JPH05186972A - Stretchable leathery sheetlike material and its production - Google Patents

Abstract

PURPOSE:To obtain the subject flexible sheetlike material rich in stretchability by laminating polyurethane elastic filaments to nonelastic fiber, laminating and entangling constituent fiber thereof in a specific state, further entangling nonelastic staple fiber with the resultant fibrous sheet, and forming a filling layer and a skin layer on the formed fibrous sheet. CONSTITUTION:A polyurethane elastomer and a nonelastic polymer (e.g. a readily dyeable polyester) are respectively melted, joined at 2:1 weight ratio and spun to provide a fibrous sheet in which conjugate filament composed of both the components is opened into single fibers, fused and entangled with the polyurethane itself. The resultant fibrous sheet is then stretched in hot water and expansion and contraction are repeated to afford a fibrous sheet in which the conjugate filament is divided and kept at a length of >=2 times that between joined points of the polyester filaments under no tension and laminated in a slacked or a loopy form. Nonelastic fiber is then laminated and entangled with both surfaces of the fibrous sheet and a polyurethane skin layer is laminated through a polyurethane bonding layer to provide the objective stretchable leathery sheetlike material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretchable leather-like sheet material comprising a nonwoven fabric of polyurethane elastic filaments as one component of a fibrous base material.

[0002]

2. Description of the Related Art Generally, a sheet-like material obtained by filling a fibrous base material such as a non-woven fabric with a polyurethane elastomer is
It is used in various fields as shoes, bags, bags, clothes, furniture, interior materials, etc., but most of them are not stretchable. On the other hand, there have been various attempts such as direct flocking on a stretchable cloth or lamination of a polyurethane elastic nonwoven fabric and a cloth in order to obtain a stretchable flocked cloth. It was unavoidable that the permeation impaired the elasticity and the texture became rough and rigid.

Japanese Unexamined Patent Publication (Kokai) No. 2-264057 discloses an elastic nonwoven fabric in which melt-blown ultrafine fibers of a saponified ethylene-vinyl acetate copolymer and meltblown ultrafine fibers of polyurethane are mixed and used as a base material for leather-like sheets. Although it is described that it can be used, it cannot be denied that the average fiber diameter is 8 μm or less and the ethylene-vinyl acetate component is heat-bonded, so that the elasticity and texture are inferior.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a leather-like stretchable sheet which is flexible and has excellent elongation recovery and a method for producing the same, which solves the conventional defects.

[0005]

That is, the sheet-like article of the present invention is a sheet-like article in which a napped sheet is formed with a filling layer made of an elastic polymer and a skin layer made of a polyurethane elastic body. Is laminated with a polyurethane elastic filament (A) and an inelastic fiber (B), the joint point of the laminated polyurethane filament (A) is fused by the polyurethane filament (A) itself, and the inelastic fiber is Non-elastic short fibers (C) on a fiber sheet in which (B) is laminated in a length of at least twice the length of the polyurethane filaments (A) under no tension between the joining points.
Is further laminated and entangled with each other.

The second sheet-like product of the present invention is a sheet-like product in which a filling layer (adhesive layer) made of an elastic polymer and a skin layer made of a polyurethane elastic material are formed on a fiber sheet. The sheet has polyurethane elastic filaments (A) and non-elastic fibers (B) laminated, the joint points of the laminated polyurethane filaments (A) are fused by the polyurethane filaments (A) themselves, and the non-elasticity is the same. It is characterized in that the fibers (B) are laminated in a length that is at least twice as long as the length of the polyurethane filaments (A) under the tension-free condition between the joining points.

