JP3226024B2 - Brushed artificial leather with high abrasion resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brushed artificial leather having high abrasion resistance. More specifically, the present invention relates to a brushed artificial leather having high abrasion resistance and suitable for use in furniture and car seat applications.

[0002]

2. Description of the Related Art Conventionally, it has been widely known that an artificial leather is obtained by impregnating a nonwoven sheet-like material mainly composed of microfibers with various types of high molecular elastomers to obtain artificial leather. The sueded or nubuck brushed artificial leather is widely used not only in the field of clothing such as coats, skirts and jackets, but also in the field of non-clothing such as shoes, bags, furniture and car seats. These brushed artificial leathers are required to use ultra-fine fibers having a single yarn denier of 0.5 denier or less in order to obtain a luxurious feeling and a lighting effect similar to that of natural leather on the surface. As the material of the ultrafine fibers, polyesters such as polyethylene terephthalate, polyamides such as nylon 6 and nylon 66, and polyacrylonitrile are preferably used. However, because of the fineness of the ultrafine single yarn of 0.5 denier or less, there is a disadvantage that the wear resistance is poor.

[0003] In particular, in applications requiring durability, such as in the interior field of furniture, car seats, etc., if used for a long period of time, wear resistance becomes a problem, and the surface fluff comes off, resulting in so-called "shininess" or "shininess". It is easy to get bald. Further, it is difficult to obtain a color developing property of a dark color, and it cannot be said that the light fastness is sufficient. When exposed to a high-temperature environment such as a car sheet, the problem tends to be particularly problematic. For example, Japanese Unexamined Patent Publication No. Hei 5-78986 discloses that when a polymer elastic body is impregnated and applied to a nonwoven fabric formed by entanglement of ultrafine fibers having an average fiber diameter of 0.1 to 6 μm obtained by a melt blow method, A nubuck-like artificial leather is disclosed in which the finer fibers are distributed more on the surface layer side than on the layer side to enhance the gripping force of the ultrafine fibers and have excellent wear resistance. But,
In this case, the ultrafine fibers are firmly adhered to the polymer elastic body, and it is difficult to obtain a natural leather-like soft texture.

On the other hand, Japanese Patent Publication No. 56-16235 discloses that when a polymer elastic material is impregnated into a nonwoven fabric of mixed fibers composed of two types of polymer materials having different solvent solubilities, one component of the mixed fibers is dissolved with a solvent. Either before or after extraction to generate microfibers, or by applying impregnation in two stages, to control the adhesion between microfibers and the elastic polymer to obtain a soft texture and reduce hair loss of microfibers An improved method is disclosed. On the other hand, in JP-A-3-137281 and JP-A-6-316877, the single yarn fineness is 0.1.
Polyurethane elastic DMF as a non-woven sheet material in which a sheet of ultra-fine short fibers of 5 denier or less is entangled and integrated with a knitted fabric
There is disclosed an artificial leather which is impregnated with a solution and dry-coagulated, or impregnated with an aqueous polyurethane emulsion and dried and dry-coagulated, and the surface of which is fluffed with sandpaper.

[0005] In this case, the adhesion between the ultrafine fibers and the polymer elastic body becomes stronger than in the dry coagulation, and the loss of the fibers is suppressed to some extent. However, there is a disadvantage that the feel of the artificial leather becomes hard. If the amount of impregnation of the elastic polymer is reduced to obtain a soft texture, there is a problem that the abrasion resistance is reduced. As described above, conventionally, brushed artificial leather has a high-quality surface quality and a soft touch like natural suede, and can withstand long-term use in furniture and car seat applications. It is hard to say that it has sufficient wear properties. .

[0006]

SUMMARY OF THE INVENTION The present invention improves the disadvantages of using the conventional artificial leather as described above in the interior field such as furniture and car seats, and has a high degree of wear resistance.
An object of the present invention is to provide a brushed artificial leather having excellent darkness and light resistance and having a soft texture.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to improve the above-mentioned drawbacks, and as a result, by applying specific ultrafine fibers made of a specific polyester polymer to artificial leather, The present invention has been found to have an unprecedented high abrasion resistance, and has reached the present invention. That is, the present invention is as follows.

[0008] Terephthalic acid is used as an acid component and trimethylene glycol is used as a glycol component in at least 8 parts.
A polyester polymer containing at least 0 mol%,
Non-woven fabric having at least a fiber layer composed mainly of polytrimethylene terephthalate ultrafine fibers having an intrinsic viscosity [η ^sp / _c ] of 0.45 to 1.2 and a single fiber fineness of 0.2 denier or less A brushed artificial leather comprising a sheet-like material and a polymer elastic body impregnated in a tissue gap of the non-woven sheet-like material and having a high level of abrasion resistance, wherein the surface is fluffed.

