JP2002020978A - Raising fabric and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a raising fabric freed from any organic solvent remaining after the artificial suede cloth production process by simplifying the production process and by controlling environmental pollution. SOLUTION: Raising woven or knitted fabric of polyester fiber with a single yarn fineness of <=0.35 dtex is impregnated with a water-based polyurethane emulsion to give the objective woven or knitted fabric impregnated with polyurethane resin, in which no residual organic solvent is detected according to the GC-MS analysis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brushed fabric suitable for interior furniture such as clothing and upholstery, interior materials for vehicles, shoe outerwear, bag outerwear, bags, miscellaneous goods and the like. Because it is not used in the processing step, the drug does not remain even in the fabric, and it responds to recent topics such as sick house syndrome, non-formaldehyde conversion, non-organic solvent conversion, and is formed of woven or knitted fabric The present invention relates to a suede-like raised fabric which is easy to lose its shape and excellent in shape retention and is friendly to a living environment.

[0002]

2. Description of the Related Art Brushed fabrics made of polyester fibers,
In particular, in the field of products called artificial suede, short-fiber nonwoven fabrics and long-fiber nonwoven fabrics, which are basically two-dimensional structures having no directionality, exist as base fabrics, and after raising the nonwoven fabric, polyurethane resin Impregnated with resin or acrylic resin, etc., and used as a laminated structure by physical treatment such as resin bonding or needle punching with other woven or knitted fabric to maintain strength, for chair covering use etc., or as it is for miscellaneous goods use To serve. Many base fabrics are made of microfiber-forming fibers, and have a cross-sectional shape in which polymers that are incompatible with each other are radially or multi-layered by composite spinning, or multiple types of melting are performed using static kneading elements. After dispersing the polymer in a dispersed state to form fibers and forming a two-dimensional structure, it is necessary to use an organic solvent to dissolve one or swell one to split and ultrafine. However, in the above method, the process of making the fibers ultrafine is indispensable, and since the wastewater from the factory contains a large amount of the organic solvent, the burden on the environment is large. Is also not preferred.

[0003] As a special spinning method, a non-woven fabric by a flash spinning method in which a polymer is discharged in the presence of a solvent to make it ultrafine or a melt-blowing method in which a molten polymer is explosively discharged by using a high-pressure gas to make it ultrafine are widely used. But
The former has a problem of residual organic solvent due to the use of a polymer solvent, and the latter can obtain fibers in a region called ultra-fine fibers, but cannot obtain a dark color even by dyeing, There is a problem that color development is difficult.

When a suede-like raised fabric is obtained, a brushing treatment is generally performed after impregnating a base material with a polyurethane resin. However, when the polyurethane resin is applied, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like are used in a wet formulation. Although a method using a polar organic solvent such as the above is generally used and the texture and swelling are finished to a satisfactory level, it is not preferable in consideration of the waste solvent in the factory and the solvent remaining in the cloth. In the dry formula, volatile organic solvents having a low boiling point, such as toluene, xylene, acetone, and methyl ethyl ketone, are generally used. There is a high possibility that the solvent will remain.

[0005] As described above, non-woven fabrics based on spunbonding, meltblowing, flash spinning, etc. are mainly used for the base fabric, and are characterized by low production costs, quick delivery, and no directivity in mechanical properties. There is
Since the two-dimensional structure is formed by entanglement of the single fibers, the tear strength is moderate but the elongation is poor, and residual strain tends to occur. Further, it has poor drapability, and is particularly unsuitable for applications requiring a beautiful silhouette on a curved surface or a sewn portion, such as an upholstery application, a general clothing application, or an application that easily loses its shape.

[0006]

A solvent or dispersant used for impregnating a woven or knitted fabric structure with a polyurethane resin in consideration of simplification of an artificial leather manufacturing process, prevention of environmental pollution, and product safety. Was changed from water to water from organic solvent system, and conventionally, organic solvent having fiber dissolving ability or swelling ability was used at the time of ultra-fine fiberization, but in the manufacturing process by making continuous fiber by direct melt spinning method To prevent pollution. Another object of the present invention is to provide a brushed fabric which is excellent in strength and visual by changing the two-dimensional structure serving as a base fabric from a conventional nonwoven fabric to a woven or knitted fabric.

[0007]