Further, in the method for producing a sheet-like material of the present invention, the thermoplastic fiber-forming polyurethane elastic body (a) and the thermoplastic fiber-forming non-elastic polymer (b) are both exposed to the outer peripheral surface of the fiber. The composite filaments (D) that are joined together in the longitudinal direction by the above are laminated without being substantially bundled, and the joining point of the laminated composite filaments (D) is determined by the polyurethane elastic body (a) itself. A step of producing a fused fibrous sheet; a step of dividing the composite filament (D) constituting the fibrous sheet into a polyurethane filament (A) and an inelastic fiber (B); A step of stretching the elastic fiber (B), a step of laminating the non-elastic short fibers (C) on the fiber sheet and intertwining them into a napped sheet, and filling the napped sheet with an elastic polymer to form a non-elastic short fiber Characterized in that comprising the step of forming a skin layer made of packed layer and the polyurethane elastomer which allowed to secure the group of (C).

The second method for producing a sheet-like product of the present invention is
A composite filament in which the thermoplastic fiber-forming polyurethane elastic body (a) and the thermoplastic fiber-forming non-elastic polymer (b) are both bonded in the longitudinal direction so as to be exposed on the outer peripheral surface of the fiber. A step of producing a fiber sheet in which (D) is laminated without being substantially bundled, and the joint points of the laminated composite filaments (D) are fused by the polyurethane elastic body (a) itself; Dividing the composite filament (D) constituting the filament into a polyurethane filament (A) and an inelastic fiber (B), elongating the fiber sheet to draw the inelastic fiber (B), and It is characterized by comprising a step of forming a filling layer (adhesive layer) for filling the elastic polymer and adhering it to the skin layer, and a skin layer made of a polyurethane elastic body.

The present invention will be described in detail below.

The thermoplastic fiber-forming polyurethane elastic body (a) used for the composite filament (D) and the polyurethane elastic filament (A) constituting the fiber sheet may be any known melt-spinnable polyurethane elastic body. Not limited.

Such a polyurethane elastic material generally comprises a low melting point polyol having a molecular weight of 500 to 6000, such as dihydroxypolyether, dihydroxypolyester, dihydropolycarbonate, dihydroxypolyesteramide, and an organic diisocyanate having a molecular weight of 500 or less,
For example, p, p'-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, 2,6-diisocyanate methylcaproate, hexamethylene diisocyanate, and a chain extender having a molecular weight of 500 or less, for example, It is a polymer obtained by reaction with glycol, aminoalcohol or triol.

Among these polymers, particularly preferable ones are polyurethanes using polytetramethylene glycol as a polyol, or poly ε-caprolactone or polybutylene adipate. When polyethylene glycol is used as the polyol, it is used for a special purpose because its hydrophilic property is improved. As the organic diisocyanate, p, p'-diphenylmethane diisocyanate is preferable. As the chain extender, p, p'-bishydroxyethoxybenzene and 1,4-butanediol are suitable. The polyurethane elastic body is synthesized from a polyol, an organic diisocyanate and a chain extender as described above, and it is preferably used in the present invention because the polyol component is 65% by weight or more of the whole, 70% by weight or more is preferable. When the content of the polyol component is small, the elongation and elongation recovery of the obtained fiber sheet are low.

The thermoplastic fiber-forming non-elastic polymer (b) and the non-elastic fiber (B) are used as polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, polypropylene, and copolymers containing these as main components. Examples thereof include a combination and a mixture, and particularly, a polyester copolymer containing polyethylene terephthalate and ethylene terephthalate units as main components (80 mol% or more) is preferable in terms of light resistance.

The composite filament (D) constituting the fiber sheet of the present invention comprises the thermoplastic fiber-forming polyurethane elastic body (a) and the thermoplastic fiber-forming non-elastic polymer (b).
In order to be separable, it is necessary for all of them to be joined with a cross-sectional shape exposed on the outer peripheral surface of the fiber as shown in FIGS. In order that the composite filaments (D) are laminated and the joint points thereof are fused to each other by the polyurethane elastic body (a) itself, the polyurethane elastic body (a) is 30% or more in the composite filament (D). It is advantageous to occupy a surface area ratio, moreover the non-elastic polymer (b) is easy to be divided, and in order to produce a large number of thin non-elastic fibers (B), a modified cross-sectional shape such as an ellipse is used. More preferably it occupies a surface area ratio of 75%.

