CA1118170A - Process for the preparation of leatherlike sheet materials - Google Patents
Process for the preparation of leatherlike sheet materialsInfo
- Publication number
- CA1118170A CA1118170A CA000308728A CA308728A CA1118170A CA 1118170 A CA1118170 A CA 1118170A CA 000308728 A CA000308728 A CA 000308728A CA 308728 A CA308728 A CA 308728A CA 1118170 A CA1118170 A CA 1118170A
- Authority
- CA
- Canada
- Prior art keywords
- fabric
- hollow composite
- segments
- hollow
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/36—Matrix structure; Spinnerette packs therefor
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the preparation of leatherlike sheet materials which comprises: preparing hollow composite fibers, each composed of 16 to 96 alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, the hollow composite fiber having a denier of 1 to 20 and each segment having a denier of 0.01 to 0.5;
forming a fabric using thus prepared hollow composite fibers, removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and applying an elastic polymer to the fabric. The resultant leatherlike sheet materials have fine touch, excellent repulsive elasticity and excellent wrinkle resistance similar to natural suede.
A process for the preparation of leatherlike sheet materials which comprises: preparing hollow composite fibers, each composed of 16 to 96 alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, the hollow composite fiber having a denier of 1 to 20 and each segment having a denier of 0.01 to 0.5;
forming a fabric using thus prepared hollow composite fibers, removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and applying an elastic polymer to the fabric. The resultant leatherlike sheet materials have fine touch, excellent repulsive elasticity and excellent wrinkle resistance similar to natural suede.
Description
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a process for the pre-paration of leatherlike sheet materlals. More particularly, the present invention is concerned with a process for manufacturing leatherlike sheet materials from hollow composite fibers of a type which generates extra fine fibers, each hollow composite fiber composed of polyester or polyamide segments and polystyrene segments.
Description of the Prior Art Heretofore, it has been known to produce leatherlike sheet materials using extra fine fibers. U.S. Patent No.
4,051,287, issued on September 27, 1977 to Hayashi et al and U.S~
Patent No. 4,109,038, issued on August 22, 1978 to Ozaki et al disclosed a suede-like woven or knitted fabric (a leatherlike sheet material) which was produced by applying an elastic polymer to a raised woven or knitted fabric comprising extra fine fibers obtained from hollow composite fibers, the hollow composite fiber being composed of at least four alternately arranged segments of fiber-forming polyester and fiber-forming polyamide which are mutually adhered side-by-side encompassing a hollow space and which extend along the longitudinal axis of the fiber to form a tubular body. This hollow composite fiber has the advantages that the segments of the hollow composite fiber are readily separable by 3~
mechanical action to form ex-tra fine fibers and all the segments are usable as extra fine fibers. The obtained extra fine fibers, however~ must be dyed by a very complicated process, because they consist of two polymers having properties different from each other.
U.S. Patent No. 3,865,67~, issued on February 11, 1975 to Okamoto et al, discloses a suede-like raised woven fabric (a leatherlike sheet material) which was produced by applying an elastic polymer to a raised woven fabric comprising extra fine fibers obtained from islands-in-sea type composite fibers. The islands-in-sea type composite fiber can be converted into a bundle of the island component fibers (extra fine fibers) b~
removing the sea component from the composite fiber.
However, the islands-in-sea type composite fiber h s the disadvantages that a spinneret having a complicated structure must be employed in the manufacturing process of the islands-in-sea type composite fiber and further the process control is very difficult.
Japanese Patent Application Laid-Open No.
484n2/76, Takemura et al, published on April 26, 1976 discloses a hollow composite fiber which is divisible into fine fibers, and a leatherlike sheet material which is obtained by applying a polyurethane to a non-woven ~5 fabric formed with the hollow composite fibers. As for a divisible polymer combination, the Japanese Patent Application discloses the combination of polyamide and polyethylene terephthalate, polyethylene terephthalate 7~
and polystyrene, and also polyamide and polystyrene.
However, the Japanese Patent Application neither teaches the denier of the ~ine fibers nor suggests the structure of the hollow composite fiber composed of polyester or polyamide and polystyrene segments.
According to the experiments conducted by the present inventors, it was very difficult to produce a hollow composite fiber having good properties composed of polyester or polyamide and polystyrene segments.
In manufacturing a hollow composite fiber composed of alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, the drawing operation of the melt-spun hollow composite fiber was very difficult, because the adhesive force between the segments of differ-ent polymers was poor and the physical properties of the segments of different polymers greatly differed from each other, and accordingly it was very difficult to obtain the hollow composite fiber suited for commercial use. SUMMARY OF THE INVENTION
It has now been found by the present inventors that a hollow composite fiber composed of polyester or polyamide and polystyrene segments and having a specific denier and specific structure has good melt-forming properties in the melt-spun and drawing processes and can be preferably used for the preparation of leather-like sheet materials having excellent properties.
The present invention relates to a process for the preparation of leatherlike sheet materials which comprises the steps of:
(l) preparing hollow composite fibers, each composed of 16 to 96 alterna-tely arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, said hollow composite fiber having a denier of l to 209 and said each segment having a denier of 0.0l to 0.5~
Field of the Invention The present invention relates to a process for the pre-paration of leatherlike sheet materlals. More particularly, the present invention is concerned with a process for manufacturing leatherlike sheet materials from hollow composite fibers of a type which generates extra fine fibers, each hollow composite fiber composed of polyester or polyamide segments and polystyrene segments.
Description of the Prior Art Heretofore, it has been known to produce leatherlike sheet materials using extra fine fibers. U.S. Patent No.
4,051,287, issued on September 27, 1977 to Hayashi et al and U.S~
Patent No. 4,109,038, issued on August 22, 1978 to Ozaki et al disclosed a suede-like woven or knitted fabric (a leatherlike sheet material) which was produced by applying an elastic polymer to a raised woven or knitted fabric comprising extra fine fibers obtained from hollow composite fibers, the hollow composite fiber being composed of at least four alternately arranged segments of fiber-forming polyester and fiber-forming polyamide which are mutually adhered side-by-side encompassing a hollow space and which extend along the longitudinal axis of the fiber to form a tubular body. This hollow composite fiber has the advantages that the segments of the hollow composite fiber are readily separable by 3~
mechanical action to form ex-tra fine fibers and all the segments are usable as extra fine fibers. The obtained extra fine fibers, however~ must be dyed by a very complicated process, because they consist of two polymers having properties different from each other.
U.S. Patent No. 3,865,67~, issued on February 11, 1975 to Okamoto et al, discloses a suede-like raised woven fabric (a leatherlike sheet material) which was produced by applying an elastic polymer to a raised woven fabric comprising extra fine fibers obtained from islands-in-sea type composite fibers. The islands-in-sea type composite fiber can be converted into a bundle of the island component fibers (extra fine fibers) b~
removing the sea component from the composite fiber.
However, the islands-in-sea type composite fiber h s the disadvantages that a spinneret having a complicated structure must be employed in the manufacturing process of the islands-in-sea type composite fiber and further the process control is very difficult.
Japanese Patent Application Laid-Open No.
484n2/76, Takemura et al, published on April 26, 1976 discloses a hollow composite fiber which is divisible into fine fibers, and a leatherlike sheet material which is obtained by applying a polyurethane to a non-woven ~5 fabric formed with the hollow composite fibers. As for a divisible polymer combination, the Japanese Patent Application discloses the combination of polyamide and polyethylene terephthalate, polyethylene terephthalate 7~
and polystyrene, and also polyamide and polystyrene.
However, the Japanese Patent Application neither teaches the denier of the ~ine fibers nor suggests the structure of the hollow composite fiber composed of polyester or polyamide and polystyrene segments.
According to the experiments conducted by the present inventors, it was very difficult to produce a hollow composite fiber having good properties composed of polyester or polyamide and polystyrene segments.
In manufacturing a hollow composite fiber composed of alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, the drawing operation of the melt-spun hollow composite fiber was very difficult, because the adhesive force between the segments of differ-ent polymers was poor and the physical properties of the segments of different polymers greatly differed from each other, and accordingly it was very difficult to obtain the hollow composite fiber suited for commercial use. SUMMARY OF THE INVENTION
It has now been found by the present inventors that a hollow composite fiber composed of polyester or polyamide and polystyrene segments and having a specific denier and specific structure has good melt-forming properties in the melt-spun and drawing processes and can be preferably used for the preparation of leather-like sheet materials having excellent properties.