Means for Solving the Problems The invention according to the substance of the present invention is a brushed fabric comprising a polyurethane resin-impregnated woven or knitted fabric in which no residual organic solvent is observed by GC-MS analysis. More specifically, it contains 5 to 30% by weight of a polyurethane resin and has at least one selected from benzotriazine, benzotriazole, benzophenol, benzophenone and derivatives thereof.
The brushed fabric or woven or knitted fabric according to the above, wherein the UV absorbent comprises 1 to 5% by weight of a seed fiber.
In the above-mentioned raised fabric and woven / knitted fabric, the aromatic-based, aliphatic-based and alicyclic-based organic solvents and other polar organic solvents do not remain. The above-mentioned raised fabric and polyester fiber, wherein the raised fabric and polyester fiber are multifilament false twisted yarns. The brushed fabric described above, wherein the polyester fiber having a single yarn fineness of 0.23 decitex or less becomes fluffy fluff and is exposed on the surface of the fabric, and the elongation recovery rate specified by JIS L-1096 A method. Is 80% or more and the residual strain rate is 15% or less, and the ratio of the elastic component to the hysteresis component (2HB / B) in bending deformation measured by a KES hand feeling evaluation system (2HB / B), and The raised fabric according to the above, wherein the bending length (√ (2HB / W)) is in the following range. (2HB / B) ≦ 1.0 √ (2HB / W) ≦ 3.0 The invention according to the production method of the present invention also comprises a step of weaving and knitting using at least a part of polyester fiber to form a fabric, and then dyeing. And then raising the surface of the fabric, impregnating it with an aqueous polyurethane emulsion substantially free of an organic solvent, and further raising the surface of the fabric. Specifically, the aqueous polyurethane emulsion is impregnated with a dry method using padding mangles or slit mangles, and then 100%.
The above-mentioned method for producing a brushed fabric, wherein the polyester fiber is a polyester multifilament false twisted yarn having a single-fiber fineness of 0.35 dtex or less, which is subjected to a drying treatment at ~ 130 ° C. A method for producing a brushed fabric, wherein an ultraviolet absorbent comprising at least one selected from benzotriazine, benzotriazole, benzophenol, benzophenone and derivatives thereof is applied to the woven or knitted fabric by an exhaustion method of 1 to 5% by weight. The above-mentioned method for producing a raised fabric, the method for producing a raised fabric according to the above, wherein the ultraviolet absorbent is dyed and exhausted in the same bath, wherein the cloth is a woven fabric, and a needle of the woven fabric. The method is characterized by cutting and raising single filaments of multifilament yarn, which mainly constitutes the weft, to form fluffy fluff on the fabric surface. Method of manufacturing a raised fabric described above to a water-based polyurethane emulsion was impregnated into woven or knitted fabric, after drying under 30 to 50 ° C. Environment 24-72
The method for producing a raised fabric according to the above, wherein the aging treatment is performed for a long time.

The most important feature of the brushed fabric according to the present invention is that although it is a woven or knitted fabric impregnated with a polyurethane resin, it is GC-M.
This is a fabric where no residual organic solvent is observed by the S analysis method. That is, in the conventional, polyurethane resin-impregnated raised fabric, a method using a polar organic solvent such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide is generally used in the wet formulation as described above, and the texture and swelling are preferable. Finishing is not preferable in consideration of factory waste liquid and solvent remaining in the fabric. In addition, low-boiling volatile organic solvents such as toluene, xylene, acetone, and methyl ethyl ketone are generally used in dry formulations, but this formulation also impairs the working environment of factories and has a large impact on ecosystems. In addition, the organic solvent remains in the cloth, and there is a concern about the influence on the human body. Furthermore, in the case of a so-called suede fabric using ultrafine fibers, a method of eluting or splitting a multicomponent conjugate fiber and making it ultrafine is dominant. However, in such a method, an ultrafine fiber process is indispensable, and since a large amount of the organic solvent is contained in the factory waste liquid, the burden on the environment is large. Is also not preferred. On the other hand, the raised fabric according to the present invention has no residual organic solvent, and the above problems have been solved at once by adopting a novel production method described later. In the present invention, "the residual organic solvent is not recognized by the GC-MS analysis" means that the fragment ion peak and the molecular ion peak of the organic solvent are not detected by the following GC-MS analysis, The amount is less than 5 ppm. The GC-MS analysis method uses a Curie point headspace sampler (JHS-100 manufactured by Nippon Kagaku Kogyo Co., Ltd.).
Of two measurement samples (brushed fabric) sampled in a 1 cm × 3 cm square using a purging and trapping method.
After a heating trap of 10 ° C. × 10 minutes, G
Each fraction separated by GC after being subjected to CMS was introduced into MS, and the structure of the compound was analyzed from the fragment ion peak, molecular ion peak, and the like using the obtained mass spectrum. GC-MS is HP-597 manufactured by Hewlett-Packard Company.
Using 3, the qualitative analysis sensitivity is set to 5 ng and the quantitative analysis sensitivity is set to 0.01 ppm for evaluation.

The fibers used in the raised fabric of the present invention are desirably polyester multifilament yarns, which are obtained by a usual melt spinning method, and are single fibers having a single yarn fineness of 0.35 dtex or less without using a composite spinning method. A fineness obtained by direct spinning is recommended. The polyester used is not particularly limited, but is preferably a polymer having ethylene terephthalate as a main repeating unit and an intrinsic viscosity [η] of 0.45 to 0.70. If necessary, titanium dioxide,
Inorganic fine particles such as barium sulfate and silicon dioxide may be contained. Of course, the cross-sectional shape is not limited, and in addition to a round cross-section, a polygonal cross-section, a flat cross-section,
A hollow cross section, other irregular cross sections, etc., may be used in an appropriate combination depending on the application and use.