The average diameter of the composite filament (D) is usually 70 μm or less, preferably 15 to 50 μm. The larger the fiber diameter, the coarser the resulting fiber sheet. The polyurethane elastic filament (A) after division is usually 50
The fineness is equal to or less than denier, and one piece is set to 25 to 50 denier when a high stress stretchable napped sheet is intended, and divided into 2-3 pieces when a low stress is intended, etc. And set the single yarn to 1 to 5 denier. On the other hand, the non-elastic fiber (B) after division usually has a fineness of 30 denier or less,
The number of divisions is increased in order to generate a high-density nap, but in the case of a soft nap, the single yarn is 0.1 to 1 denier, and in the case of a soft nap, it is 5 to 5. It can be set to 30 denier or can be used together.
The diameters of the composite filaments (D) constituting the fiber sheet are not the same, and for example, when the average diameter of 20 μm is observed with an electron microscope, they are distributed in the range of 10 to 25 μm. The basis weight of the fiber sheet is in the range of ^{20 to} 200 g / m ² , and the polyurethane elastic filament (A) component preferably accounts for 30 to 70% by weight.

In the fiber sheet used in the present invention, the thermoplastic fiber-forming polyurethane elastic body (a) and the thermoplastic fiber-forming non-elastic polymer (b) are respectively melted and weighed, and then joined at the spinneret part, for example, The melt blow spinning device described in JP-A-60-99057 or JP-A-2-289107 is used to discharge the powder from a spinning nozzle, and the heated filaments jetted from both sides of the nozzle thin the composite filament. The thinned composite filaments are substantially unfocused and separated from the gas stream on a moving conveyor net or other collection device and laminated onto the net. The contact points of the polyurethane elastic body (a) are joined by fusion bonding of the polyurethane elastic body itself in a state in which the laminated composite filaments are laminated by the heat of the self.
After stacking on the collection device, before or after cooling and solidifying, heating and pressurization may be performed using a roller or the like to join them. In order to strengthen the joining of the contact points between the composite filaments, the distance from the spinning nozzle to the position where the filaments are stacked on the collecting device should not be too long, and is at most 1 m, preferably 50 cm or less. A gas flow guide passage may be provided between the nozzle and the collector, but it is not necessary.

In the present invention, a thermoplastic polyurethane elastic body is used. Further, when a polyisocyanate compound is added to a melted polyurethane elastic body and kneaded and then discharged from a spinning nozzle, heat resistance and solvent solubility resistance are improved. An improved fiber sheet is obtained.

In the fibrous sheet used in the present invention, it is preferable that the above-mentioned composite filaments are opened and laminated without being focused substantially in the longitudinal direction of the fibers. When the single yarns are fused without being opened, they are less flexible and the splitting of the composite filament is significantly impaired.

Next, as a method of dividing at least a part of the composite filaments constituting the fiber sheet, a combination of a polyurethane elastic body (a) and an inelastic polymer (b) is selected. That is, in the case of a combination such as polyurethane / polyethylene terephthalate or polyurethane / polypropylene having poor adhesiveness, a fiber sheet is stretched and the non-elastic fiber (B) is split at the same time as being stretched. The combination may be a mechanical method such as stretching, bending, twisting or rubbing, a chemical method of utilizing the difference in swelling / shrinking property by immersing in benzyl alcohol or phenol, or a combination of these methods.

As a method for stretching the fiber sheet to stretch the non-elastic fiber (B) of the composite filament, if necessary, the fiber sheet is heated by contact with a heating fluid or by a heating roller and the like, and the non-elastic fiber between the rollers is not heated. It is possible to apply a known method in which the stretched non-elastic fiber (B) is stretched in at least one direction to develop the fiber performance. If necessary, the biaxial stretching method used for the film can be used.