Preferably, the nonwoven sheet is a brushed artificial leather in which a woven or knitted material is integrally embedded in an inner layer region or a back layer region. Further, the polymer elastic material is a water-dispersed polyurethane elastic material. Impregnated, wherein the adhesion rate of the elastic body is 3 to 20 wt% of the weight of the nonwoven sheet.
Brushed artificial leather. The water-dispersed polyurethane elastic material is a brushed artificial leather having a heat generation peak temperature of 200 ° C. or more by a differential scanning calorimeter (DSC) and a heat generation value of the heat generation peak of 60 mj / mg or less. DETAILED DESCRIPTION OF THE INVENTION The ultrafine fiber of the present invention needs to be a polytrimethylene terephthalate containing at least 80 mol% or more of trimethylene glycol as a glycol component.

In the present invention, trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol and a mixture thereof. From the viewpoint of stability, 1,3-propanediol is particularly preferred. The content of trimethylene glycol must be at least 80 mol% of the glycol component. When the content ratio is less than 80 mol%, abrasion resistance, easy dyeability,
The color fastness and the like are reduced, and the object of the present invention is not achieved. It is preferably at least 90 mol%, more preferably at least 95 mol%.

In the polytrimethylene terephthalate used in the present invention, if necessary, isophthalic acid, succinic acid, adipic acid, 2,6-naphthalenedicarboxylic acid may be used as an acid component within a range not to impair the effects of the present invention. An acid or a glycol component such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, or polyoxyalkylene glycol may be copolymerized as a glycol component. If necessary, various additives such as a matting agent, a heat stabilizer, a flame retardant, an antistatic agent and an antifoaming agent may be copolymerized or mixed.

The polytriethylene terephthalate used in the present invention can be polymerized by a known method. Further, in order to obtain a high degree of polymerization, a solid phase polymerization method may be used without any problem in the present invention. It is. The ultrafine fiber of the present invention is produced from the above-mentioned polytrimethylene terephthalate by a conventionally known melt spinning method. For example, a method of directly spinning extra-fine multifilaments as disclosed in JP-B-62-35481, or
A method of obtaining an ultrafine fiber web by a melt blow method as disclosed in JP-A-53-34218, or Japanese Patent Publication No. Sho 61-34218.
No. 36084, and Japanese Patent Publication No. 59-14570.

That is, a mixed conjugate fiber composed of a polytrimethylene terephthalate polymer and one or more other component polymers, or a fiber cross-sectional shape selected from a group such as a laminated type, a split type, a wedge type, a core-sheath split type, and a sea-island type. The other component polymer is dissolved or decomposed and extracted and removed by a solvent or a chemical from a conjugate fiber in which each polymer component is continuous in the fiber length direction, or by a mechanical force such as high-pressure water. By exfoliating and dividing, the polytrimethylene terephthalate ultrafine fiber of the present invention can be obtained. At this time, as other component polymers, polyolefins such as polyethylene and polypropylene having different compatibility with the polytrimethylene terephthalate polymer, ring-containing vinyl polymers such as polystyrene, poly-α-methylstyrene and polyvinyl toluene, nylon 6, nylon 66, nylon 610 And polyamides such as nylon 612, and further, polyethylene glycol copolymerized polyesters and sulfoisophthalic acid copolymerized polyesters having alkali-hydrolyzing properties.

In the present invention, the relative viscosity [η ^sp / _c ] of the polytrimethylene phthalate ultrafine fiber obtained by the above method needs to be in the range of 0.45 to 1.2. If the relative viscosity [η ^sp / _c ] exceeds 1.2, the fine fiber fluff becomes entangled during surface wear, causing pilling, and conversely, the number of wear-resistant ends decreases, and the brushed touch becomes poor. Not suitable for the invention. In addition, the dyeability also decreases. on the other hand,
If the relative viscosity [η ^sp / _c ] is less than 0.45, the single fiber strength of the ultrafine fibers is significantly reduced, so that the fluff becomes fuzzy at the time of surface abrasion, resulting in defects of “bald” and “shiny”. The high abrasion resistance aimed at by the present invention cannot be obtained. Relative viscosity [η ^sp / _c ] of the preferred ultrafine fiber of the present invention
Is 0.50 to 1.10, more preferably 0.55
To 1.0, and most preferably 0.60 to 0.9.
5 range.