The present invention relates to a process for the preparation of leatherlike sheet materials which comprises the steps of:
(l) preparing hollow composite fibers, each composed of 16 to 96 alterna-tely arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, said hollow composite fiber having a denier of l to 209 and said each segment having a denier of 0.0l to 0.5~
(2) forming a fabric using thus prepared hollow composite fibers;
~ 3) removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and lS (4) applying an elastic polymer to the fabric.
BRIEF DESCRIPTION OF THE DRA~1INGS
Figure l is a schematic cross-sectional view of a hollow co~posite fiber used in the present invention.
Figure 2 is an axial cross-sectional view of a spinneret used for producing a hollow composite fiber.
Figure 3 is a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line ~-A'.
Figure 4 is a partial transverse cross~sectional view of the spinneret of Figure 2 taken at line B-B'.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The hollow composite fiber employed in the presen-t invention has a schematic cross-section as illustrated in Figure l (a hollow composite fiber having the total segments of 32). In Figure 1, the hollow composite fiber 1 is composed of polyester or polyamide segments 2, polystyrene segments 3 and a center hollow space 4.
The polyester or polyamide and polystyrene segments 2 and 3 as well as the center hollow space 4 extend along the longitudinal axis of the fiber 1. Th~ polyester or polyamide segments 2 and the polystyrene seg~ents 3 are arranged alternately around the center hollow space 4 and mutually adhered side-by-side so as to form a tubular fiber body. In the embodiment of Figure 1~ the hollow space ~ is formed around the longitudinal axis of the fiber 1, and the polyester or polyamide segments 2 and polystyrene segments 3 are re~ularly and alternately arranged around the center hollow space 4. ~owever, the hollow space 4 may also be formed eccentrically with respect to the longitudinal axis, and the polyester or polyamide segments 2 and polystyrene segments 3 may be arranged around such an off-centered hollow space 4 to have irregular and different cross-sectional configurations and areas.
The hollow composite fiber employed in the present invention is composed of 8 to 48, and prefer-ably 16 to 36, of the polyester or polyamide segments and of the corresponding number of polystyrene segments.
When the total nu~ber of the segments is less than 16, the composite fiber tends to separate into each segment or break in the process of melt-spinning and/or drawing.
On the contrary, when the total number of the segments 7~
'7 is more than 969 two or more segments of polyester or polyamide in the composite fiber tend to adhere to each otherg and accordingly i-t is difficult to obtain extra fine uniform fibers having a desired denier.
The denier of each seement in the hollow composite fiber must be in the range of 0.01 to 0.~, preferably 0.05 to 0.3. When the denier is less than 0.01, two or more segments of polyester or polyamide in the composite fiber tend to adhere to each otherg and further the manufacturing process control is very difficult.
On the contrary, when the denier is more than 0.5~
the composite fiber tends to separate into each segment in the process of melt-spinning and/or drawing. The denier of hollow composite fiber is in the range of 1 to 20. When the denier is less than 1 or more than 20, it is difficult to produce the hollow composite fiber. The ratio cf the total weight of the polyester or polyamide segments to that of the polystyrene segments is not necessarily limited a although a ratio of be-tween 50 : SO and 70 : 30 is preferable.
In the hollow composite fiber employed in the present invention, there is no limitation on the hollow ratio, i.e., the ratio by volume of the hollow space to the sum of the volume of the polyester or polyamide segments, the polystyrene segments and the hollow space. It is, however~ preferable that the hollow ratio be between 1 and 30% by volume, or more preferablyg between 2 and
~ 3) removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and lS (4) applying an elastic polymer to the fabric.
BRIEF DESCRIPTION OF THE DRA~1INGS
Figure l is a schematic cross-sectional view of a hollow co~posite fiber used in the present invention.
Figure 2 is an axial cross-sectional view of a spinneret used for producing a hollow composite fiber.
Figure 3 is a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line ~-A'.
Figure 4 is a partial transverse cross~sectional view of the spinneret of Figure 2 taken at line B-B'.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The hollow composite fiber employed in the presen-t invention has a schematic cross-section as illustrated in Figure l (a hollow composite fiber having the total segments of 32). In Figure 1, the hollow composite fiber 1 is composed of polyester or polyamide segments 2, polystyrene segments 3 and a center hollow space 4.
The polyester or polyamide and polystyrene segments 2 and 3 as well as the center hollow space 4 extend along the longitudinal axis of the fiber 1. Th~ polyester or polyamide segments 2 and the polystyrene seg~ents 3 are arranged alternately around the center hollow space 4 and mutually adhered side-by-side so as to form a tubular fiber body. In the embodiment of Figure 1~ the hollow space ~ is formed around the longitudinal axis of the fiber 1, and the polyester or polyamide segments 2 and polystyrene segments 3 are re~ularly and alternately arranged around the center hollow space 4. ~owever, the hollow space 4 may also be formed eccentrically with respect to the longitudinal axis, and the polyester or polyamide segments 2 and polystyrene segments 3 may be arranged around such an off-centered hollow space 4 to have irregular and different cross-sectional configurations and areas.
The hollow composite fiber employed in the present invention is composed of 8 to 48, and prefer-ably 16 to 36, of the polyester or polyamide segments and of the corresponding number of polystyrene segments.
When the total nu~ber of the segments is less than 16, the composite fiber tends to separate into each segment or break in the process of melt-spinning and/or drawing.
On the contrary, when the total number of the segments 7~
'7 is more than 969 two or more segments of polyester or polyamide in the composite fiber tend to adhere to each otherg and accordingly i-t is difficult to obtain extra fine uniform fibers having a desired denier.
The denier of each seement in the hollow composite fiber must be in the range of 0.01 to 0.~, preferably 0.05 to 0.3. When the denier is less than 0.01, two or more segments of polyester or polyamide in the composite fiber tend to adhere to each otherg and further the manufacturing process control is very difficult.
On the contrary, when the denier is more than 0.5~
the composite fiber tends to separate into each segment in the process of melt-spinning and/or drawing. The denier of hollow composite fiber is in the range of 1 to 20. When the denier is less than 1 or more than 20, it is difficult to produce the hollow composite fiber. The ratio cf the total weight of the polyester or polyamide segments to that of the polystyrene segments is not necessarily limited a although a ratio of be-tween 50 : SO and 70 : 30 is preferable.
In the hollow composite fiber employed in the present invention, there is no limitation on the hollow ratio, i.e., the ratio by volume of the hollow space to the sum of the volume of the polyester or polyamide segments, the polystyrene segments and the hollow space. It is, however~ preferable that the hollow ratio be between 1 and 30% by volume, or more preferablyg between 2 and
3~ 7~3 15% by volume. The hollow ratio can be determined by the following method. A cross-sectiollal profile at some point along the fiber is observed, from which the cross-sectional area of the hollow space and that of the fiber body are measured. ~he ratio of the cross-sectiGnal area of the hollow space to tha-t of the fiber body is determined from these measured values.
The same procedures are repeated 20 times at different points along the fiber. The hollow ratio of the fiber represents a mean value of the determined values of the ratios. When the hollow composite fibers have a hollow ratio of between 1 and 30% by volume, the hollow composite fibers can be processed by, for example 3 a melt-spinning operation, a drawing operation, and a weaving operation without the individual segments being separated from each other. The polystyrene segments in thus obtained hollow composite fiber are readily dissolved with a solvent thereof to form extra fine fibers composed of individual polyester or polyamide segments, In the present invention, the polyester used for the polyester segments may be selected ~rom the group consisting of (1) alkylene terephthalate homo-polyes-ters, in which the alkylene group is derived from polymethylene glycol of the formula: HO (CH2) -OH, where p represents an integer of from 2 to 10 and (2) alkylene terephthalate - third ingredient copolyesters, in which the alkylene group is the same as defined _ 9 _ above and the third ingredient is derived from at least one compound selected from the group consisting of adipic acid, sebacic acid, isophthalic acidg diphenylsulfone-dicarboxylic acid, naphthalene-dicarboxylic acidg hydroxybenzoic acid, propyleneglycol, cyclohexane~dimethanol and neopentyl glycol, in an amount o~ 10% or less by mole based on the amount of the alkylene terephthalate ingredient. The polyester used for the polyester segments may also be a blend o~
two or more of the above-mentioned homopolyes-ters and the copolyesters. Among these polyesters~ polyethylene terephthalate is particularly preferable. The prefer-able polyesters in the present invention have an intrinsic viscosity of between 0.4 and 1.2 when measured at 35C in 0-chlorophenol.