The draw ratio depends somewhat on the conditions and applications of melt blow spinning, but the draw ratio (Rmax) showing the maximum stress (strength) in the tensile test for measuring the breaking strength and elongation.
Is usually set to about 70 to 120% (however, the elongation limit of the polyurethane elastic filament (A) is not exceeded). For example, polyethylene terephthalate is 3 to 7
Double, nylon 6 2.5-6 times, polypropylene 4-4
It is about 12 times, but its upper limit is about 6 times because it is combined with polyurethane elastic filaments.

In the fiber sheet, the non-elastic fibers (B) are laminated by splitting and stretching at a length twice or more than the length of the polyurethane elastic filaments (A) at the joining points without tension. The non-elastic fiber (B) exists in the form of slack, loop or fluff. Draw ratio of Rmax 90
When it is set to a large value of not less than%, a part of the non-elastic fiber (B) is cut to obtain a fiber sheet having a lot of fluffy nap. When it is further 150% or more, the strength of the fiber sheet may be lowered and the holding power of the fluff may be lowered.

The fiber sheet of the present invention may further include a step of further injecting a fluid such as air or water so that the inelastic fiber (B) is unevenly distributed on one side. It is more effective if the fibrous sheet is stretched by, for example, 1.5 to 2.0 times, so that the texture of the woven fabric can be further imparted.

The fibrous sheet used in the present invention has a breaking elongation of usually 300% or more, preferably 500 to 700%, and the breaking strength varies depending on the thickness of the fibrous sheet, but is 0.5.
It is at least kg / cm, preferably at least 1.0 kg / cm. Also, the recovery rate at 100% elongation is usually 80% or more,
It is preferably a fiber sheet having a stretch recovery of 85% or more. Another characteristic of the fiber sheet is that it has extremely excellent air permeability and a soft texture.

The napped sheet of the present invention is manufactured by laminating the non-elastic short fibers (C) on the above fiber sheet and intertwining them. As such non-elastic short fibers, polyester fibers, nylon fibers, acrylic fibers, and polyolefins are used. A multi-component fiber that can be divided into a series fiber and an ultrafine fiber of 0.01 to 0.8 denier, or a staple fiber such as cotton, rayon, wool and silk is used. Artificial leather is suitable for splittable multi-component fibers, cotton and / or rayon for applications requiring sweat absorption, and cotton and / or wool because they do not cause discomfort when in contact with human skin.

The group of inelastic short fibers in the fibrous web laminated on one side or both sides of the fibrous sheet is at least partially formed by a known method such as a needle punching method or a fluid feeding method in a stretched state. Penetrating between, and polyurethane elastic filaments (A), inelastic fibers (B)
And non-elastic short fibers (C) are entangled with each other to form a napped sheet. The fluid supply method means a hole diameter of 0.01 to 1.0 m
By injecting water or air from an injection nozzle of about m at a pressure of about 10 to 80 kg / cm ² . The weight of the fibrous web is selected depending on the purpose and application, but is usually 5 to 5.
Is a 200 g / m ² approximately, in order to impart good stretchability in a sheet-like material is preferably 40 to 100 g / m ^2. The extension ratio is selected depending on the final use, but is usually 1.2 to 3.5 times.

In order to fix the napped sheet or fiber sheet to the skin layer, the present invention is preferably an elastic polymer exhibiting rubber-like elasticity such as urethane type, silicon type, acrylic type and synthetic rubber type in an expanded state. The above solution or emulsion is impregnated by a dipping method, a coating method, a gravure method, a spray method or the like and dried to form a packed layer. In order not to impair the stretchability, air permeability and flexibility of the napped sheet, the napped sheet may be partially fixed in a sea-island shape, a dot shape, a linear shape or a lattice shape (50 to 90% in area ratio). The thickness of the filling layer is usually 10 to 80 μm or the weight of the filling is usually 6 to 6
It is 0 g / m ² , and if it exceeds this range, the stretchability decreases, while if it is too small, the fixation becomes insufficient. The elongation ratio in this step is preferably 1.5 to 3.0 times.

