate selected from aromatic and alicyclic diisocyanates such as 4'-diphenylmethane diisoanate, isophorone diisoanate, and hexamethylene diisoanate; Polyurethanes obtained by reacting at least one kind of low molecular compound having at least one active hydrogen atom with at least a predetermined molar ratio and modified products thereof are listed. In addition, polyester elastomers, styrene-isoprene block copolymers An elastic polymer such as a hydrogenated product and a resin such as an acrylic resin may also be used. Further, a polymer composition obtained by mixing these may be used. However, the above polyurethane is preferably used in view of flexibility, elastic recovery, sponge forming property, durability and the like.

A cloth is impregnated with a polymer solution obtained by dissolving or dispersing the above polymer in a solvent or dispersant and treated with a non-solvent of a resin to form a sponge by wet coagulation, or heat drying as it is Then, a fiber sheet is obtained by a method of gelling to form a sponge. If necessary, additives such as a colorant, a coagulation regulator, an antioxidant, and a dispersant may be added to the polymer liquid. The ratio of the elastic polymer in the fiber sheet after the removal of the sea component is 10% or more, preferably 30 to 50% by weight as a solid content. When the elastic body ratio is less than 10%, a dense elastic sponge is not formed, and the fine fibers are likely to be pulled out after the generation of the fine fibers.

Next, the fiber sheet containing the elastic polymer is treated with a chemical which is a non-solvent for the copolyester and the elastic polymer as the microfiber components and a solvent or a decomposer for the other polymer component of the conjugate fiber. An ultrafine fiber bundle is generated by the removal treatment. In the present invention, the fineness of the ultrafine fiber formed by removing the sea component from the sea-island structural fiber is preferably 0.5 to 0.0001 denier, particularly preferably 0.25 to 0.01 denier, And is preferred in that a suede-like nap having excellent durability in long-term wearing can be obtained.

The leather-like sheet of the present invention can give a suede-like artificial leather by fluffing the surface. As a method of shaving, buffing using sandpaper, needle cloth, or the like can be used. The leather-like sheet material of the present invention can be easily dyed in a usual dyeing step of a disperse dye or a cationic paint, and is reduced and washed.
One-bath one-stage method, one-bath two-stage method, two-bath one-stage method may be used, but in the case of one bath, it is necessary to use an appropriate dispersant so that the disperse dye and the cationic dye do not aggregate. There is. The present invention, by using a disperse dye and a cationic dye in combination, can not be expressed by a conventional dye dyed only with a disperse dye or a dye dyed only with a cationic dye. A leather-like sheet having excellent dyeability is obtained. Such a leather-like sheet material can be used for not only miscellaneous goods such as shoes, bags, and accessories, but also for interior goods such as sofa covering materials and clothing.

[0037]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
In the examples, "parts" and "%" relate to weight unless otherwise specified. [Content (mol%) of compound represented by structural formula 1] 1H of polyester using deuterated trifluoroacetic acid as a solvent
-Calculated based on NMR measurement results. [Melting point, glass transition temperature, crystallinity of polyester] D
Using a SC (TA3000, Perkin Elmer), measurement was performed under a nitrogen atmosphere at a temperature of 10 ° C./min with a sample of 10 mg. [Density] The average value of the weights of five test pieces cut into 15 cm squares according to JIS L-1906 was calculated using the area (0.01 m
Divided by ² ). [Strength and elongation] Width 25 according to JIS L-1906
The test piece of mm was cut out from the MD direction and the CD direction, the strong elongation was obtained, and the average value in the MD direction and the CD direction was used. [Measurement of L *] CIE197 according to JIS 8722
L * of the 6L * a * b * system was measured using a Hitachi 307 color analyzer (automatic recording type spectrophotometer: manufactured by Hitachi, Ltd.). The smaller the value of L * is, the darker it is, and it is an index of the color development and deep color of the black dye. [Measurement of K / S] The spectral reflectance (R) was measured using a color analyzer (automatic recording type spectrophotometer, Model C-2000, manufactured by Hitachi, Ltd.), and the following equation (Kubelka-Mu) was obtained.
nk). The greater this value, the greater the deep chromaticity. K / S = (1−R) ² / 2R (R is the reflectance at the position of the maximum absorption wavelength in the reflectance curve of the visible portion of the sample.) [Light fastness] Light fast carbon fade according to JIS L-0842, The evaluation was performed under the condition of a black panel temperature of 63 ° C. [Fastness of friction] It was evaluated in a wet state according to JIS L-0801. [Dyeing ratio] The dye solution before and after dyeing was diluted with a mixed solvent of acetone / water (volume ratio 1/1), and the absorbance of the diluted solution was measured to calculate by the following formula. Dyeing ratio (%) = {(DC) / C} × 100 C: Absorbance at maximum absorption wavelength after dyeing of dye solution D: Absorbance at maximum absorption wavelength before dyeing of dye solution

Reference Examples 1 to 11 A slurry comprising the compounds shown in Table 1, a sulfonic acid group-containing dicarboxylic acid, terephthalic acid, and ethylene glycol was heated under pressure (2.5 kg / cm ² absolute pressure) at a temperature of 250.
The esterification reaction was carried out at 90 ° C. until the esterification ratio reached 95% to produce a low polymer. Next, 350 pp as a catalyst
m of antimony oxide was added, and the low polymer was polycondensed at 280 ° C. for 1.5 hours under a reduced pressure of 1 torr to obtain a polyester having an intrinsic viscosity of 0.70 dl / g. This polyester was extruded from a nozzle into a strand and cut to obtain a cylindrical chip having a diameter of 2.8 mm and a length of 3.2 mm.