The polyamide used for the polyamide segments may be selected from the group consisting of nylon ~, nylon 6, nylon 669 nylon 79 nylon 610, nylon 11, nylon 12, polyamides of bis(p-aminocyclohexyl) methane with a dicarboxylic acid such as lg7-heptanedicarboxylic acid and l,10-decamethylenedicarboxylic acid, copoly-amides o~ two or more of the above-mentioned polyamides and mixtures of two or more of the above-mentioned polyamides and copolyamides. Among these polyamides, nylon 6 and nylon 66 are particularly preferable. The preferable polyamides in the present invention have an intrinsic viscosity of between 1.0 and 1.3 when measured at 35C in m-cresol.
The polyester or polyamide segm~nts may contain therein an anti-static agent~ a delustering agent such as titanium dioxide, a coloring agent such as carbon black, and an anti-oxidizing agen' having thermal stability.
In the present invention, the polystyrene used for the polys-tyrene segments may be selected from the group consisting of (1) a homopolymer of styrene and (2) styrene-copolymers obtained by copolymerizing more than 80~ by weight of styrene with less than 20% by weight of other vinyl compounds. As for vinyl compounds copolymerizable with styrene, there are exemplified vinyltoluene 9 chlorostyrene~ acrylonitrile, ethylene, propylene~ butylene~ butadiene and isoprene.
The preferable polystyrenes in the present invention have a melt index of between 10 and 30.
The process for the preparation of the hollow composite fiber as shown in Figure 1 is illustrated in the following paragraphs.
Figure 2 shows an axial cross-sectional view of a spinneret used for producing the hollow composite fiber as shown in Figure 1 (the hollow composite fiber having the total segments of 32). Figure 3 shows a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line A-A'. Figure 4 shows a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line B-B'.
In the spinneret of Figure 2~ the top plate 12 is fixed to the bottom plate 11 with a set-screw 21 17`~
and is sealed against the bottom plate 11 by gasket 20.
The bottom plate 11 has a recessed region which forms a narrow fluid passage 14 between the ~ottom plate 11 and top plate 12.
This fluid passage 14 is formed in the form of circular groove as shown in Figure 4. The bottom plate 11 has a plurality of spinning orifices 13, each of which has four circularly arranged slits 17 in the bottom portion as shown in Figure 4 and an upper opening which communicates with the fluid passage 14 passing through a plateau-like protrusion 18. The number of slits is in 0 the range of 1 to 8, and preferably 4. The top plate 12 has a guide hole 15 for the first melted polymer and a plurality of guide holes 16 for the second melted polymer which are provided for each spinning orifice 13. The guide holes 16 for the second melted polymer are formed in fours around the guide hole 15 for the first melted polymer as shown in Figure 3. The number of guide holes for the second melted polymer is not necessarily limited, although a number of between 1 and 6 corresponding to each guide hole for the first melted polymer is preferable. The guide hole 15 for the first melted polymer communicates with the ~0 fluid passage 14 through sixteen circularly arranged small ori-fices 19 (as shown in Figure 3) which are formed in the bottom of the guide hole 15 for the first melted polymer. The small ori-fices 19 are so arranged that the first melted polymer extruded through the small orifices 19 may impinge on ~ - 11 -the plateau of the protrusion 18. Upper opening of the guide hole 15 for the first melted polymer communicates with the supply means (not shown~ of the first melted polymer. Lower and upper openings of the guide hole 16 for the second melted polymer are communicated with unprotruded regions of the fluid passage 14 and the supply means (not shown) of the second melted polymer respectively.
The number of small orifices 19 formed in the bottom of each guide hole 15 for the first melted polymer must be 2~ same as the number of segments fo-,~med from the first melted polymer in the ob-tained hollow composite fiber. Accordingly 9 the number of small orifices is in the range of 8 to 48, preferably 16 to 36 in the present invention.
The first melted polymer is supplied to the guide hole 15 for the first melted polymer from the supply means (not shown) and impinges on the plateau of the protrusion 18 through the small orifices 19 to form sixteen fine streams of the first melted polymer, which streams are led to the spinning origice 13. The second melted polymer is supplied to the guide holes 16 for the second melted polymer from the supply means (not shown) and led to the fluid passage 14, and contacts with the first melted polymer after its flow having been streamlined uniformly by the protrusion 18.
The both melted polymersg contacting each other, form a composite stream composed of the sixteen first melted ~3~L7 polymer ~ine streams, each being surrounded by the second mel-ted polymer~ which composite stream is led to the spinning orifice 13 and extruded through four slits 17 to make a hollow COTnpOSite Eiber having 32 segments as shown in Figure 1.
In the present invention, polyesters or polyamides and polystyrenes are used as the polymers for the first and the second melted polymers respectively.
Polyesters or polyamides used for the first melted polymer have preferably a melt viscosity of 1000 to 3500 poises, and po]ystyrenes used for the second melted polymer have preferably a melt viscosity of 500 to 1500 poises. In the melt spinning operation, it is preferable that the melt spinning temperature is between 280 and 300C and the take-up speed of spun filaments tundrawn filaments) is between 500 and 2000 m/min.
In the ~resent invention., the ratio of the feeding speed (g/min) of polyesters or polyamides to that of polystyrenes is in a range of between 50 : 50 and 70 : 30. It is possible to obtain a hollow composite fiber having segments of desired cross-sectional configurations and areas by varying the ratio within the abovementioned range. Thus obtained undrawn filaments are drawn at a draw ratio of 2 to 5 to form the hollow composite fibers (drawn filaments) used in the present invention. In the drawing operation, it is preferable that -tne drawing temperature is between 40 17~
and 130C under wet or dry conditions and the take-up speed of drawn filaments in between 300 and 1000 m/lllin.
In the present invention, a fabric is formed using thus obtained hollow composite fibers. The fabric means a non-woven, woven and knitted fabrics as well as a composite thereof in the present invention.
As for non-woven fabrics, there are a web and a felty product made from the hollow composite fibers of the present invention or a mixture of the hollow composite fibers and conventional fibers each having a denier of more than about 1. The web may be formed by using a conventional apparatus for producing non-woven fabrics, such as a carding machine, cross wrapper and random webber, or formed by a method of direct fabrica-lS tion. The felty product may be formed by needlepunch-ing a plurality of webs arranged in layers.
The felty product may also be formed by needlepunching the webs together with a web a woven or knitted fabric consistin~ of conventional fibers arranged in layers.
The density of needlepunching can be determined in accordance with the requirements of the end uses of ~ j. is the non-woven fabrics, and preferably/between 200 to 800 needles/cm2. The for~ation of the felty products can also be performed by the stitch bonding method using such machines as '1Arachne," "Maliwatt'i or "Mlipol". One or both surfaces of the felty product may be raised by using a conventional raising machine, such as a roller sander machine with sand paper or / r c/ O/C in ~r ~
7~
emery clothO
The woven fabric is prepared from a multifilament yarn or a spun yarn consisting of the hollow composite fibers of the present invention as the warp and/or S weft of the woven fabric by using a conventional loom.
One or both surfaces of the woven fabric may be raised by using a conventional raising machine, such as emery raising machine, tea~el raising machine, wire raising machine, or a roller sander machine with sand paper or emery cloth. As for the woven fabrics used for the raised woven fabrics~ a satin fabric is preferably used, which is composed of a multifilament yarn or a spun yarn consisting of the hollow composite fibers of total denier ranging from 50 to 500 as the weft, and a multifilament yarn, a mixed multifilament yarn, a spun yarn or a mixed spun yarn consisting of the conventional fibers (whose monofilament denier is more than about 1) of total denier ranging from 50 to 300 as the warp. When it is desired to raise two surfaces (a surface and back surface) of the fabric~ a double faced woven fabric having a satin structure in both surfaces is preferably used. Among the satin fabrics, 3-ply satin and 4-ply satin fabrics are particularly preferable. In particular, a textured yarn having crimps which consists of polyesters~ such as poly-ethylene terephthalate or polyamides~ such as nylon 6 and nylon 66 is preferably used as the warp yarn.
The knitted fabric is prepared from a multifilament yarn or a spun yarn consisting of the hollow composite fibers of th~ present invention by using a conventional knitter. When a warp knitted fabric is employed9 it is preferable that the front yarns thereof are formed with a multifilament yarn or a spun yarn consisting of the hollow composite fibers and the back yarns thereof are for,ned with a multi-filament yarn, a mixed multifilament yarn~ a spun yarn or a mixed spun yarn having the conventional denier.