The polyurethane elastic body suitable for the filling layer and the skin layer of the leather-like sheet is a known polymer composed of a polyol, an organic diisocyanate and a chain extender, which is polymerized mainly by a urethane bond. Select according to the requirements (for example, “Synthesis / Blending and Functionalization / Application Development of Polyurethane”, Technical Information Institute Co., Ltd., 1989, P. 446).
~ 449). The polymer may be the main component, and another polymer may be mixed in an appropriate amount, for example, 5 to 30% depending on the purpose. The other polymer is preferably compatible with the polyurethane elastomer.

For the skin layer (silver surface layer), for example, a napped sheet is coated with a solution of an elastic polymer or an aqueous emulsion by a coater, dried, and then a solution of a water-miscible organic solvent containing 10 to 35% by weight of a polyurethane elastic body is used. Apply about 50 to 1000 g / m ² using a reverse roll coater or knife coater, immerse this in water or a mixed system of water and solvent to wet coagulate, then wash with water (desolvent) and dry. Or by applying an organic solvent solution of polyurethane elastic material on a release paper with a coater with a coater and drying to form a skin layer, and then applying a solution of an elastic polymer or an aqueous emulsion on the skin layer with a coater. Then, after drying, a napped sheet in an expanded state (preferably 1.3 to 3.0 times) is thermocompression-bonded to the applied surface to form a laminate. In the present invention, the latter method is preferred, in which the polyurethane elastic filaments contained in the napped sheet are not affected by the solvent of the elastic polymer such as polyurethane during formation of the filling layer.

If necessary, the leather-like sheet material of the present invention may be subjected to a known kneading process to impart drapeability. Further, when the back surface is made into a suede tone, the sheet-like material is further buffed and raised, but it is carried out by a known method in which a protrusion structure made of sandpaper or a polymer elastic body is run at a high speed by a roll method or a belt method. ..

[0031]

The leather-like sheet material of the present invention comprises a nonwoven fabric of polyurethane elastic filaments as a constituent component of the fibrous base material, and in the stretched state, non-elastic short fibers are laminated and entangled and filled with an elastic polymer. Therefore, it is rich in elastic and elastic recovery from rubber and has a high density of naps and flexibility. Further, according to the production method of the present invention, a stretchable leather-like sheet material having the above properties can be produced industrially easily and at low cost. The stretchable sheet material of the present invention is useful as a material for shoes, bags, bags, furniture, interiors, car seats, clothes and the like.

The sheet-like material of the present invention is evaluated by the following physical property values. (Break strength and elongation) A sample with a width of 2 cm was JIS L-
According to 1096, gripping interval is 5 cm, pulling speed is 20c
It is stretched at m / min, and the strength and elongation per 1 cm width at break are measured. (100% (or 50%) elongation recovery rate) A sample having a width of 2 cm is stretched by 100% (or 50%) at a gripping interval of 5 cm and a tensile speed of 10 cm / min, and immediately recovered to the original length at the same speed. The residual elongation L (%) is obtained from the recorded load-elongation curve, and the elongation recovery rate of 100% (or 50%) is calculated by the following formula.

## EQU1 ## 100% (or 50%) elongation recovery rate (%) = 100-L (rigidity and softness) 45 ° cantilever method of JIS L-1096.