The fineness of single fibers of the polytrimethylene terephthalate ultrafine fibers of the present invention must be 0.2 denier or less. If the single fiber fineness exceeds 0.2 denier, the quality and feel of the surface of the brushed artificial leather become poor, and not only a good writing effect cannot be obtained, but also the texture becomes hard. In addition, surface-raised fibers are also not preferable because they tend to cause pilling in terms of abrasion resistance. The smaller the single fiber fineness is, the better the texture of brushed artificial leather, surface touch, lighting effect etc. are good, but if it is too thin, the single yarn strength of the ultrafine fiber becomes extremely weak, and the drawback that the brushed hair is easily worn off due to abrasion is preferable. Not. Preferred single fiber fineness of the polytrimethylene terephthalate ultrafine fibers of the present invention is 0.001 to 0.2 denier, more preferably 0.01 to 0.2 denier, and most preferably 0.05 to 0.2 denier.
It is in the range of 0.15 denier.

The nonwoven sheet of the present invention has at least a fiber layer on the surface of which the above-mentioned polytrimethylene terephthalate ultrafine fibers are mainly entangled. In the fiber layer on the surface, single fibers of polytrimethylene terephthalate ultrafine fibers may be three-dimensionally intertwined with each other, but fiber bundles in which the single fibers are gathered may be three-dimensionally entangled with each other. The single fiber and the fiber bundle may be mixed and entangled. The fiber layer on the surface may be entangled with a polytrimethylene terephthalate ultrafine fiber different from the polytrimethylene terephthalate ultrafine fiber so as not to impair the effects of the present invention. The constituent weight ratio in the layer is at least 50% or more, preferably 70% or more, more preferably 80% or more. If the constituent ratio of the polytrimethylene terephthalate ultrafine fiber is 50% or less, it is difficult to obtain the high abrasion resistance aimed at by the present invention.

In the present invention, any constituent fiber layer may be used as a layer connected to the ultrafine fiber layer on the surface.
For example, the entire nonwoven sheet may be constituted by a fiber layer having the same structure as a fiber layer constituted by intertwining mainly polytrimethylene terephthalate ultrafine fibers constituting the surface,
Alternatively, the entire nonwoven sheet may be constituted by a fiber layer in which constituent fibers different from the surface fiber layer are entangled. Alternatively, as a layer connected to the surface fiber layer, a layer made of a knitted fabric that is entirely covered with the surface fiber layer and that is three-dimensionally entangled may be arranged. Furthermore, a fiber layer having an arbitrary configuration may be entangled to form a nonwoven sheet. As described above, the woven or knitted fabric is disposed in the inner layer area or the back layer area of the nonwoven sheet, and the constituent fibers of the woven and knitted article and the ultrafine fibers are entangled and embedded integrally to such an extent that they are not easily separated. In addition, excellent strength physical properties and dimensional stability can be realized, falling off of ultrafine fibers can be suppressed, and the effect of improving abrasion resistance of the present invention becomes even more remarkable.

The present invention provides a brushed artificial leather in which a high molecular weight elastic body is impregnated in the tissue gap of the nonwoven sheet-like material, and the surface of the ultrafine fiber layer is fluffed and has high abrasion resistance. In addition, the following can be used alone or as a mixture as the polymer elastic body. That is, as the polymer elastic body of the present invention, polyurethane elastic body, acrylonitrile butadiene copolymer, styrene butadiene copolymer, polybutadiene, synthetic rubber such as neoprene,
Elastic bodies such as polyacrylates can be used. The preferred adhesion rate of the elastic polymer to the nonwoven sheet is 3 to 30 wt%, more preferably 4 to 20 wt%.
%, More preferably in the range of 5 to 15 wt%.

Further, in the present invention, in order to obtain a soft, brushed artificial leather having a high abrasion resistance which can never be obtained by conventional brushed artificial leather, a polyurethane elastic material is used among the above polymer elastic materials. Can be preferably used. For example, as the polyol component, polyester diols such as polyethylene adipate glycol and polybutylene adipate glycol; polyether glycols such as polyethylene glycol (PEG), polypropylene glycol (PPG) and polytrimethylene glycol (PTMG); and polycarbonate diol (PCG) ) And the like, and diphenylmethane-4, 4 ′ as an isocyanate component.
Aromatic isocyanates such as diisocyanate (MD
I) an alicyclic isocyanate such as dicyclohexylmethane-4,4′-diisocyanate (H12-MDI);
Aliphatic diisocyanates such as hexamethylene isocyanate (HMDI) can be used, and glycols such as ethylene glycol, ethylene diamine,
Diamines such as 4,4 ′ diaminodiphenylmethane,
Further, trifunctional alcohols, amines and the like can be appropriately selected.

Further, the water-dispersed polyurethane elastic body obtained by forced emulsion polymerization from the above-mentioned polyol component, diisocyanate component and chain extender has a strong fiber gripping force, and the woven or knitted fabric is integrated into the inner layer area or the back layer area. When impregnated into the interstitial space of the non-woven sheet-like material embedded in the material, the adhesion rate of the water-dispersible polyurethane can be suppressed to the range of 3 to 20%, and if it has high abrasion resistance. In addition, it is possible to obtain a brushed artificial leather having a soft texture and excellent dimensional stability. In this case, a preferable adhesion rate of the water-dispersed polyurethane elastic body to the nonwoven sheet is 4 to 4.
It is in the range of 15 wt%, more preferably 5 to 12%.