When a circular knitted fabric is employed a it is preferable that both the front and back portions or only the front portion thereof are formed with a multifilament yarn or a spun yarn consisting of the hollow composite fibers. One or both surfaces of the knitted fabric may be raised as in the case of the woven fabric.
In the present specification, the multifilament yarn means, for example~ a single twist filament yarn, an untwisted filament yarn, a twin filament yarng a triple filament yarn, a "Taslan1' textured yarn ~trade-mark of Du Por,t~ or a textured yarn having crimps obtained by a method such as false-twisting, stuffer crimping, edge crimping and air jet-crimping. The mixed multifilament yarn means a multifilament yarn consisting of two or more different filaments.
In the present invention~ thus obtained fabric is treated with a sol~ent of polystyrenes to remove the polystyrene segments of the hollow composite fibers 7~
contained in the fabric. All the polystyrene segments of the hollow composite fibers are substantially removed with a solven-t such as benzeneg toluene, trichloro-ethylene and perchlorethylene at room or elevated temperature. Accordingly~ the fabric containing extra fine fibers is obtained~ which extra fine fibers consist essentially of polyester or polyamide segments 7 each having a denier of 0.01 to 0.5. This ope~ation of removing the polystyrene segments of the hollow composite fibers may be conducted after the process of applying an elastic polymer to the fabric as described below.
The abovesaid operation of raising the fabric may be conducted after the operation of remo~ing the polystyrene segments and before the process of applying an elastic polymer to the fabric. If desired or necessary, shearingg buffing or brushing operation may be conducted on the raised fabric after the operation of removing the polystyrene segments from the hollow composite fibers.
In the present invention, an elastic polymer i5 applied to thus obtained fabric (a fabric obtained before or after the operation of removing the poly-styrene segments from the hollow composite fibers). As for the elastic polymers 3 there are natural rubber and synthetic elastic polymers such as acrylonitrile-butadiene copo~ymers, polychloroprene, styrene-butadiene copolymersg polybutadiene, polyisopreneg ethylene-J
~ 8~70 propylene copolymers, acrylate-type copolymers 9 silicone, polyurethanes, polyacrylates~ polyvinyl acetate, polyvinyl chloride, polyester-polyether block copolymers, 4n~
ethylenevinyl acetate copolymers~ ~. The method which comprises applying an urethane pre-polymer to the fabric and then heating the applied fabric to form a polyurethane in the fabric is also preferably employed in the present invention.
The elastic polymer is applied to the fabric in the form of a solution such as an organic solvent solution, aqueous solution or emulsion of the elastic polymer. For applying the solution of the elastic polymer, there may be adopted a method of impregnating the fabric with the solution~ a method of coating the surface or back-side surface of the fabric with the solution or a method of spraying the solution on the fabric. The impregnating method and bac~-side coating method are preferably employed in the present invention.
In the impregnating or spraying method, it is preferable to use a solution having an elastic polymer concentration within a range of 1 to 50% by weight of the solution.
In the coating method 9 it is preferable to use a solu-tion having an elastic polymer concentration within a range of 5 to 50% by weight of the solution. The amount of the elastic polymer (dry weight) applied to the fabric is determined in accordance with the required end use of the ob~ained leatherlike sheet materials, although an amount of D.S to lS~ baseù o~ the weight of .
7~
the fabric is preferable. After the application, the elastic polymer i5 solidified or coagulated by any well-known method to form a leatherlike sheet material.
As for the urethane pre-polymers, there are preferably exemplified hydroscopic and heat-active urethane pre-polymers having one or more isocyanate groups ~locked by bisulfites a and particularly having an oxyethylene group of 10 to 40% by weight in the molecule as disclosed in Japanese Patent ~pplication Laid-Open Nos. 108395/75 and 155794/75. The urethane pre-polymer is applied to the fabric in the form of an aqueous solution or emulsiong and thereafter the applied fabric is dried and heated at a -temperature of 100 to 180C
for 10 seconds to 15 minutes. Upoil heat-treating, the urethane pre-polymer in the fabric releases bisulfites blocking isocyanate groups to regenerate active isocyanate groups9 and accordingly to form a poly-urethane by a self-cross-linking reaction.
The fabric of the present invention may be dyed or printed according to any conventional method before or after the process of applying the elastic polymer.
If desired or necessary9 the elastic polymer applied fabric - the leatherlike sheet material - is buffed or brushed by any conventional method. If necessary9 decatizin~ operation may be conducted on the brushed leatherlike sheet material. Furtherg in the present invention~ it is possible on or after the process of applying the elastic polymer to carry out ~18~7~
water repellent, water proofing9 soil resistant~ anti-static9 slirne imparting, flame resistant an~ fire proofing treatments.
The lea-therli~e sheet material obtained in accordance with the present invention has fine touch, excellent repulsive elasticity and excellent wrinkle resistance. Accordingly 9 the leatherlike sheet material obtained in accordance with the present invention has wide varieties of use as clothing, such as jackets 9 jumpers9 blazers, skirts 9 trousers9 shorts, slacks, dresses~ suits 9 vests, coats and gloves, bags, boots and chair covers.
The following examples are illustrative of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1 ~Preparation of hollow composite fibers]
Hollow composite filaments were prepared with polyethylene terephthalate having an intrinsic viscosity of 0.60 ~at 35C in 0-chlorophenol) as the polymer for the first melted polymer and polystyrene having a melt index of 20 as the polymer for the second melted polymer by using the spinneret as shown in Fi~ure 2 (The number of spirming orifices was 20). The number of small orifices 19 formed in the bottom of each guide hole 15 for the first melted polymer was six, eight9 sixteeng thirty-two and forty in the Experiment ` :
1~8~7~
Nos. 1, 2~ 3~ 4 and 5 respectively. The first and second melted polymers were supplied to the respective ~uide holes at a reeding speed of 9 g/min~ and hollow composite filaments were spun at a temperature of 285C
at a take-up speed of 900 m/min. The obtained undrawn filaments were drawn at a temperature of 110C at a draw ratio of 4, n to obtain hollow composite filaments 3 each having a denier of 2.3 and a hollow ratio of 5%.
The physical properties of the obtained hollow composite filaments are shown in Table 1.
__ ~
Y o o o o a:
,a u~ ~, ~1 ~1 ~1 ~ r~
.,1 ~-rl a~
.~ 3 c~
h ~ a) U U
O ~ X X
_ _ __ ~ o a) ~ c~, ~1 o o c~
*
,1 S o o o o o ,1 ~ ~
a ~ __ ___ _ ~ e c~ O
~ ~ D OD . ' E~ O
_ __ _ _ _______ __ ~
_~
., Footnotes on Tables 1 and 2:
*1: A value calculated from the denier of the hollow composite fiber and the total number of segments of the hollow composite fiber. The calculated value equals the measured value when the separa-bility of segments is 100%.
*2: Workability in melt-spinning and drawing of the hollow composite fibers.
Excellent - The hollow composite fibers hardly separate into each segment and can be smoothly processed in the melt-spinning and drawing operations.
Good - The hollow composite fibers slightly separate into each segment but can be processed practically in the melt-spinnin~ and drawing operations.
Poor - The hollow composite fibers consi~er-ably separate into each segment, and hence the process control in the melt-spinning and drawing operations is difficult.
*3: Separability of segments is shown as a percentage of a value which is calculated dividing the total number of obtained polyester or polyamide segments after all the polystyrene segments are removed from the hollow composite fiber by the total number of polyester or polyamide segments contained in the hollow composite fiber. 100~ separability a~
means that all the segments completely separate into each segment. 50% separability means -that segments are found adhering to each other in twos on the average.
In Experiment No. 1 (where the total number of segments was out of the scope of the present invention) in Table 1, it was very difficult to obtain the hollow composite ~ibers due to poor workability in melt-spinning and drawing of the fibers. On the other hand9 in Experiment Nos. 2 to 5 ~where the total number of segments were within the scope of the present invention) 9 good hollow composite fibers were smoothly obtained due to good workability in melt-spinning and drawing of the fibers. Among these 9 the hollow composite fibers obtained according to Experiment No. 5 ( where the total number of segments was 80) had separability of segments of 80%. It means that a part of polyethylene terephthalate segments are found e~isting in twos on the average adhering to each other. Accordingly 9 when the total number of segments is too many (when the total number of segments is more than 96) 9 separability of segments of the hollow composite fiber becomes to be poor9 which is not preferred in the present invention.