[0033]

【Example】

Comparative Example 1 Dehydrated polybutylene adipate 116 having a hydroxyl value of 56
0 part (all the following parts mean parts by weight) and 179 parts of 1,4 butanediol were charged into a kneader with a jacket, sufficiently dissolved with stirring, and then kept at a temperature of 85 ° C. , P'-diphenylmethane diisocyanate was added and reacted. Approximately 3 with continuous stirring
In 0 minutes, a powdery polyurethane was obtained, which was molded into pellets by an extruder and was placed in dimethylformamide at 25 ° C.
The relative viscosity at a concentration of 1 g / 100 cc measured by
The thermoplastic polyurethane elastic body of was obtained.

Using the polyurethane elastic pellets thus obtained as a raw material, a melting blow spinning device having slits for jetting heated gas on both sides of a spinning nozzle having a diameter of 0.6 mm arranged in a row is used and the melting temperature is 245. ℃, air discharged from the nozzle, heated to 200 ℃ air 1.8kg / cm
^It was sprayed from the slit with a pressure of ² to make it thinner. The thinned filaments were collected on a conveyor consisting of a 30-mesh wire mesh installed 25 cm below the nozzle, and were caught by a roller with a basis weight of 60 g / m ² , 100% elongation recovery rate 91.
% Non-woven fabric was obtained. In this non-woven fabric, monofilaments of polyurethane elastic fibers having an average diameter of 20 μm were opened and laminated, and the entanglement points between the filaments were joined to each other by fusion bonding.

The above-mentioned polyurethane non-woven fabric was laminated on both sides with an easily dyeable polyester web (Basis weight: 45 g / m ² ) described below.
Perform needle punching of 1000 needles / cm ² from above and below,
A non-woven fabric having a thickness of 1.2 mm was obtained. 100% of this non-woven fabric
The elongation recovery rate was 69%.

On the other hand, a polyurethane organic solvent solution having the following composition was coated on a squeezed release paper with a knife coater so that the dry thickness was 30 μm, and this was dried with hot air at 100 ° C. for 3 minutes to form a polyurethane skin layer. Formed.

Polyurethane organic solvent solution (Dainichi Seika Kogyo Co., Ltd., Resamine ME-8115LP, solid content 30%): 100 parts Colorant (Dainichi Seika Kogyo Co., Ltd., Seika Seven DUT-4891 Brown): 15 parts・ Dimethylformamide / methylethylketone = 3 /
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Further, a polyurethane adhesive having the following composition was applied on the surface of the skin layer with a knife coater so that the dry weight was 20 g / m ^2, and dried with hot air at 100 ° C. for 3 minutes.

Polyurethane organic solvent solution (Resamine UD-8300LP, Dainichiseika Kogyo KK, solid content 50%): 100 parts Crosslinking agent (Resamine UD-crosslinking agent, Dainichiseika Kogyo KK): 8 parts Crosslinking accelerator (Resamine UD-103 accelerator, Dainichiseika Kogyo KK):
2 parts ・ Dimethylformamide / methylethylketone = 5 /
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The above-mentioned sheet-like material was bonded to the upper surface of the polyurethane adhesive layer by thermocompression bonding at 120 ° C., and after the adhesive was cured, the release paper was peeled off to give a silver-sided sheet-like material (thickness: 0. 60
mm) was manufactured.

Example 1 The thermoplastic polyurethane elastic body of Comparative Example 1 was heated to 245 ° C.
Polyethylene terephthalate (easily dyed polyester) obtained by copolymerizing 5% by weight of polyethylene glycol having a molecular weight of 600 was heated and melted at 285 ° C., respectively, and bonded to a spinning nozzle at a weight ratio of 2: 1 as shown in FIG. Then, in the same manner as in Comparative Example 1 below, a fiber sheet composed of composite filaments having an average diameter of 24 μm was obtained. In this fibrous sheet, the composite filaments were opened and laminated into single yarns, and the entanglement points between the composite filaments were bonded by fusion of the polyurethane elastic material components.