[0010] Among the polyester multifilament yarns constituting the brushed fabric of the present invention, fibers having a single yarn fineness of 0.35 dtex or less are 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight of the brushed fabric. % Is desirable. If the proportion of fibers having a single yarn fineness of 0.35 dtex or less is less than 50% by weight, the fluffy fluff cannot sufficiently cover the fabric surface even during brushing or brushing, and the texture of the woven or knitted fabric becomes conspicuous. Sisters,
It is difficult to finish the appearance desirable. The upper limit is not particularly limited, but if the fiber having a single yarn fineness of 0.35 dtex or less is 90% by weight or more, the physical strength of the brushed fabric cannot be sufficiently maintained. It is desirable to keep to the extent.

In order to obtain the raised fabric of the present invention, it is desirable that the hair-growing fluff mainly forming the surface of the fabric has a smaller fineness in terms of appearance and quality, and a single-fiber fineness of 0.35 dtex or less, more preferably It is desirable that the fineness of the single yarn be 0.23 decitex or less. The lower limit of the single-filament fineness is not particularly limited. However, in order to obtain ultrafine fibers without any chemical treatment, the direct melt spinning is limited to about 0.12 decitex, and the finer than this value is required. Those with fineness are difficult to stably discharge and stretch stably. Therefore, the single fiber fineness is 0.12 to 0.35 dtex, more preferably 0.12 to 0.2 dtex.
3 dtex or less is preferably used.

When the polyester multifilament yarn directly melt-spun is subjected to weaving and knitting as a false twisted yarn, the sensation of turbulence peculiar to raw yarn is suppressed.
It is desirable that at least a part of the 5-decite filament is false twisted. The false twisting method is not particularly limited, and can be carried out using a commercially available model such as a belt false twister, a friction disk false twister, and a pin false twister. The weaving and knitting is not particularly limited to a model, and can be carried out by using a known model.

The polyurethane resin used in the brushed fabric of the present invention is not particularly limited, but is preferably a diisocyanate such as an aliphatic diisocyanate or an alicyclic diisocyanate, and a polyisocyanate such as polytetramethylene glycol or polypropylene glycol. A polymer obtained by polymerizing a glycol and an aliphatic diamine is exemplified.

The ultraviolet absorber used in the present invention is to absorb at least one selected from benzotriazine, benzotriazole, benzophenol, benzophenone and their derivatives into the fiber in the same step as the dyeing. It is desirable that the compound is a low-molecular compound having the ability to absorb light energy of 400 nm or less and convert it to heat energy or the like. By containing 1 to 5% by weight of an ultraviolet absorber in a fabric, deterioration of light fastness is suppressed even in dispersion dyeing of polyester ultrafine yarn, and the fabric does not fade or discolor even when exposed to ultraviolet light for a long time in a high temperature environment. It is possible. If the content of the ultraviolet absorbent exceeds 5%, it is difficult to apply even the above low molecular weight compounds by the exhaustion method, and it is necessary to perform melt spinning in a state where the compound is kneaded in advance in a polymer. However, the spinning condition is unfavorably impaired. On the other hand, if the content of the ultraviolet absorber is less than 1% by weight, the above-mentioned light fastness is not satisfactory, causing color fading and discoloration.

After weaving and knitting the base fabric for obtaining the raised fabric of the present invention, scouring, relaxing and dyeing treatments are performed by known methods. Dyeing is carried out under a high pressure condition of 130 ° C. or more in order to exhaust the disperse dye and the ultraviolet absorber. There is no particular limitation on the machine used in the dyeing process, but the use of a jet dyeing machine is particularly desirable. After dyeing, carry out reduction washing with sodium hydroxide and thiourea dioxide to remove excess disperse dye and UV absorber, hot water washing, acid neutralization, water washing, and then charge by padding dry method An inhibitor, a leveling agent and the like are provided. The application of the antistatic agent and the smoothing agent contributes to the stabilization of the process of the next step of raising the needle cloth, and without the chemical treatment, the cloth releasability is extremely deteriorated and the brush is uniformly raised. Becomes difficult.

The cloth which has been subjected to the raising treatment and the shearing is set in an expanded state using a heat setter, and the rough cloth is removed, the texture is corrected, and the width is adjusted. After the base fabric is applied with the aqueous polyurethane emulsion by slit mangle or padding mangle, the temperature is 100 ° C or more and 130 ° C or more.
Dry at a temperature below ℃. The drying temperature needs to be 130 ° C. or less, preferably 120 ° C. or less, in consideration of dye transfer and sublimation to the polyurethane resin. In terms of drying efficiency, it is desirable to perform the treatment at a high temperature in a short time, but drying in a region exceeding 130 ° C. is undesirable because the transfer and sublimation of the disperse dye becomes extremely poor, and a low-temperature treatment of less than 100 ° C. If a long processing time is required, a commercial process speed cannot be obtained. The brushed fabric after drying the polyurethane resin is once wound up in a roll shape. In order to promote the intermolecular crosslinking of the polyurethane resin and to maintain the strength of the obtained brushed fabric, the brushed fabric is heated at 30 to 50 ° C. in an environment of 30 to 50 ° C. More preferably, the aging treatment is performed for 72 hours.