[Preparation of a ~oven fabric]
A woven fabric was prepared with hollow composite filaments obtained according to Experiment No. 3. As for the weft yarn, a single twist filament yarn of this L~
hollow composite multifilaments ~600 deniers/260 filaments) having a twist number of S 150 T/m was used.
As for the warp yarn, a twin filament yarn (~00 deniers) consisting of two 100 denier~24 ~ilament wooly (false twisted) yarns of polyethylene tere-phthalate and having a twist number of S 150 T/m was used. A 4-ply satin was prepared from the warp and weft yarns a the woven density of which was 70 warps/
inch and 56 wefts/inch.
The resultant woven fabric was relaxed in a hot water bath at a ternperature of 98C for 30 minutes 9 and dried at a temperature Gf 120C for 3 minutes.
Thereafter, the woven fabrîc was washed 5 times with trichloroethylene to substantially remove all the polystyrene segments. After drying~ an oiling agent mainly containing mineral oil was applied to the dried fabric. Thereafter 9 one surface of t'~;e fabric was raised 15 times with a wire raising machine having a plurality of 33 count wires at a running speed of 30 m/minute. The raised fabric was then pre-heat set at a temperature of 170C for 30 seconds using a pin ~ tenter type heat setter.
; Thereafter 9 the pre-heat set fabric was dyed at a temperature of 130C for 60 minutes in an aqueous ~' 25 dyeing bath containing 4% (based on the weight of the fabric) of Duranol Blue G (C.I. No. 63305~ trademark for a disperse dye produced by I.C.I.)~ 0.2 mQ~Q of acetic acid, and 1 g/Q of a dispersing agent mainly 71~
containing a condensation product of naphthalene sulfonic acid with formamide. The fabric was then soaped with an aqueous solution containing a nonionic detergent at a temperature of ~0C for 20 minutes, and dried at a temperature of 120C for 3 minutes.
[Preparation of a leatherlike sheet material]
The raised and dyed woven fab-~ic was finished with a polyurethane in the following manner. The fabric was immersed in a 3.6% by wei~ht aqueous emulsion of a mixture of 2.3% by weight polyurethane (reaction product of methylene-diphenyldiisocyanate5 polyethylene glycol 9 and 1 a 4-butane diol) a 1 ~ 0% by weight polybutyl acrylate, and 0.3% by weight of a polyester-polyether block copolymer (a block copolymer consisting of 40%
by weight of a polyester of terephthalic acid and 1~4-butane diolg and 60% by weight of polyte.tramethylene-glycol~. The fabric was then squeezed to an emulsion pick-up ratio of 70% based on the weight of the fabric and dried at a temperature of 120C for 3 minutes a after which it was heat-set at a temperature of 150C
for 30 seconds to obtain a leatherlike sheet material.
The leatherlike sheet material was buffed one time by a roller sander machine with sand paper of 100 mesh size a followed by brushing.
The obtained leatherlike sheet material had suede-like appearance, fine touch5 excellent suppleness and excellent pilling resistance.
Exam~le 2 A leatherlike sheet material was prepared in accordance with the method for applying an urethane pre-polymer to the raic.ed and dyed fabric as obtained in F,xample 1 ~Preparation of an urethane pre-polymer]
An ure-thane pre-polymer having isocyanate groups was prep~red by reacting a mixture at a tempera-ture of 100 to 105C for one hour in a stream of nitrogen gas~ which mixture consists of the following compounds: (1) 21 parts of a block-copolymerized polyether diol having a number average molecular weight of 2,400 which was obtained by reacting poly-propylene glycol having a number aver~ge molecular weight of about 1,200 with ethylene oxide; (2) 56 parts of a polyester diol which was obtained by reacting adipic acid, 1,6-hexane diol and neopentyl glycol in a molar ratio of 10 : 7 : 4 respectively; (3) 3 parts of 1,6-hexane diol; and (4) 20 parts of hexamethylene diisocyanate.
The isocyanate group and oxyethylene group contents in the resultant urethane pre-polymer were 5.02% and 10.2% by wei~ht respectively.
After cooling to 40C, 20 parts of dioxane was added to the resultant urethane pre-polymer to form a solution of the pre~polymer. The obtained solution was mixed thoroughly with 65 parts of an aqueous solution of sodium bisulfite having z concentration of 25% by weight at a temperature of 40C for 30 minutes. There-after, 202 parts of water was added to the reaction mixture to obtain an aqueous solution of the urethane prepolymer having a concentration of about 30% by weight.
LPreparation of a leatherlike sheet material]
The raised and dyed woven fabric as obtained in Example 1 was immersed in an 8% by weight aqueous solution of the abovementioned urethane pre-polymer, and then squeezed to a pick-up ratio of 70~ based on the weight of the fabric. The squeezed fabric was dried at a temperature of 100C for 3 minutes and heat-treated at a temperature of 140C for 30 seconds to obtain a leatherlike sheet material. The raised surface of the leatherlike sheet material was then buffed one time by a roller sander machine with sand paper of 100 mesh size, followed by brushing.
The obtained leatherlike sheet material ~-d fine touch, excellent repulsive elasticity, excellent wrinkle recovery and excellent writing effect similar to natural suede.
Example 3 [Preparation of a non-woven fabric]
After forming a fiber bundle consisting of the undrawn hollow composite yarns as obtained in Experi-ment No. 3 of Example 1 using a creel stand~ the fiber bundle was drawn at a temperature of 60C in a water bath at the drawing ratio of 3.75~ and bestowed 15 crimps/inch using a stuf.in~, box and cut into length of ~8 m~ -to make staple fibers.
The staple fibers were fed to a cross-wrapper to make webs. Two of the webs were laid one over the other and needlepunched with a needlepunching density of 800 needles/em2 to obtain a felty product having a weight of 200 g/m .
[Preparation of a lea-therlike shee-t material]
The obtained felty ?roduct - non-woven fabric -was immersed in a 20% by weight dimethylformamide solution of polyurethane (reaction product of methylene-diphenyl-diisocyanate a polyethylene glycol a and 1,4-butane diol). The fabric wcaS then squeezed to a solution pick~up ratio of 100% based on the weight of the fabric~ and thereafter immersed in water *o coagulate the polyurethane in the fabric. After drying, q~ 7Lr, c ~, / o ro ~ ; /e r~ c ~-~ the fabric was immersed in tric]loroet~lene at room temperature for 3 hours to substantially remove all the polystyrene segments in the hollow composite fibers. The surface of the obtained leatherlike sheet material was buffed one time by sand paper.
The resultant leatherlike sheet material, which was made from a non-woven fabric~ had fine touch and excellent repulsive elasticity similar to natural suede.
Example 4 [Preparation of hollow composite fibers]
r~_ 7~3 ~o Hollow composite filaments were prepared from poly-~-caproamide (nylon 6) having an intrinsic viscosity of 1.10 ~at 35C in m-cresol) as the po]ymer for the first melted polymer and polystyrene having a melt index of 30 as the polymer for the second melted polymer by using the spinneret as shown in Figure 2 (The number of spinning orifices was twenty and the number of small oridices 19 formed in the bottom of each guide holc 15 for the first melted polymer was sixteen).
The first and second melted polymers were supplied to the respective guide holes at a feeding speed of 10.8 g/min and 1.2 g/min respectively 9 and hollow composite filaments were spun at a temperature of 2S5C at a take-up speed of 1000 m/min. The obtained undrawn filaments were drawn at a temperature ; of 110C at a draw ratio of 3.0 to obtain hollow composite filaments 9 each having a denier of 2.6 and a hollow ratio of 6.5%. Each polyamide and polystyrene segment had a denier of 0.10 and 0.06 respectively.
The physical properties of the obtained hollow composite i filaments are shown in Table 2~ Experiment No. 6.
On the other hand~ two kind of hollow composite ' filaments were prepared by the same procedure as the abovementioned process, except that the feeding speed of the first and second melted polymers were 13.5 g/
min and 4.5 g/min respectively for one l~ind and the feeding speed of the first and second melted pGlymers ~ lB~ ~
were B.l g/min and 9.9 g/min respectively fGr the other. l'he former hollow composite filament had a denier of22.6 and a hollow ratio of 8.5~. Each poly-arnide and polystyrene segment in the former ilad a denier of 0.13 and 0.04 respectively. The latter hollow composite filament had a denier of 2.G and a hollow ratio of 3.0%. Each polyamide and polystyrene segment in the latter had a denier of 0.08 and 0.0~
respectively. The physical properties of the obtained hollow composite filaments are shown in Table 2, Experiment Nos. 7 (the former) and 8 (the latter).