Next, the fiber sheet was stretched 3.0 times in a hot water of 80 ° C. by a rotating roller and was sandwiched between a stainless steel plate which was moved up and down twice a second to repeat the expansion and contraction of the fiber sheet (3.0 ˜4.0 times elongation), the composite filaments constituting the fiber sheet were split. The polyurethane elastic filaments produced by splitting have a fineness with an average distribution of 4 denier and the split and stretched easily dyed polyester fibers have an average of 0.8 denier. It was stacked.

Then, the easily dyeable polyester web (fineness: 1.5 denier, fiber length: about 51 mm, crimp number: 20 threads / inch, basis weight: 15 g / m) in a state in which the divided / stretched fiber sheet was stretched 2.0 times. ² ) was laminated on both sides, and a columnar water stream was jetted at a pressure of 45 kg / cm ² from three rows of jet nozzles having a hole diameter of 0.25 mm arranged at intervals of 2 mm, and then water entanglement was similarly performed from the opposite side. The obtained napped sheet showed a 100% elongation recovery rate of 82% and had a texture of flocked cloth.

With the napped sheet being stretched 1.5 times, a filling layer (adhesive layer) and a skin layer were formed by thermocompression bonding in the same manner as in Comparative Example 1, and a silver surface with a slightly strong lateral drawing was formed. A sheet material was manufactured.

Example 2 An aqueous polyurethane (Elastron CT-Daiichi Kogyo Seiyaku Co., Ltd.) was used with the napped sheet of Example 1 stretched 1.5 times.
After impregnating 5% aqueous solution of 7) so that the impregnation rate becomes 200%, hot air drying is performed at 150 ° C. for 3 minutes, and then a filling layer and a skin layer are formed in the same manner as in Example 1, and the silver surface An attached sheet-like material (thickness 0.55 mm) was manufactured.

Example 3 The following water-soluble polyester copolymer was polymerized for the multi-component fiber used for the non-elastic staple fiber.

38.74 parts by weight of dimethyl terephthalate,
Dimethyl isophthalate 31.95 parts by weight, 5-sulfoisophthalic acid dimethyl sodium salt 10.34 parts by weight, ethylene glycol 54.48 parts by weight, calcium acetate-
Water salt 0.073 parts by weight, manganese acetate tetrahydrate 0.024
After carrying out the transesterification reaction while distilling off methanol by distillation at 170 to 220 ° C. under a nitrogen stream, 0.05 part by weight of trimethyl phosphate, 0.04 part by weight of antimony trioxide as a polycondensation catalyst and 1, Add 17.17 parts by weight of 4-cyclohexanedicarboxylic acid 220-235 ° C
At the reaction temperature of 1, the theoretical amount of water was distilled off to effect the esterification. After that, the pressure inside the reaction system is further reduced and the temperature is raised to 28
Polycondensation was carried out at 0 ° C. and 0.2 mmHg for 2 hours.

Polyethylene terephthalate and the above water-soluble polyester copolymer were compounded by a known composite spinning method to produce a multi-component fiber. That is, the volume ratio of polyethylene terephthalate / water-soluble polyester copolymer is 3 /
1, and a water-soluble polyester copolymer was used as the C ₂ component to form a cross section as shown in FIG.
It was wound on a spinneret plate at 0 ° C. at a speed of 1,000 m / min while applying a water emulsion containing 15% of a spinning oil agent. This unstretched yarn was heated to 3.2 by using a hot stretching roller at 80 ° C.
It was drawn twice to obtain a drawn yarn of 100d / 50f.

A web obtained by stapling the above multi-component fibers (fiber length 51 mm, crimp number 20 threads / inch,
After changing the basis weight to 20 g / m ² ) and performing needle punching, 9
A leather-like sheet was prepared in the same manner as in Example 1 except that the water-soluble polyester copolymer component of the web was eluted and removed by immersing it in hot water of 5 ° C. for 2 minutes to produce a polyethylene terephthalate component divided into nine pieces. Was manufactured.