The solid content ratio of the polyurethane resin to the brushed fabric of the present invention is preferably in the range of 5% by weight to 30% by weight, more preferably in the range of 10% by weight to 20% by weight. The aqueous polyurethane emulsion is applied in an appropriate amount to the base fabric by the above-mentioned mangle. However, if the resin solid content is less than 5% by weight, a proper flesh feeling and sufficient strength cannot be maintained, and the amount exceeds 30% by weight. If the resin concentration is not increased in the range, the resin cannot be provided by mangle. If the resin concentration is increased, the water-based polyurethane emulsion will thicken and cannot be uniformly applied to the base fabric. It does not penetrate into the interior, and the brushed fabric is peeled off and can be finished only with a feeling of stiffness. The aqueous polyurethane emulsion liquid can contain an appropriate amount of an antistatic agent, an antifoaming agent, or the like, if necessary. In this case, it is necessary to select and adjust a drug and an applied amount which do not cause gumming up of the liquid, and naturally consider the stability of the emulsion liquid.

After the resin is impregnated into the base fabric and subjected to a drying treatment, the surface of the fabric is ground using a sanding machine or the like to form a large number of dense hair-like fluffs. In order to remove it, the same reduction washing as after dyeing is performed. Thereafter, if necessary, a water repellent, an antistatic agent and the like are applied by a padding dry method.
The finishing set is performed in a temperature range of 140 ° C. or less. Regarding the finishing set, considering the prevention of migration and sublimation to the polyurethane resin and the productivity, the treatment in the above range is desirable. In the range exceeding 140 ° C., the above-described migration sublimation fastness becomes extremely poor, and the range of less than 100 ° C. Although there is no problem in the transfer sublimation fastness, the processing time becomes extremely long, which is not desirable in view of productivity.

The brushed fabric of the present invention is characterized in that the base fabric made of a woven or knitted fabric is used for impregnating a polyurethane resin, so that the hysteresis curve of the fabric is completely different from that of a conventional brushed fabric made of a nonwoven base. It has rich drapability and flexibility compared to conventional products. The bending characteristics are evaluated using a KES-FB2 system.

The bending return property (2HB / B) is obtained from hysteresis (2HB) and rigidity (B) obtained from a hysteresis curve in bending characteristics.
This value is regarded as residual strain in the process of recovery deformation from bending deformation, and the smaller the residual strain, that is, the smaller the characteristic value of the reversion property (2HB / B), the better the rebound.
It is said that the shape and wrinkles hardly occur. Nonwoven fabric-based brushed fabrics are susceptible to sagging due to the brushing process, and have a property of bending back (2
The characteristic value of HB / B) is larger than that of the woven or knitted fabric base, resulting in poor rebound. In order to give the feeling and strength to the nonwoven fabric, it is necessary to make a structure called a scrim laminated with other woven or knitted fabric, or to back up other woven or knitted fabric with resin, for applications requiring strength such as chair upholstery It is difficult to use it alone. From the above viewpoint, it is desirable that the bending return property (2HB / B) value is 1.0 or less, more preferably 0.8 or less.

3 (B / W) and √ (2HB / W)
Is described as a function of the hanging form of the cloth modeled on the bending state of the cantilever. In particular, the larger the value of √ (2HB / W), the more unstable the drape form, and the movement of the cloth when it operates. Is said to lack liveliness. Since the nonwoven fabric-based raised fabric has a slightly larger value of √ (2HB / W) than the woven or knitted fabric base, the woven or knitted fabric is suitable from the viewpoints of drapability, hangability, liveliness, tailoring and the like. √ (2HB / W) is referred to as unbending length, and the numerical value is 3.0 or less, more preferably 2.5 or less.
The following ranges are desirable from the above viewpoint. Here, W represents the weight per unit area (g / cm ² ) of the raised fabric.

As described above, since the stretchability of the brushed fabric is a nonwoven fabric-based fabric, since the two-dimensional structure is formed by entanglement of the single fibers, the entangled state is likely to be displaced by the elongation. Even when impregnated with the polyurethane resin, the elongation recovery rate remains low and the residual strain becomes large. In the present invention, in consideration of the above, since the base fabric is a woven or knitted fabric, the degree of misalignment is small due to the effect of the texture point or the loop of the yarn, and the elongation recovery property is significantly improved in comparison with the nonwoven fabric, and the residual The distortion is also mild. The elongation recovery rate and the residual strain rate are measured by the JIS L-1096 A method, and when the elongation recovery rate is 80% or more, more preferably 85% or more, and still more preferably 90% or more, excellent performance is obtained. It can be a brushed fabric. The residual strain rate is 1
By setting the content to 5% or less, more preferably 10% or less, the set in continuous use is reduced, which is preferable.