Further, the peak temperature of the heat generated by the differential scanning calorimeter (DSC) of the water-dispersed polyurethane elastic material is 200 ° C.
As described above, the calorific value of the exothermic peak is 60 mj / mg.
When impregnated into the interstitial space of the non-woven sheet-like water-dispersible polyurethane elastic body having excellent hot water resistance as follows,
Further, it is possible to obtain a brushed artificial leather which is improved in abrasion resistance and has excellent heat resistance and light resistance having a soft and soft texture. More preferably, the water-dispersible polyurethane elastic body is a non-yellowing polyurethane elastic body of a polyether type obtained from polyether glycol such as PPG or PTMG and HMDI, H12-MDI, or a non-yellowing polyurethane elastic body of a polycarbonate type. The body is heat resistant,
It can be suitably used in the present invention because of its hot water resistance and light resistance.

In a preferred embodiment, an antioxidant, a light stabilizer and the like as a heat resistance improver are used in combination with the water-dispersible polyurethane elastic body. These additives and the like can be added at the time of polymerization of the aqueous polyurethane, can be added in the form of an emulsion after the completion of the polymerization, or can be added in both steps. Antioxidants generally include hindered amines, hindered phenols, and hydrazines. Hindered amine-based high molecular weight grades exhibit particularly excellent effects. In any case, when the water-dispersed polyurethane elastic material has a heat generation peak temperature of 200 ° C. or more measured by a differential scanning calorimeter (DSC) and the heat generation value of the heat generation peak is 60 mj / mg or less. Demonstrates excellent effects. Preferably, the exothermic peak temperature by DSC is 215 ° C. or higher, and the exothermic amount of the exothermic peak is 5
0 mj / mg, and more preferably 30
It is preferred that no exothermic peak appears at 0 ° C. or lower.

The raised artificial leather of the present invention can be produced, for example, by the following method. A polyester polymer containing terephthalic acid as an acid component and at least 80 mol% of trimethylene glycol as a glycol component has a relative viscosity [η ^sp / _c ] of from 0.45 to 0.5 by a direct spinning method as described above. 95, single fiber fineness is 0.
A polytrimethylene terephthalate ultrafine fiber of 0.05 to 0.2 denier is obtained, cut into short fibers of 20 mm or less, and then formed into an ultrafine fiber web by a wet method.

A woven or knitted fabric is inserted between the two ultrafine fiber webs, and the surface of the nonwoven sheet obtained by entanglement and integration by needle punching or high pressure water flow is subjected to buffing treatment with sandpaper or the like. Then, the nonwoven sheet-like material having a raised surface is impregnated with an emulsion of a water-dispersed polyurethane elastic material and dried, or wet-solidified by impregnating a solution-type polyurethane elastic material dissolved in a solvent such as DMF. Finally, the brushed artificial leather of the present invention can be obtained by performing post-processing such as dyeing treatment and antistatic water-repellent treatment.

Alternatively, the relative viscosity [η ^sp / _c ] of the above polyester polymer is 0.45 by a melt blow method.
To obtain a polytrimethylene terephthalate ultrafine fiber web having an average fiber degree of 0.001 to 0.05 denier calculated from the average fiber diameter and the fiber density. The non-woven sheet is obtained by three-dimensionally intertwining the ultrafine web with a needle punching method and a fluid entanglement method using a high-pressure water flow, and can be obtained by the same method as described above.

On the other hand, a sea-island fiber having a sea component of block polyether polyethylene terephthalate polymer obtained by copolymerizing 10% by weight or more of polyethylene glycol or polystyrene and the like and the polytrimethylene terephthalate polymer as an island component is melt-spun. The relative viscosity [η ^sp / _c ] is 0.45 to 1.2 and the single fiber fineness is 0.1 to 5% by dissolving and removing the block copolymer ester or polystyrene with a hot alkali aqueous solution of 5 to 5% or trichloroethylene. Polytrimethylene terephthalate ultrafine fibers of 001 to 0.2 denier can be obtained. The ultrafine fibers thus obtained can also be cut into short fibers of 20 mm or less, and the brushed artificial leather of the present invention can be obtained in the same manner as the ultrafine fibers obtained by the direct spinning method as described above.