Example 4 A composite sheet with a silver surface was produced in the same manner as in Example 1 except that the weight ratio of the composite filament was 1: 1, the average diameter was 28 μm, and the composite shape was changed as shown in FIG. did.

[0051]

[Table 1]

[Brief description of drawings]

FIG. 1 shows an example of a cross-sectional shape of a composite filament suitable for the present invention.

FIG. 2 shows an example of a cross-sectional shape of a divisible inelastic short fiber suitable for the leather-like sheet material of the present invention.

[Explanation of symbols]

A polyurethane elastic filament component B non-elastic fiber component C ₁ polyethylene terephthalate C ₂ water-soluble polyester copolymer

Claims (6)

[Claims] 1. A sheet-like material comprising a napped sheet having a filling layer made of an elastic polymer and a skin layer made of a polyurethane elastic body, the napped sheet comprising polyurethane elastic filaments (A) and non-elastic fibers (B). ) Are laminated, and the joint points of the laminated polyurethane filaments (A) are fused by the polyurethane filaments (A) themselves, and the inelastic fibers (B) are between the joint points of the polyurethane filaments (A). The non-elastic short fiber (C) is further laminated and entangled with the fiber sheet that is laminated at least twice as long as the length under no tension. 2. The sheet-like article according to claim 1, wherein the sheet-like article has a 50% elongation recovery rate of 70 to 100%. 3. A sheet-like product comprising a fibrous sheet on which a filling layer made of an elastic polymer and a skin layer made of a polyurethane elastic material are formed, the fibrous sheet comprising polyurethane elastic filaments (A) and non-elastic fibers (B). ) Are laminated, and the joint points of the laminated polyurethane filaments (A) are fused by the polyurethane filaments (A) themselves, and the inelastic fibers (B) are between the joint points of the polyurethane filaments (A). The sheet-like material, which is laminated by a length that is at least twice as long as the length under no tension. 4. A thermoplastic fiber-forming polyurethane elastic body (a) and a thermoplastic fiber-forming non-elastic polymer (b) are bonded to each other in the longitudinal direction with a shape exposed on the outer peripheral surface of the fiber. To produce a fiber sheet in which the composite filaments (D) are laminated without being substantially bundled, and the joint points of the laminated composite filaments (D) are fused by the polyurethane elastic body (a) itself. A step of dividing the composite filament (D) constituting the fiber sheet into a polyurethane filament (A) and an inelastic fiber (B), a step of stretching the fiber sheet and stretching the inelastic fiber (B), A step of laminating non-elastic short fibers (C) on the fiber sheet and intertwining them into a napped sheet; and a filling layer for filling the napped sheet with an elastic polymer to fix a group of non-elastic short fibers (C) And po And a step of forming a skin layer made of a polyurethane elastic body. 5. The step of forming a filling layer and a skin layer comprises applying a solution of a polyurethane elastic material in an organic solvent onto a release paper with a squeeze and drying it to form a skin layer, and then forming an elastic layer on the skin layer. The method according to claim 4, which is a step of applying a solution of a molecule or an aqueous emulsion, then drying, and then pressing and bonding a napped sheet in an elongated state to the applied surface. 6. A thermoplastic fiber-forming polyurethane elastic body (a) and a thermoplastic fiber-forming non-elastic polymer (b) are bonded to each other in a longitudinal direction with a shape exposed on the outer peripheral surface of the fiber. To produce a fiber sheet in which the composite filaments (D) are laminated without being substantially bundled, and the joint points of the laminated composite filaments (D) are fused by the polyurethane elastic body (a) itself. A step of dividing the composite filament (D) constituting the fiber sheet into a polyurethane filament (A) and an inelastic fiber (B), a step of stretching the fiber sheet and stretching the inelastic fiber (B), And a step of forming a filling layer for filling the fibrous sheet with an elastic polymer to adhere it to the skin layer, and a step of forming a skin layer made of a polyurethane elastic body. Law.