The brushed fabric of the present invention is suitably used for upholstery applications, car interior materials such as car seats, shoe outerwear, bag outerwear, bags, and other miscellaneous goods. The water repellent may be applied simultaneously with the aqueous polyurethane emulsion liquid treatment or in any step after the treatment.

[0024]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the following embodiments. The physical property values and experimental values in the examples and the text are values obtained by the following methods.

(Fastness of Dyeing) (Fastness to Friction) 1996 JIS L 0849
The friction fastness (discoloration, stain) of each of the dry sample and the wet sample was evaluated using a friction tester type II (Gakushin type) described in (1). (Dyeing fastness to ultraviolet carbon arc lamp light) 1
According to the method described in JIS L 0842 in the 996 edition, the temperature of the black panel thermometer was set to 83 ± 3 ° C., and the evaluation (discoloration) was performed by exposure for 300 hours. (Robustness against sublimation during storage) 1975 edition JIS L
The evaluation was performed using a sweat tester according to the 0854 method.

(Wear strength) JIS L10, 1999 edition
The wear strength was evaluated according to the 96 E method (Martindale method). The pressing load is 12.0 ± 0.3 for furniture use.
kPa was adopted. (Tear Strength) In accordance with JIS L 1096 D method (Pendulum method), 1999 version, measured values were derived and evaluated based on an average value of five experiments.

(Bending characteristics) KES-FB manufactured by Kato Tech
System (Kawabata's evaluatio)
Using n system for fabric), measurement and evaluation were performed in an environment of a temperature condition of 20 ° C. ± 0.5 ° C. and a humidity condition of 65 ± 0.5% RH. The data for measurement is 2 before measurement.
After the temperature and humidity were sufficiently adjusted in the above environment for 4 hours, the samples were subjected to measurement.

(Sewability test (break of ground thread)) Using a single-needle lockstitch sewing machine for industrial use, four fabrics are piled up, and the number of needles is 15 stitches / 3cm, the number of rotations is 3500 times / min, and the test length is 20cm. The number of yarn breaks was evaluated. Sewing thread is JIS version 2000
Polyester spun sewing thread # 60/3 specified by L-2511, needle used is 1998 version JIS B-90
DB × 1 KN # 11 designated at 76 was used.

(Elongation recovery rate and residual strain rate) 1999
The evaluation was performed according to the JIS L-1096 A method (repeated constant-speed constant elongation method) for the fiscal year.

(Polyurethane resin solid content weight ratio (mixing ratio))
It was measured based on JIS L-1030-2 (dissolution method, mixture of two types).

(Residual solvent analysis) Evaluation was performed by GC-MS analysis. Using a Curie Point Headspace Sampler (Model JHS-100, manufactured by Nippon Kagaku Kogyo Co., Ltd.), a heating trap of 80 ° C. for 10 minutes was carried out by a purge-and-trap method for two measurement samples (brushed fabric) taken in 1 cm × 3 cm square After that, the mixture was directly subjected to GCMS and each fraction separated by GC was introduced into MS, and the structure of the compound was analyzed from the fragment ion peak, molecular ion peak, and the like using the obtained mass spectrum. GC-MS was evaluated using HP-5973 manufactured by Hewlett-Packard Co., with the qualitative analysis sensitivity set to 5 ng and the quantitative analysis sensitivity set to 0.01 ppm.

Example 1 1.25 mol of polytetramethylene glycol having an average molecular weight of 2000 was mixed with 2.00 mol of dicyclohexylmethane diisocyanate.
Water was added while stirring using a homogenizer in the presence of methyl ethyl ketone as a solvent, and the emulsion was inverted from a water-in-oil type (W / O) to an oil-in-water type (O / W) to obtain a milky white emulsion. Thereafter, the emulsion was cooled to 35 ° C., and 0.75 mol of isophoroneamine (molar ratio to 2.00 mol of dicyclohexylmethane diisocyanate) was obtained.
A chain extension reaction was promoted while stirring a solution obtained by diluting 10 times with water to obtain a polyurethane aqueous emulsion, and methyl ethyl ketone as a solvent was completely removed from the reaction system by distillation under reduced pressure, and the solid component (nonvolatile content) was reduced to 40%. Was obtained.

Polyester multifilament semi-dull false twisted yarn 84 dtex 3 as a base material for raising
A polyester multifilament semi-dull false twisted yarn 167 with 6 filaments (false twist direction Z → S) as warp yarns
Three decitex 720 filaments (single yarn fineness: 0.22 decitex) (false twist direction Z → S) are aligned, and 200 turns / m real twist is inserted in the Z twist direction to form a triple yarn. In an air jet loom, the fabric was woven into a weft satin structure of 104 warps / in and 57 wefts / in. The weight ratio of fibers having a single-fiber fineness of 0.35 decitex or less in the entire greige was 75.2% by weight.