Further, before the ultrafine treatment, the conjugate fiber is cut into short fibers of 20 to 80 mm to form a conjugate fiber web by a known dry method such as a card method or an air lay method. A nonwoven fabric sheet is obtained by laminating it on the back layer part or by three-dimensionally entangled by a needle punch method or a columnar flow entanglement method without laminating. Similarly, the nonwoven fabric sheet has a relative viscosity η ^sp / _c of 0.45 to 1.2 and a single-fiber fineness of 0.1 by dissolving and removing the block copolymer ester or polystyrene with a hot alkali aqueous solution, trichloroethylene or the like. It is possible to obtain a nonwoven sheet-like material in which 001 to 0.2 denier polytrimethylene terephthalate ultrafine fibers are entangled, and to obtain a brushed artificial leather according to the present invention by brushing the surface before and after impregnation of the polyurethane elastic body. Can be.

Next, composite fibers (volume ratio of 8: 2) arranged in a petal-type (seven-split) as a second component of a mixed polyamide polymer of nylon 6 and nylon 612 using a polytrimethylene terephthalate polymer as a first component. Was. The conjugate fiber is cut to a length of 10 mm, a papermaking sheet is formed by a wet method, and a woven or knitted fabric is inserted between the two sheets, and the single fiber fineness is 0.2 denier or less by a columnar flow entanglement treatment or the like. By splitting into ultrafine fibers of polytrimethylene terephthalate and ultrafine fibers of polyamide at the same time and confounding three-dimensionally, it is possible to obtain a nonwoven sheet-like material which can be used for obtaining brushed artificial leather in the present invention. As described above, the method for producing the artificial leather of the present invention has been described, but the present invention is not limited to this.

[0029]

The present invention will be described in more detail with reference to the following examples and comparative examples, which do not limit the scope of the present invention in any way. The measuring method of each measured value used in the description of the examples and the like is as follows. Abrasion resistance: JIS-L-1096 (Martindale method). Flexibility: JIS-L1079-A method (45 ° cantilever method). Relative viscosity [η ^sp / _c ]: value obtained by dividing the viscosity at 35 ° C. of a diluted solution of polytrimethylene terephthalate dissolved in O-chlorophenol having a purity of 98% or more by the viscosity of the solvent itself measured at the same temperature. .

Darkness: relative comparison by K / S. The spectral reflectance of the dyed sample fabric was measured, and the K / S was determined from the following Kubelka-Munk formula. If K / S was 20 or more, it was determined that the sample had good color developability. As R, the value at the maximum absorption wavelength of the dye was used. K / S = (1-R) ² / 2R Light fastness: JIS-L-0842 method (carbon arc, 83 ° C. * 100 Hrs method)

Heat generation peak temperature, heat generation: Differential scanning calorimeter (DSC; for example, DSC manufactured by SEIKOI & E)
200 / TG / DTA200), sample weight 5
Using 10 to 10 mg, the temperature is raised up to 300 ° C. by an air flow at a rate of 10 ° C./min, and the expression peak is analyzed. The urethane elastomer to be measured is coated on a glass plate with a 0.75 mm applicator of a stock solution of an aqueous dispersion emulsion,
Dry at 25 ° C. room temperature for 20 hours to form a film. Next, the film is put into a hot air dryer at 130 ° C. together with the glass plate and heat-treated for 20 minutes. Peel the polyurethane film from the glass plate, treat it in hot water at 130 ° C for 20 minutes, then treat it at 80 ° C for 15 minutes, wash it with water, and air-dry it. Heat resistance of the product: 110 ° C of the obtained artificial leather At 10
The change in texture before and after the heat treatment for 0 hour was evaluated using a cantilever. When the texture was hardened by the heat treatment, it was represented by x, and when there was no change in the texture, it was represented by ○.

[0032]

Example 1 1,3-propanediol and dimethyl phthalate were polymerized by a conventional method to obtain a polytrimethylene terephthalate polymer. This polytrimethylene terephthalate polymer was spun at a spinning temperature of 280 ° C. and had a pore size of 0.1
The extruded material was extruded at a discharge rate of 11.7 g / min using a spinner having 350 holes with a diameter of 350 mm. Cooling is performed while blowing cooling air toward the spinning surface just below the spinning nozzle, and the winding speed is 12
An ultrafine multifilament undrawn yarn was obtained at 00 m / min.
Subsequently, the obtained undrawn yarn was drawn at a draw ratio of 2.5 times to obtain a drawn yarn of 35.0 denier / 350 filaments. The relative viscosity [η ^sp / _c ] of the obtained ultrafine fiber of polytrimethylene terephthalate is 0.54, the single fiber fineness is 0.10 denier, the strength is 3.2 g / d, the elongation is 25%,
Met. The obtained ultrafine fiber was cut into a length of 5 mm, and then dispersed in water to prepare a papermaking slurry for the surface layer and the back layer.