Since the ratio of the feeding speed of polyamide to that of polystyrene was 75 : 25 in Experiment No. 7 and 45 : 55 in Experiment No. 8, which were out of the preferred scope of the present invention 9 the hollow composite fibers had poor workability in melt-spinning and drawing.
~lilLB~L~
_ ~
~ 0 ~C o\ -x o o o V~ O
_ _ _ _ _____ ~1 bO
. ,~ ~ W ~ O
~ 4~ o ,1 O bO O ~ ~ h .. .. ..
.t:l ~ C~
E~ ~ ~ o _ ~ ~ C~
,1 ~
~ tn 0 4~
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_ _ __ ~D t- ao o z æ
~ =
. ____ I
- 33 ~
~Preparation of a knitted fabric]
A tricot having a weight of 250 g/m was prepared by using as a front yarn~ a single twist filament yarn (S 150 T/m) of the ho'low composite multifilaments (600 deniers/260 fila~ents) as obtained in Experiment No. 6, and as a back yarn~ a filament yarn (150 deniers/
48 filaments) of nylon 6.
The -tricot was relaxed in a hot water bath at a temperature of 80C for 20 minutes, and dried at a temperature of 120C for 3 minutes. Thereafter, the tricot was washed 5 times with trichloroethylene to substantially remove a]l the polystyrene segments in the hollow composite fibers. The tricot was then dyed at a temperature of 100C for 40 minutes in an aqueous dyeing bath containing 4% (based on the weight of the tricot~ of Suminol Milling Brilliant Red B (C.I. No.
18134~ trademark for an acid dye produced by Sumitomo Chemical Co.) and 2 mQ/Q of acetic acid. Ihe tricot was then washed with an aqueous solution containing a nonionic detergent at a temperature of 70C for 20 minutes, and dried at a temperature of 120C ~or 3 minutes.
[Preparation of a leatherlike sheet material]
The dyed tricot was immersed in a 2.4~ by weight aqueous emulsion of a mixture of 102% by weight of an ethylene-vinyl acetate copolymer (a copolymer of equivalent moles of each component), 0.9% by weight polybutyl acrylate, and 0.3% by weight of a polyester-~"
lllB170 ~ 34 -polyether block copolymer as used in Example 1, and was squeezed to an emulsion pick-up ratio of 70% based on the weight of the tricot and dried at a temperature of 120C for 3 minutes, and then heat-set at ~ temperature of 150C for 30 seconds~ The resultant leatherlike sheet material was buffed one time by a roller sander machine with sand paper of 100 mesh size, followed by brushing.
The leatherlike sheet material had fine touch and excellent suppleness.
The same procedures are repeated 20 times at different points along the fiber. The hollow ratio of the fiber represents a mean value of the determined values of the ratios. When the hollow composite fibers have a hollow ratio of between 1 and 30% by volume, the hollow composite fibers can be processed by, for example 3 a melt-spinning operation, a drawing operation, and a weaving operation without the individual segments being separated from each other. The polystyrene segments in thus obtained hollow composite fiber are readily dissolved with a solvent thereof to form extra fine fibers composed of individual polyester or polyamide segments, In the present invention, the polyester used for the polyester segments may be selected ~rom the group consisting of (1) alkylene terephthalate homo-polyes-ters, in which the alkylene group is derived from polymethylene glycol of the formula: HO (CH2) -OH, where p represents an integer of from 2 to 10 and (2) alkylene terephthalate - third ingredient copolyesters, in which the alkylene group is the same as defined _ 9 _ above and the third ingredient is derived from at least one compound selected from the group consisting of adipic acid, sebacic acid, isophthalic acidg diphenylsulfone-dicarboxylic acid, naphthalene-dicarboxylic acidg hydroxybenzoic acid, propyleneglycol, cyclohexane~dimethanol and neopentyl glycol, in an amount o~ 10% or less by mole based on the amount of the alkylene terephthalate ingredient. The polyester used for the polyester segments may also be a blend o~
two or more of the above-mentioned homopolyes-ters and the copolyesters. Among these polyesters~ polyethylene terephthalate is particularly preferable. The prefer-able polyesters in the present invention have an intrinsic viscosity of between 0.4 and 1.2 when measured at 35C in 0-chlorophenol.
The polyamide used for the polyamide segments may be selected from the group consisting of nylon ~, nylon 6, nylon 669 nylon 79 nylon 610, nylon 11, nylon 12, polyamides of bis(p-aminocyclohexyl) methane with a dicarboxylic acid such as lg7-heptanedicarboxylic acid and l,10-decamethylenedicarboxylic acid, copoly-amides o~ two or more of the above-mentioned polyamides and mixtures of two or more of the above-mentioned polyamides and copolyamides. Among these polyamides, nylon 6 and nylon 66 are particularly preferable. The preferable polyamides in the present invention have an intrinsic viscosity of between 1.0 and 1.3 when measured at 35C in m-cresol.
The polyester or polyamide segm~nts may contain therein an anti-static agent~ a delustering agent such as titanium dioxide, a coloring agent such as carbon black, and an anti-oxidizing agen' having thermal stability.
In the present invention, the polystyrene used for the polys-tyrene segments may be selected from the group consisting of (1) a homopolymer of styrene and (2) styrene-copolymers obtained by copolymerizing more than 80~ by weight of styrene with less than 20% by weight of other vinyl compounds. As for vinyl compounds copolymerizable with styrene, there are exemplified vinyltoluene 9 chlorostyrene~ acrylonitrile, ethylene, propylene~ butylene~ butadiene and isoprene.
The preferable polystyrenes in the present invention have a melt index of between 10 and 30.
The process for the preparation of the hollow composite fiber as shown in Figure 1 is illustrated in the following paragraphs.
Figure 2 shows an axial cross-sectional view of a spinneret used for producing the hollow composite fiber as shown in Figure 1 (the hollow composite fiber having the total segments of 32). Figure 3 shows a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line A-A'. Figure 4 shows a partial transverse cross-sectional view of the spinneret of Figure 2 taken at line B-B'.
In the spinneret of Figure 2~ the top plate 12 is fixed to the bottom plate 11 with a set-screw 21 17`~
and is sealed against the bottom plate 11 by gasket 20.
The bottom plate 11 has a recessed region which forms a narrow fluid passage 14 between the ~ottom plate 11 and top plate 12.
This fluid passage 14 is formed in the form of circular groove as shown in Figure 4. The bottom plate 11 has a plurality of spinning orifices 13, each of which has four circularly arranged slits 17 in the bottom portion as shown in Figure 4 and an upper opening which communicates with the fluid passage 14 passing through a plateau-like protrusion 18. The number of slits is in 0 the range of 1 to 8, and preferably 4. The top plate 12 has a guide hole 15 for the first melted polymer and a plurality of guide holes 16 for the second melted polymer which are provided for each spinning orifice 13. The guide holes 16 for the second melted polymer are formed in fours around the guide hole 15 for the first melted polymer as shown in Figure 3. The number of guide holes for the second melted polymer is not necessarily limited, although a number of between 1 and 6 corresponding to each guide hole for the first melted polymer is preferable. The guide hole 15 for the first melted polymer communicates with the ~0 fluid passage 14 through sixteen circularly arranged small ori-fices 19 (as shown in Figure 3) which are formed in the bottom of the guide hole 15 for the first melted polymer. The small ori-fices 19 are so arranged that the first melted polymer extruded through the small orifices 19 may impinge on ~ - 11 -the plateau of the protrusion 18. Upper opening of the guide hole 15 for the first melted polymer communicates with the supply means (not shown~ of the first melted polymer. Lower and upper openings of the guide hole 16 for the second melted polymer are communicated with unprotruded regions of the fluid passage 14 and the supply means (not shown) of the second melted polymer respectively.
The number of small orifices 19 formed in the bottom of each guide hole 15 for the first melted polymer must be 2~ same as the number of segments fo-,~med from the first melted polymer in the ob-tained hollow composite fiber. Accordingly 9 the number of small orifices is in the range of 8 to 48, preferably 16 to 36 in the present invention.