The obtained greige was subjected to scouring / relaxation treatment by a jet dyeing machine (uniace jet dyeing machine manufactured by Nissen), and then dyed at a dyeing temperature of 130 ° C. by a jet dyeing machine using the following dye recipe. Processing was performed. In the dyeing step, an ultraviolet absorber (a benzotriazole-based ultraviolet absorber manufactured by Nikka Kagaku (trade name: Sunlife LP-20)
0)) at 2% owf. Formulated by the exhaustion method. Dyes used (Sumitomo Chemical Disperse Dye UL Color 3 primary colors) Sumikalon UL Yellow 3RF 0.75% owf. Sumikalon UL Red RF 0.63% owf. Sumikalon UL Blue RF 1.35% owf. After the dyeing is completed, the dye solution is drained, and 0.5
A prescribed sodium hydroxide aqueous solution is injected at a liquid temperature of 20 ° C. ± 5 ° C., and after stirring for 5 minutes, an aqueous thiourea dioxide solution is injected into the system, and the mixture is stirred while being heated to 80 ° C. and reduced for 30 minutes. Washing was performed. After the waste liquid, washing with hot water, acid neutralization with an aqueous solution of acetic acid and washing with water were carried out, and after dehydration, a suitable amount of a brushing agent (trade name: Millinal FW-1) and an antistatic agent (trade name: Ellenon No. 20) manufactured by Meisei Chemical Company, Ltd. The solution was applied by padding mangle and dried at 120 ° C.

After that, using a Franz Mueller-type needle cloth napping machine manufactured by Nankai Tekko Co., Ltd., both sides of the woven fabric are brushed to expose fine hairs on the surface, and long cut fluffs are aligned by shearing.
The tent was set at 130 ° C. with a heat setter manufactured by Hirano Techseed to obtain a base fabric for polyurethane resin processing. Subsequently, a suitable amount of a softening agent, a water repellent, an antistatic agent and an antifoaming agent was prepared in the aqueous polyurethane emulsion obtained by the above-mentioned formulation, and the resultant was impregnated with the dough, followed by drying at 130 ° C. Polyurethane resin solid content weight ratio to polyurethane fabric base fabric is 12% by weight
Met. The brushed fabric after the impregnation and drying was subjected to an aging treatment in a 40 ° C. environment for 48 hours.

Next, the surface of the polyurethane-containing fabric is ground in a wet state by a combination of fine mesh and forward rotation using a wet gran prix machine manufactured by Sanwa Machinery Co., Ltd. to generate dense fuzz on the surface and to remove grinding debris. Similar to the reduction washing after the dyeing, the mixture is stirred for 5 minutes using a 0.5 N aqueous solution of sodium hydroxide (solution temperature: 20 ° C. ± 5 ° C.), and then stirred while increasing the temperature to 80 ° C. by adding a thiourea dioxide aqueous solution. Then, reduction washing was performed for 30 minutes. Thereafter, washing with hot water, acid neutralization with acetic acid, washing with water, and dehydration were performed, and drying was performed at 130 ° C. using a heat setter manufactured by Hirano Tecseed Co., Ltd., and the fabric surface was lightly brushed to finish.

The fur was completely covered on the surface of the woven fabric, and the finished fabric was a suede-like raised fabric having an elegant luster and moderate swelling. The finished brushed fabric has a cloth thickness of 0.1.
82 mm, basis weight is 281 g / m ² (0.0281 g /
cm ² ) and a single yarn fineness of 0.3 with respect to the entire raised fabric.
The weight ratio of fiber of 5 dtex or less is 67.2% by weight.
Met. The properties obtained are summarized in Table 1. GC-MS
As a result of residual solvent analysis by the method, no residual solvent was detected,
It has been confirmed that it can be sufficiently used for clothing and living materials. In the evaluation of the sewability, there was no breakage of the ground yarn, the processability was good, and the quality of the sewn portion was good.

(Example 2) Polyester multifilament semi-dull false twisted yarn 167 decitex 720 using polyester multifilament semi-dull false twisted yarn 84 decitex 36 filaments (false twist direction Z → S) as warp as base material for raising. The filament (single yarn fineness 0.22 decitex) (false twist direction Z → S) is given a real twist of 200 turns / m in the Z twist direction and used as a weft. 95 / in
Weaved in the Satsu organization. The weight ratio of fibers having a single yarn fineness of 0.35 dtex or less in the entire greige machine is 63.8.
% By weight. A brushed fabric was obtained in the same manner as in Example 1 except that the base fabric was changed. The weight ratio of the solid content of the polyurethane resin to the base fabric subjected to the polyurethane resin processing was 15% by weight.

In the same manner as in Example 1, a suede-like raised fabric having an elegant glossiness and a moderate swelling feeling was obtained by covering the surface of the fabric with fluffy fluff. The finished brushed fabric has a fabric thickness of 0.58 mm and a basis weight of 163 g / m ² (0.0163).
g / cm ² ), and the weight ratio of fibers having a single yarn fineness of 0.35 dtex or less to the whole raised fabric is 55.5.
% By weight. Table 1 summarizes the obtained physical property values. As in Example 1, no residual solvent was detected as a result of the analysis of the residual solvent by the GC-MS method, and it was confirmed that the residual solvent could sufficiently be used for clothing and living materials. In addition, there is no breakage in the sewability, and the processability is good,
Moreover, the quality of the sewn part was good.