The basis weight of the surface layer is 100 g / m ² and the basis weight of the back layer is 50 g.
/ M ^2, and a gauze-like woven fabric made of 100d / 48f PET fiber was inserted into the middle to obtain a three-dimensional entangled nonwoven fabric by spraying a high-speed water stream. The high-speed water flow is 40 kg / cm ² from the surface layer and 30 kg from the back layer by a straight flow jet nozzle with a hole diameter of 0.15 mmφ.
/ Cm ² pressure, and then 6 sheets between the sheet and the nozzle.
A 0-mesh wire net was inserted, treated at a water pressure of 25 kg / cm ² , dried with a pin tenter, and a nonwoven sheet having a basis weight of 200 g / m ² and a thickness of 0.8 mm was continuously produced.

After buffing the surface layer of this sheet material with # 400 emery paper, "Evaphanol AP-12" (Nippon Kagaku's non-yellowing type nonionic polyether non-yellowing type polyurethane elastic material manufactured by Nichika Chemical Co., Ltd.) The emulsified liquid was prepared by adding sodium sulfate as a heat-sensitive coagulant at a concentration of 7% of the emulsion of (name). The squeezing adhesion rate was adjusted with a mangle so that the impregnation rate became 160%, and then the coating was continuously heated and dried at 130 ° C. for 3 minutes using a pin tenter dryer.
Brushed artificial leather obtained by dyeing this artificial leather raw fabric using a liquid jet dyeing machine has a soft texture, a luxurious soft touch and a surface quality of excellent writing effect,
In addition, it had unprecedented high abrasion resistance, darkness, and light resistance. Table 1 shows the performance data of this artificial leather.

[0035]

Example 2 A block ether ester (hereinafter abbreviated as a copolymer ester) obtained by copolymerizing 15% by weight of polyethylene glycol with a polytrimethylene terephthalate polymer as a first component and polymerizing in the same manner as in Example 1 was used as a second component. As the component, a 48-denier / 48-filament conjugate spun fiber (first component /
The second component is 80% by weight / 20% by weight, and after the copolyester is decomposed and removed, it becomes 0.13 d / f). After rewinding the filament yarn to about 6000 d, using a rotary cutter, a fiber length of 10.0 mm is used. Cut into short fibers.

The obtained short fiber was prepared by a papermaking method with a basis weight of 200.
g / m ² sheet was formed, and a three-dimensional entangled nonwoven fabric was obtained by jetting a high-speed water flow. The high-speed water flow is 45 kg / cm ² from the surface layer of the straight flow jet nozzle with a hole diameter of 0.15 mm, and 4 kg from the back layer.
After treatment at a pressure of 0 kg / cm ² , the pore size is 0.20 mm
Using a straight-flow jet nozzle, a 30-mesh wire mesh is inserted between the fiber sheet and the nozzle, and the front and back surfaces have a water pressure of 60 kg /
was treated with cm ^2, and finally changing the wire mesh 60 mesh to give a non-woven sheet made of composite fibers by entangling process the front and rear surfaces with water pressure 25 kg / cm ^2.

This nonwoven sheet was obtained by decomposing and removing the copolymerized polyester component with a 4.5% by weight aqueous solution of sodium hydroxide at a treatment temperature of 90 ° C. and a treatment time of 40 minutes.
The nonwoven sheet made of polytrimethylene terephthalate ultrafine fibers had a relative viscosity [η ^sp / _c ] of 0.76. A solution-type polyether-based polyurethane “Chrisbon 1836 manufactured by Dainippon Ink Co., Ltd.” is applied to the nonwoven sheet.
P; trade name) was impregnated and wet coagulated, and the surface layer was buffed with # 400 emery paper and dyed and finished to obtain a brushed artificial leather. The brushed artificial leather had elasticity and soft texture in addition to excellent abrasion resistance and high-grade quality. Table 1 shows the performance data of this artificial leather.

[0038]

Example 3 In Example 1, an antioxidant "Timasorb 944L" was added to a polyurethane emulsion impregnating solution.
D "(manufactured by Ciba-Geigy Corporation; trade name) was obtained in the same manner as in Example 1 except that 1.0% based on the urethane solid content was obtained, so that abrasion resistance was further improved. It exhibited a flexible and high-grade performance with excellent heat resistance. The performance data is shown in Table 1.

[0039]

Comparative Example 1 In Example 1, the relative viscosity [η ^sp / _c ] of the polytrimethylene terephthalate ultrafine fiber was 0.55, and the single fiber fineness was 0.15 by extruding at a discharge rate of 34 g / min. A fiber having 3 deniers, a strength of 3.5 g / d and an elongation of 26% was obtained. The brushed artificial leather obtained in the same manner as in Example 1 is
Although the end point of the abrasion resistance was good, a defect that the appearance changed like pilling at the time of initial abrasion was recognized. Although excellent in deep color and light fastness, the surface had a rough feel to the touch and the lighting effect was low. The performance data is shown in Table 1.