The first melted polymer is supplied to the guide hole 15 for the first melted polymer from the supply means (not shown) and impinges on the plateau of the protrusion 18 through the small orifices 19 to form sixteen fine streams of the first melted polymer, which streams are led to the spinning origice 13. The second melted polymer is supplied to the guide holes 16 for the second melted polymer from the supply means (not shown) and led to the fluid passage 14, and contacts with the first melted polymer after its flow having been streamlined uniformly by the protrusion 18.
The both melted polymersg contacting each other, form a composite stream composed of the sixteen first melted ~3~L7 polymer ~ine streams, each being surrounded by the second mel-ted polymer~ which composite stream is led to the spinning orifice 13 and extruded through four slits 17 to make a hollow COTnpOSite Eiber having 32 segments as shown in Figure 1.
In the present invention, polyesters or polyamides and polystyrenes are used as the polymers for the first and the second melted polymers respectively.
Polyesters or polyamides used for the first melted polymer have preferably a melt viscosity of 1000 to 3500 poises, and po]ystyrenes used for the second melted polymer have preferably a melt viscosity of 500 to 1500 poises. In the melt spinning operation, it is preferable that the melt spinning temperature is between 280 and 300C and the take-up speed of spun filaments tundrawn filaments) is between 500 and 2000 m/min.
In the ~resent invention., the ratio of the feeding speed (g/min) of polyesters or polyamides to that of polystyrenes is in a range of between 50 : 50 and 70 : 30. It is possible to obtain a hollow composite fiber having segments of desired cross-sectional configurations and areas by varying the ratio within the abovementioned range. Thus obtained undrawn filaments are drawn at a draw ratio of 2 to 5 to form the hollow composite fibers (drawn filaments) used in the present invention. In the drawing operation, it is preferable that -tne drawing temperature is between 40 17~
and 130C under wet or dry conditions and the take-up speed of drawn filaments in between 300 and 1000 m/lllin.
In the present invention, a fabric is formed using thus obtained hollow composite fibers. The fabric means a non-woven, woven and knitted fabrics as well as a composite thereof in the present invention.
As for non-woven fabrics, there are a web and a felty product made from the hollow composite fibers of the present invention or a mixture of the hollow composite fibers and conventional fibers each having a denier of more than about 1. The web may be formed by using a conventional apparatus for producing non-woven fabrics, such as a carding machine, cross wrapper and random webber, or formed by a method of direct fabrica-lS tion. The felty product may be formed by needlepunch-ing a plurality of webs arranged in layers.
The felty product may also be formed by needlepunching the webs together with a web a woven or knitted fabric consistin~ of conventional fibers arranged in layers.
The density of needlepunching can be determined in accordance with the requirements of the end uses of ~ j. is the non-woven fabrics, and preferably/between 200 to 800 needles/cm2. The for~ation of the felty products can also be performed by the stitch bonding method using such machines as '1Arachne," "Maliwatt'i or "Mlipol". One or both surfaces of the felty product may be raised by using a conventional raising machine, such as a roller sander machine with sand paper or / r c/ O/C in ~r ~
7~
emery clothO
The woven fabric is prepared from a multifilament yarn or a spun yarn consisting of the hollow composite fibers of the present invention as the warp and/or S weft of the woven fabric by using a conventional loom.
One or both surfaces of the woven fabric may be raised by using a conventional raising machine, such as emery raising machine, tea~el raising machine, wire raising machine, or a roller sander machine with sand paper or emery cloth. As for the woven fabrics used for the raised woven fabrics~ a satin fabric is preferably used, which is composed of a multifilament yarn or a spun yarn consisting of the hollow composite fibers of total denier ranging from 50 to 500 as the weft, and a multifilament yarn, a mixed multifilament yarn, a spun yarn or a mixed spun yarn consisting of the conventional fibers (whose monofilament denier is more than about 1) of total denier ranging from 50 to 300 as the warp. When it is desired to raise two surfaces (a surface and back surface) of the fabric~ a double faced woven fabric having a satin structure in both surfaces is preferably used. Among the satin fabrics, 3-ply satin and 4-ply satin fabrics are particularly preferable. In particular, a textured yarn having crimps which consists of polyesters~ such as poly-ethylene terephthalate or polyamides~ such as nylon 6 and nylon 66 is preferably used as the warp yarn.
The knitted fabric is prepared from a multifilament yarn or a spun yarn consisting of the hollow composite fibers of th~ present invention by using a conventional knitter. When a warp knitted fabric is employed9 it is preferable that the front yarns thereof are formed with a multifilament yarn or a spun yarn consisting of the hollow composite fibers and the back yarns thereof are for,ned with a multi-filament yarn, a mixed multifilament yarn~ a spun yarn or a mixed spun yarn having the conventional denier.
When a circular knitted fabric is employed a it is preferable that both the front and back portions or only the front portion thereof are formed with a multifilament yarn or a spun yarn consisting of the hollow composite fibers. One or both surfaces of the knitted fabric may be raised as in the case of the woven fabric.
In the present specification, the multifilament yarn means, for example~ a single twist filament yarn, an untwisted filament yarn, a twin filament yarng a triple filament yarn, a "Taslan1' textured yarn ~trade-mark of Du Por,t~ or a textured yarn having crimps obtained by a method such as false-twisting, stuffer crimping, edge crimping and air jet-crimping. The mixed multifilament yarn means a multifilament yarn consisting of two or more different filaments.
In the present invention~ thus obtained fabric is treated with a sol~ent of polystyrenes to remove the polystyrene segments of the hollow composite fibers 7~
contained in the fabric. All the polystyrene segments of the hollow composite fibers are substantially removed with a solven-t such as benzeneg toluene, trichloro-ethylene and perchlorethylene at room or elevated temperature. Accordingly~ the fabric containing extra fine fibers is obtained~ which extra fine fibers consist essentially of polyester or polyamide segments 7 each having a denier of 0.01 to 0.5. This ope~ation of removing the polystyrene segments of the hollow composite fibers may be conducted after the process of applying an elastic polymer to the fabric as described below.
The abovesaid operation of raising the fabric may be conducted after the operation of remo~ing the polystyrene segments and before the process of applying an elastic polymer to the fabric. If desired or necessary, shearingg buffing or brushing operation may be conducted on the raised fabric after the operation of removing the polystyrene segments from the hollow composite fibers.
In the present invention, an elastic polymer i5 applied to thus obtained fabric (a fabric obtained before or after the operation of removing the poly-styrene segments from the hollow composite fibers). As for the elastic polymers 3 there are natural rubber and synthetic elastic polymers such as acrylonitrile-butadiene copo~ymers, polychloroprene, styrene-butadiene copolymersg polybutadiene, polyisopreneg ethylene-J
~ 8~70 propylene copolymers, acrylate-type copolymers 9 silicone, polyurethanes, polyacrylates~ polyvinyl acetate, polyvinyl chloride, polyester-polyether block copolymers, 4n~
ethylenevinyl acetate copolymers~ ~. The method which comprises applying an urethane pre-polymer to the fabric and then heating the applied fabric to form a polyurethane in the fabric is also preferably employed in the present invention.
The elastic polymer is applied to the fabric in the form of a solution such as an organic solvent solution, aqueous solution or emulsion of the elastic polymer. For applying the solution of the elastic polymer, there may be adopted a method of impregnating the fabric with the solution~ a method of coating the surface or back-side surface of the fabric with the solution or a method of spraying the solution on the fabric. The impregnating method and bac~-side coating method are preferably employed in the present invention.
In the impregnating or spraying method, it is preferable to use a solution having an elastic polymer concentration within a range of 1 to 50% by weight of the solution.
In the coating method 9 it is preferable to use a solu-tion having an elastic polymer concentration within a range of 5 to 50% by weight of the solution. The amount of the elastic polymer (dry weight) applied to the fabric is determined in accordance with the required end use of the ob~ained leatherlike sheet materials, although an amount of D.S to lS~ baseù o~ the weight of .
7~
the fabric is preferable. After the application, the elastic polymer i5 solidified or coagulated by any well-known method to form a leatherlike sheet material.
As for the urethane pre-polymers, there are preferably exemplified hydroscopic and heat-active urethane pre-polymers having one or more isocyanate groups ~locked by bisulfites a and particularly having an oxyethylene group of 10 to 40% by weight in the molecule as disclosed in Japanese Patent ~pplication Laid-Open Nos. 108395/75 and 155794/75. The urethane pre-polymer is applied to the fabric in the form of an aqueous solution or emulsiong and thereafter the applied fabric is dried and heated at a -temperature of 100 to 180C
for 10 seconds to 15 minutes. Upoil heat-treating, the urethane pre-polymer in the fabric releases bisulfites blocking isocyanate groups to regenerate active isocyanate groups9 and accordingly to form a poly-urethane by a self-cross-linking reaction.