Comparative Example 1 1.25 mol of polytetramethylene glycol having an average molecular weight of 2000 was mixed with 2.00 mol of dicyclohexylmethane diisocyanate.
While stirring with a homogenizer in the presence of methyl ethyl ketone as a solvent, the mixture was cooled to 35 ° C., and 0.75 mol of isophoroneamine (molar ratio to 2.00 mol of dicyclohexylmethane diisocyanate) was added to accelerate the chain extension reaction to promote the methyl ethyl ketone of polyurethane. A solution was obtained. The solid component (non-volatile content) in the solution is 40%.

As a base material for raising, a base material was prepared in the same manner as in Example 1, and a softener, a water repellent, and an antistatic agent were appropriately adjusted in the solution obtained by the above formulation, and impregnated with the material. After that, methyl ethyl ketone as a solvent was dried and removed under a temperature condition of 130 ° C. Methyl ethyl ketone released outside the system was recovered and reused as a solvent. The weight ratio of the solid content of the polyurethane resin to the base fabric subjected to the polyurethane resin processing was 14% by weight. The brushed fabric after impregnation and drying was subjected to an aging treatment at 40 ° C. for 48 hours in order to promote intermolecular crosslinking.

Then, the surface of the polyurethane-containing fabric is ground in a wet state by a combination of fine mesh and normal rotation using a wet gran prix machine manufactured by Sanwa Machinery Co., Ltd. to generate dense fuzz on the surface and to remove grinding debris. Similar to the reduction washing after the dyeing, the mixture is stirred for 5 minutes using a 0.5 N aqueous solution of sodium hydroxide (solution temperature: 20 ° C. ± 5 ° C.), and then stirred while increasing the temperature to 80 ° C. by adding a thiourea dioxide aqueous solution. Then, reduction washing was performed for 30 minutes. Thereafter, washing with hot water, acid neutralization with acetic acid, washing with water, and dehydration were performed, and drying was performed at 130 ° C. using a heat setter manufactured by Hirano Tecseed Co., Ltd., and the fabric surface was lightly brushed to finish.

The fur was covered on the surface of the woven fabric, giving a suede-like raised fabric having an elegant luster and swelling.
The finished brushed fabric has a fabric thickness of 0.76 mm, a basis weight of 273 g / m ² (0.0273 g / cm ² ), and a weight ratio of fibers having a single yarn fineness of 0.35 decitex or less to the whole raised fabric. It was 66.0% by weight. The properties obtained are summarized in Table 1. As a result of analysis of the residual solvent by the GC-MS method, it was confirmed that methyl ethyl ketone remained as a residual solvent, which was not suitable for use in clothing or living materials. Became inferior. Regarding the sewability evaluation, there was no breakage of the ground yarn, the processability was good, and the quality of the sewn portion was good.

Example 3 A padding mangle was used to adjust the amount of the aqueous polyurethane emulsion to be applied and to change the polyurethane resin solid content weight ratio to the polyurethane resin-treated base fabric to 3% by weight. Example 1 A brushed fabric was obtained in the same manner. Although hair growth covered the surface of the woven fabric, it was thin and did not give a feeling of swelling, and the strength was insufficient unless a laminated structure such as a backing or scrim was used. Finished brushed fabric thickness is 0.60m
m, basis weight is 200 g / m ² (0.0200 g / cm ² )
The weight ratio of fibers having a single yarn fineness of 0.35 dtex or less to the whole raised fabric was 72.8% by weight. The properties obtained are summarized in Table 1. As a result of the analysis of the residual solvent by the GC-MS method, no residual solvent was detected, but the physical properties such as tear strength were not sufficient, and it was difficult to say that it was suitable for use as a living material.
In addition, the sewability evaluation did not show ground yarn breakage, and the process passability was good, but the fabric was easily deformed in the bias direction, and the seams were not as clean as those in Examples 1 and 2. .

(Example 4) Polyester multifilament semi-dull false twisted yarn 167 decitex 288 using polyester multifilament semi-dull false twisted yarn 84 decitex 36 filament (false twist direction Z → S) as warp as base material for raising. Three filaments (single yarn fineness: 0.58 dtex) (tri-twist direction Z → S) are aligned, and real twist of 200 turns / m is inserted in the Z-twist direction to form a triple yarn. It was woven into a weft satin structure of 104 warps / in and 57 wefts / in in a jet loom. The weight ratio of fibers having a single yarn fineness of 0.35 dtex or less in the entire greige machine is 0% by weight. A brushed fabric was obtained in the same manner as in Example 1 except that the above greige was used. Since the single yarn fineness was rather large, the fluff was hardly in the form of downy hair, and had a luster that lacked a sense of luxury. Although the feeling of swelling was moderate, the surface roughness was conspicuous and was not desirable in appearance quality. The finished brushed fabric has a fabric thickness of 0.80 mm and a basis weight of 279 g / m ² (0.0279).
g / cm ² ), and the weight ratio of fibers having a single yarn fineness of 0.35 dtex or less to the whole raised fabric is 0% by weight.
It is. The properties obtained are summarized in Table 1. As a result of analysis of the residual solvent by the GC-MS method, no residual solvent was detected, and it was confirmed that the solvent could be sufficiently used for clothing and living materials. Regarding the sewability evaluation, there was no breakage of the ground thread, the processability was good, and the quality of the sewn portion was good.