[0040]

Comparative Examples 2 and 3 Brushed artificial leathers were obtained in the same manner as in Examples 1 and 2, except that the polyester polymer was prepared from ethylene glycol and dimethyl phthalate, using a polyethylene terephthalate polymer polymerized in the same manner.
This product is excellent in surface properties, texture and appearance quality, but its abrasion resistance is sufficient for garments such as skirts, pants and coats, but non-clothing which requires durability such as furniture and car seats The level was not enough for use.
The performance data is shown in Table 1.

[0041]

Example 4, Comparative Examples 3 and 4 Relative viscosity was obtained in the same manner as in Example 1 or by further treating the obtained polytrimethylene terephthalate polymer under reduced pressure at 200 ° C. for 2 to 10 hours. 7 kinds of high-viscosity polymer chips were obtained. A block ether ester obtained by copolymerizing 15% by weight of polyethylene glycol (hereinafter abbreviated as a copolymerized ester) is used as a sea component, and seven types of polytrimethylene terephthalate polymers having different relative viscosities are respectively used.
3.0 d / f sea-island fibers as 37 island components (to become 0.05 d / f after copolyester decomposition removal,
(Island = 35% by weight / 65% by weight)
After rewinding to 000d, it was cut into 3mm sea-island short fibers using a rotary cutter.

The obtained sea-island staple fiber is sealed in a polypropylene fiber dyeing bag, and the copolyester component is decomposed with a 4.5% by weight aqueous sodium hydroxide solution at a treatment temperature of 90 ° C. and a treatment time of 40 minutes. Removed. Subsequently, washing with hot water was repeated three times, and finally, centrifugal dehydration was performed. Relative viscosity [η ^sp / _c ] of obtained polytrimethylene terephthalate ultrafine short fiber = 1.12, 0.91, 0.76, 0.6
Nos. 4 and 0.45 were used for the brushed artificial leathers obtained in the same manner as in Example 1, respectively. 1 to No. It was set to 5. On the other hand, the relative viscosity [η ^sp / _c ] of the obtained ultrafine short fibers of polytrimethylene terephthalate was 1.22 and 0.40, and
Brushed artificial leather obtained in the same manner as in Comparative Example 4,
Comparative Example 5 was set. The performance is shown in Table 2.

[0043]

Example 5 The polytrimethylene terephthalate polymer of Example 2 was charged into an extruder and melted at a temperature of 280 ° C.
With a discharge rate of 0.15 g / min / orifice into 0.3 mmφ orifices arranged in a line at 1500 pitches at 1 mm pitch,
It began to spit out during the high-speed steam flow. The steam has a temperature of 3
Jetting was performed at 30 ° C. and a pressure of 3.0 kg / cm ² from a slit opened near the polymer discharge orifice. The generated fiber group was continuously collected on a moving collecting surface located 60 cm below the orifice, and was wound up as a random web having a basis weight of 100 g / m ² . The resulting ultrafine fiber web relative viscosity _{^{[η sp / c] = 0.56}} , is formed from the ultrafine fibers having an average fiber diameter of 2.2 .mu.m, a rope-like fibers was extremely small.

A gauze-like woven fabric composed of 100 d / 48 f PET fibers and a 50 g / m ² papermaking sheet as in Example 1 were laminated on the lower surface of the ultrafine fiber web, and then three-dimensional entangled nonwoven fabric was injected by high-speed water jet. I got High-speed water flow is 40k from the surface using a straight-flow jet nozzle with a hole diameter of 0.2mm.
g / cm ² , a treatment from the back layer at a pressure of 25 kg / cm ² , a 60-mesh wire mesh inserted between the sheet and the nozzle, treatment at a water pressure of 25 kg / cm ² , drying with a pin tenter, and a basis weight of 200 g / m ² A non-woven sheet having a thickness of 0.8 mm was obtained. Brushed artificial leather was obtained from this nonwoven sheet in the same manner as in Example 2. Table 1 shows the performance data of the brushed artificial leather.

[0045]

Example 6 In Example 5, the polytrimethylene terephthalate obtained as a result of blow spinning was prepared by changing the melting temperature to 300 ° C., changing the steam temperature to 330 ° C., and changing the pressure to 4.5 kg / cm ^2. The microfiber web has a relative viscosity [η ^sp
/ _C] = 0.49, an average fiber diameter of 1.0 .mu.m. Hereinafter, brushed artificial leather was obtained in the same manner as in Example 5, and its performance data is shown in Table 1.