[0039]

【table 1】

Examples 1-6, Comparative Examples 1-5 28 islands using the polyester (island component) obtained in Reference Examples 1-11 and high-flow low-density polyethylene (sea component, Mitsui Chemicals Mirason FL60). A sea-island composite spun fiber (sea-island ratio of 2: 1) was obtained by a melt spinning method, stretched 2.5 times in 70 ° C. warm water, mechanically crimped and dried, and then dried for 51 m.
The staples were cut into m, staples were formed, and a web having a basis weight of 500 g / m ² was formed by a cross lap method. Then, needle punching of 2450 p / cm ² was performed alternately from both sides. After shrinking in hot water at 95 ° C., the mixture was pressed with a calender roll to form an entangled nonwoven fabric having a smooth surface. The basis weight of this entangled nonwoven fabric is 520
g / m ² and apparent specific gravity was 0.34. The entangled nonwoven fabric is impregnated with a solution of polyurethane in a dimethylformamide (abbreviated as DMF) having a solid content of 12% mainly composed of polytetramethylene ether-based polyurethane, immersed in a DMF / water mixture, and wet-solidified. The sea component in the conjugate spun fiber was eluted and removed in hot toluene to develop an ultrafine fiber bundle, and a fiber sheet having a thickness of 1.5 mm was obtained. The average denier of the ultrafine fibers (determined by dividing the total cross-sectional area of the ultrafine fibers present in one fiber bundle by the number thereof) was 0.20 denier. The weight ratio of polyurethane in the fiber sheet is 3
5%. This fiber sheet was sliced into two pieces, and then buffed and raised. This was dyed with a disperse dye (black) under the conditions shown below, and then reduced and washed. Dyeing; Composition of dye solution Cationic dye: Diacryl Black BSL-F (Dystar Japan) 8% ow f Disperse dye: Kayalon Polyester Black G-SF (Nippon Kayaku) 25% ow f Aggregation / precipitation inhibitor: Meisanol CW Chemical industry) 3% owf acetic acid 0.5 cc / L sodium acetate 1.0 g / L sodium sulfate 1.0 g / L bath ratio 50: 1 temperature × time 120 ° C. × 40 minutes reduction washing; ammonia water 1 cc / L amylazine D 1 g / L Sodium hydrosulfite 1g / L Temperature x time 70 ° C x 20 minutes

The obtained suede-like artificial leather had a high-class appearance, was a dark black color, and had excellent light fastness and friction fastness. Table 2 shows the results. This is probably because the dyeing seat is different between the disperse dye and the cationic dye. However, a suede-like artificial leather having a deeper color and a higher quality than that obtained by dyeing only with the disperse dye or only with the disperse dye was obtained. The polymer of Reference Example 9 could not be thread-produced and no suede was obtained. In Reference Example 11, the melt viscosity was too high to allow the polymer to come out of the nozzle, and no suede was obtained.

[0042]

[Table 2]

Examples 7 to 11 and Comparative Examples 6 to 12 Artificial leathers were obtained in exactly the same manner as in Example 2 and Comparative Example 2, except that the concentrations of the disperse dye and the cationic dye were changed as shown in Table 3. Tricyclodecane dimethanol (TC
When the content of the (DDM) component is less than 1 mol%, the amount of disperse dye absorbed is small, so that even if the concentration of the disperse dye is increased, the dyeing rate does not increase, and thus L * does not decrease. Further, when the disperse dye and the cationic dye are used in combination, the L * becomes lower and the color becomes deeper as compared with the case of using the disperse dye alone or the cationic dye alone.

[0044]

[Table 3]

Example 12 and Comparative Example 13 The polyester obtained in Reference Examples 2 and 10 was used as an island component, and polystyrene was used as a sea component (sea-island ratio of 2: 1) to produce 28 islands-island composite fibers. Yarn about 4.0dr / f, island fineness about 0.25d
r / f), and cut to 51 mm after giving the opportunity crimp. The raw cotton was formed into a sheet-like web using a roller card and sufficiently needle-punched (2000 P / cm ² ). This was introduced into a hot solution of polyvinyl alcohol (20%), glued simultaneously with shrinkage (plasticization), and further dried. Thereafter, it was introduced into trichlorethylene to give a polyurethane. Coagulation of polyurethane and removal of polyvinyl alcohol in a water-DMF bath, and after drying, slicing,
Next, it was buffed and raised. Dyeing was carried out in exactly the same manner as in Example 1 except that the dye was changed to the following red dye to obtain a suede-like artificial leather. The obtained artificial leather was luxurious, vivid and deep red, and had sufficient fastness. (Table 4) Disperse dye: Dianix Red G-SE (Mitsubishi Kasei Co., Ltd.) 25% ow f Cationic dye: Catilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.) 8% owf

[0046]

[Table 4]

[0047]

The polyester-like leather-like sheet of the present invention has a high dyeing rate with respect to a disperse dye, can absorb more dye than conventional artificial leather made of polyester, and has a high disperse dye. Since it also dyes cationic dyes with different dyeing seats, it is possible to provide a high-quality suede-like artificial leather having a dark and vivid color and having excellent fastness.

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Claims (1)

[Claims] 1. A leather-like sheet obtained by impregnating an elastic polymer with a base fabric containing polyester fibers having a single fiber fineness of 0.5 denier or less, wherein the polyester fibers have a compound having the following structural formula (1). A leather-like sheet comprising a polyester obtained by copolymerizing 1 to 10 mol% and a sulfonic acid group-containing compound at 1 to 5 mol%, and wherein the fibers are dyed with a disperse dye and a cationic dye. Stuff. [Formula 1] (Wherein, R1 to R10 are groups selected from an ester-forming functional group, a hydrogen atom, and an alkyl group, and one or two of R1 to R10 are ester-forming functional groups.
x is 0 or 1, and y is an integer satisfying 1 ≦ x + y ≦ 3. )