Example 5 A brushed fabric was obtained in the same manner as in Example 1 except that in the dyeing step, dyeing was carried out without using an ultraviolet absorbent. The hair growth completely covered the surface of the woven fabric, giving a suede-like raised fabric having an elegant glossiness and a moderate swelling feeling. The finished brushed fabric has a fabric thickness of 0.81 mm and a basis weight of 282 g / m ² (0.02
82 g / cm ² ), and the weight ratio of fibers having a single yarn fineness of 0.35 dtex or less to the whole raised fabric is 67.
It was 2% by weight. The properties obtained are summarized in Table 1. G
As a result of the residual solvent analysis by the C-MS method, no residual solvent was detected, and it was confirmed that the residual solvent was sufficiently usable for clothing use. In the evaluation of the sewability, there was no breakage of the ground yarn, the processability was good, and the quality of the sewn portion was good. However, because it does not use an ultraviolet absorber, it has poor light fastness and fades, and there is a great concern about discoloration.
It has become difficult to develop such materials as vehicle interior materials, car seats, and clothing.

[0047]

[Table 1]

[0048]

According to the present invention, it is possible to simplify the process of producing an artificial suede and to prevent environmental pollution, and it is possible to finish the obtained raised fabric without any organic solvent.

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Claims (15)

[Claims] 1. A raised fabric comprising a polyurethane resin-impregnated woven or knitted fabric in which no residual organic solvent is observed by GC-MS analysis. 2. An ultraviolet absorbent containing 5 to 30% by weight of a polyurethane resin and comprising at least one ultraviolet absorber selected from benzotriazine, benzotriazole, benzophenol, benzophenone and derivatives thereof.
2. The raised fabric according to claim 1, comprising 5% by weight. 3. The raised fabric according to claim 1, wherein the woven or knitted fabric contains 50% by weight or more of polyester fibers having a single yarn fineness of 0.35 dtex or less. 4. The brushed fabric according to claim 1, wherein the woven or knitted fabric does not contain an aromatic, aliphatic, or alicyclic organic solvent and another polar organic solvent. 5. The raised fabric according to claim 3, wherein the polyester fiber is a multifilament false twisted yarn. 6. The raised fabric according to claim 1, wherein polyester fibers having a single yarn fineness of 0.23 decitex or less are exposed on the surface of the fabric as fluffy fluff. 7. The brushed fabric according to claim 1, wherein an elongation recovery rate specified by JIS L-1096 A method is 80% or more and a residual strain rate is 15% or less. 8. The ratio (2) of an elastic component and a hysteresis component in bending deformation measured by a KES texture evaluation system.
HB / B) and unbending length (√ (2HB /
2. The raised fabric according to claim 1, wherein W)) is in the following range. (2HB / B) ≦ 1.0√ (2HB / W) ≦ 3.0 9. A fabric obtained by weaving and knitting using at least a part of a polyester fiber to form a fabric, and then, after dyeing, raising the surface of the fabric and impregnating it with an aqueous polyurethane emulsion liquid containing substantially no organic solvent. And a method for producing a brushed fabric, further comprising raising the fabric surface. 10. The method for producing a brushed fabric according to claim 9, wherein the aqueous polyurethane emulsion is impregnated by a dry method using padding mangles or slit mangles, and then dried at 100 to 130 ° C. 11. The method for producing a brushed fabric according to claim 9, wherein the polyester fiber is a polyester multifilament false twisted yarn having a single yarn fineness of 0.35 dtex or less. 12. The woven or knitted fabric is provided with an ultraviolet absorber comprising at least one selected from benzotriazine, benzotriazole, benzophenol, benzophenone and derivatives thereof by a 1 to 5% by weight exhaustion method. The method for producing a raised fabric according to claim 9. 13. The method for producing a brushed fabric according to claim 12, wherein the ultraviolet absorbent is exhausted in the same bath as the dyeing. 14. The fabric is a woven fabric, and a multifilament yarn mainly constituting a weft is cut and raised by a single-thread raising of the woven fabric to form fluffy fluff on the surface of the fabric. A method for producing the brushed fabric according to the above. 15. The brushed fabric according to claim 9, wherein the woven or knitted fabric is impregnated with the aqueous polyurethane emulsion liquid, dried, and then subjected to an aging treatment in a 30 to 50 ° C. environment for 24 to 72 hours. Production method.