[0046]

Example 7 Polytrimethylene terephthalate of Example 2 was used as a first component, and nylon 6 and nylon 612 were used as a second component.
A petal-shaped easily splittable conjugate fiber having a denier of 1 denier (volume ratio of 8: 2) having a cross section of 5% was cut into 5 mm and dispersed in water to prepare a papermaking slurry for the surface layer and the back layer. The surface layer having a basis weight 100g / m ^2, the backing layer having a basis weight 50g / m ²
A gauze-like woven fabric made of 100d / 48f PET fibers was inserted into the middle of the sheet to form a laminated fiber sheet. Then, the sheet was divided simultaneously with three-dimensional entanglement by high-speed water jet to obtain a nonwoven sheet.

The high-speed water flow is 50 kg / cm ² from the surface layer and 45 k from the back layer by a straight flow jet nozzle having a hole diameter of 0.15 mmφ.
g / cm ² , a 60-mesh wire mesh was inserted between the sheet and the nozzle, treated at a water pressure of 25 kg / cm ² , dried with a pin tenter, and weighed 200 g / m ² , having a thickness of 0.8 mm. A woven sheet was produced. The relative viscosity [η ^sp / _c ] of the polytrimethylene terephthalate after dissolving and removing the polyamide component was 0.72, and the surface layer had a single fineness of 0.13 d.
The structure was such that ultrafine fibers of polyamide were intertwined at a weight ratio of 80:20. From this non-woven sheet material, brushed artificial leather was obtained in the same manner as in Example 1 below. The resulting artificial leather,
The brushed surface finished into a suede having an elegant lighting effect unique to ultrafine yarn, had a natural leather-like texture and flexibility, and had excellent abrasion resistance. Table 1 shows the performance data of the brushed artificial leather.

[0048]

Example 8 A brushed artificial leather manufactured in the same manner as in Example 3 except that the addition amount of the antioxidant to the urethane solid content was 0.5 wt% and 3 wt% in Example 3, . 1, No. Table 2 shows the performance.
In Example 3, the adhesion rate of the polyurethane elastic body to the nonwoven sheet was 3 wt%, 5 wt%, and 8 wt%.
%, And 15% by weight, respectively. 4, no. 5, no. 6, no. 7, no. Table 3 shows the performance. Further, the polyol component of the water-dispersed polyurethane is polycarbonate diol (P
CG), dicyclohexylmethane-4,4′-diisocyanate (H12-MD) as an isocyanate component
I) and a 7% emulsion of a polycarbonate-based non-yellowing type polyurethane obtained by forced emulsion polymerization from a chain extender such as a diamine or a trifunctional alcohol was obtained by impregnating the same nonwoven sheet as in Example 1. No. brushed artificial leather. The performance is shown in Table 3 as No. 9.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

As described above, the present invention preferably employs a structure in which a polyurethane elastic material is impregnated into the fiber gaps of a nonwoven sheet-like material entangled with a specific polytrimethylene terephthalate ultrafine fiber. By inserting and integrating the woven or knitted material into the inner layer area or the back layer area of the non-woven sheet-like material and impregnating with a specific polyurethane elastic body, a high-grade surface brushed grade for clothing use that is close to natural leather,
An object of the present invention is to provide a brushed artificial leather having high abrasion resistance, light resistance, and dark color development that can sufficiently withstand interior uses such as furniture and car sheets requiring durability while maintaining flexibility. I can do it.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) D06N 3/00-3/18 D04H 1/42 D06C 11/00 D06M 15/564

Claims (4)

(57) [Claims] 1. A polyester polymer containing terephthalic acid as an acid component and at least 80 mol% of trimethylene glycol as a glycol component, having a relative viscosity [η ^sp / _c ] of 0.45 to 1.2, and A nonwoven sheet having at least a fiber layer composed of polytrimethylene terephthalate ultrafine fibers having a fiber fineness of 0.2 denier or less and mainly entangled with a nonwoven sheet is impregnated into the tissue gap of the nonwoven sheet. Brushed artificial leather comprising a high-molecular elastic body and having a high degree of abrasion resistance in which the surface is fluffed. 2. The brushed artificial leather according to claim 1, wherein the woven or knitted fabric is integrally embedded in the inner layer region or the back surface layer region of the nonwoven sheet. 3. The method according to claim 1, wherein the polymer elastic body is obtained by impregnating a water-dispersed polyurethane elastic body, and the adhesion of the elastic body is 3 to 20 wt% of the weight of the nonwoven sheet. 3. The brushed artificial leather according to claim 1 or claim 2. 4. The water-dispersed polyurethane elastic material has a peak heat generation temperature of 200 ° C. or more measured by a differential scanning calorimeter (DSC) and a heat generation value of the heat generation peak of 60 mj / mg or less. A brushed artificial leather according to claim 3.