The fabric of the present invention may be dyed or printed according to any conventional method before or after the process of applying the elastic polymer.
If desired or necessary9 the elastic polymer applied fabric - the leatherlike sheet material - is buffed or brushed by any conventional method. If necessary9 decatizin~ operation may be conducted on the brushed leatherlike sheet material. Furtherg in the present invention~ it is possible on or after the process of applying the elastic polymer to carry out ~18~7~
water repellent, water proofing9 soil resistant~ anti-static9 slirne imparting, flame resistant an~ fire proofing treatments.
The lea-therli~e sheet material obtained in accordance with the present invention has fine touch, excellent repulsive elasticity and excellent wrinkle resistance. Accordingly 9 the leatherlike sheet material obtained in accordance with the present invention has wide varieties of use as clothing, such as jackets 9 jumpers9 blazers, skirts 9 trousers9 shorts, slacks, dresses~ suits 9 vests, coats and gloves, bags, boots and chair covers.
The following examples are illustrative of the present invention, but are not to be construed as limiting the scope of the present invention.
Example 1 ~Preparation of hollow composite fibers]
Hollow composite filaments were prepared with polyethylene terephthalate having an intrinsic viscosity of 0.60 ~at 35C in 0-chlorophenol) as the polymer for the first melted polymer and polystyrene having a melt index of 20 as the polymer for the second melted polymer by using the spinneret as shown in Fi~ure 2 (The number of spirming orifices was 20). The number of small orifices 19 formed in the bottom of each guide hole 15 for the first melted polymer was six, eight9 sixteeng thirty-two and forty in the Experiment ` :
1~8~7~
Nos. 1, 2~ 3~ 4 and 5 respectively. The first and second melted polymers were supplied to the respective ~uide holes at a reeding speed of 9 g/min~ and hollow composite filaments were spun at a temperature of 285C
at a take-up speed of 900 m/min. The obtained undrawn filaments were drawn at a temperature of 110C at a draw ratio of 4, n to obtain hollow composite filaments 3 each having a denier of 2.3 and a hollow ratio of 5%.
The physical properties of the obtained hollow composite filaments are shown in Table 1.
__ ~
Y o o o o a:
,a u~ ~, ~1 ~1 ~1 ~ r~
.,1 ~-rl a~
.~ 3 c~
h ~ a) U U
O ~ X X
_ _ __ ~ o a) ~ c~, ~1 o o c~
*
,1 S o o o o o ,1 ~ ~
a ~ __ ___ _ ~ e c~ O
~ ~ D OD . ' E~ O
_ __ _ _ _______ __ ~
_~
., Footnotes on Tables 1 and 2:
*1: A value calculated from the denier of the hollow composite fiber and the total number of segments of the hollow composite fiber. The calculated value equals the measured value when the separa-bility of segments is 100%.
*2: Workability in melt-spinning and drawing of the hollow composite fibers.
Excellent - The hollow composite fibers hardly separate into each segment and can be smoothly processed in the melt-spinning and drawing operations.
Good - The hollow composite fibers slightly separate into each segment but can be processed practically in the melt-spinnin~ and drawing operations.
Poor - The hollow composite fibers consi~er-ably separate into each segment, and hence the process control in the melt-spinning and drawing operations is difficult.
*3: Separability of segments is shown as a percentage of a value which is calculated dividing the total number of obtained polyester or polyamide segments after all the polystyrene segments are removed from the hollow composite fiber by the total number of polyester or polyamide segments contained in the hollow composite fiber. 100~ separability a~
means that all the segments completely separate into each segment. 50% separability means -that segments are found adhering to each other in twos on the average.
In Experiment No. 1 (where the total number of segments was out of the scope of the present invention) in Table 1, it was very difficult to obtain the hollow composite ~ibers due to poor workability in melt-spinning and drawing of the fibers. On the other hand9 in Experiment Nos. 2 to 5 ~where the total number of segments were within the scope of the present invention) 9 good hollow composite fibers were smoothly obtained due to good workability in melt-spinning and drawing of the fibers. Among these 9 the hollow composite fibers obtained according to Experiment No. 5 ( where the total number of segments was 80) had separability of segments of 80%. It means that a part of polyethylene terephthalate segments are found e~isting in twos on the average adhering to each other. Accordingly 9 when the total number of segments is too many (when the total number of segments is more than 96) 9 separability of segments of the hollow composite fiber becomes to be poor9 which is not preferred in the present invention.
[Preparation of a ~oven fabric]
A woven fabric was prepared with hollow composite filaments obtained according to Experiment No. 3. As for the weft yarn, a single twist filament yarn of this L~
hollow composite multifilaments ~600 deniers/260 filaments) having a twist number of S 150 T/m was used.
As for the warp yarn, a twin filament yarn (~00 deniers) consisting of two 100 denier~24 ~ilament wooly (false twisted) yarns of polyethylene tere-phthalate and having a twist number of S 150 T/m was used. A 4-ply satin was prepared from the warp and weft yarns a the woven density of which was 70 warps/
inch and 56 wefts/inch.
The resultant woven fabric was relaxed in a hot water bath at a ternperature of 98C for 30 minutes 9 and dried at a temperature Gf 120C for 3 minutes.
Thereafter, the woven fabrîc was washed 5 times with trichloroethylene to substantially remove all the polystyrene segments. After drying~ an oiling agent mainly containing mineral oil was applied to the dried fabric. Thereafter 9 one surface of t'~;e fabric was raised 15 times with a wire raising machine having a plurality of 33 count wires at a running speed of 30 m/minute. The raised fabric was then pre-heat set at a temperature of 170C for 30 seconds using a pin ~ tenter type heat setter.
; Thereafter 9 the pre-heat set fabric was dyed at a temperature of 130C for 60 minutes in an aqueous ~' 25 dyeing bath containing 4% (based on the weight of the fabric) of Duranol Blue G (C.I. No. 63305~ trademark for a disperse dye produced by I.C.I.)~ 0.2 mQ~Q of acetic acid, and 1 g/Q of a dispersing agent mainly 71~
containing a condensation product of naphthalene sulfonic acid with formamide. The fabric was then soaped with an aqueous solution containing a nonionic detergent at a temperature of ~0C for 20 minutes, and dried at a temperature of 120C for 3 minutes.
[Preparation of a leatherlike sheet material]
The raised and dyed woven fab-~ic was finished with a polyurethane in the following manner. The fabric was immersed in a 3.6% by wei~ht aqueous emulsion of a mixture of 2.3% by weight polyurethane (reaction product of methylene-diphenyldiisocyanate5 polyethylene glycol 9 and 1 a 4-butane diol) a 1 ~ 0% by weight polybutyl acrylate, and 0.3% by weight of a polyester-polyether block copolymer (a block copolymer consisting of 40%
by weight of a polyester of terephthalic acid and 1~4-butane diolg and 60% by weight of polyte.tramethylene-glycol~. The fabric was then squeezed to an emulsion pick-up ratio of 70% based on the weight of the fabric and dried at a temperature of 120C for 3 minutes a after which it was heat-set at a temperature of 150C
for 30 seconds to obtain a leatherlike sheet material.
The leatherlike sheet material was buffed one time by a roller sander machine with sand paper of 100 mesh size a followed by brushing.
The obtained leatherlike sheet material had suede-like appearance, fine touch5 excellent suppleness and excellent pilling resistance.
Exam~le 2 A leatherlike sheet material was prepared in accordance with the method for applying an urethane pre-polymer to the raic.ed and dyed fabric as obtained in F,xample 1 ~Preparation of an urethane pre-polymer]
An ure-thane pre-polymer having isocyanate groups was prep~red by reacting a mixture at a tempera-ture of 100 to 105C for one hour in a stream of nitrogen gas~ which mixture consists of the following compounds: (1) 21 parts of a block-copolymerized polyether diol having a number average molecular weight of 2,400 which was obtained by reacting poly-propylene glycol having a number aver~ge molecular weight of about 1,200 with ethylene oxide; (2) 56 parts of a polyester diol which was obtained by reacting adipic acid, 1,6-hexane diol and neopentyl glycol in a molar ratio of 10 : 7 : 4 respectively; (3) 3 parts of 1,6-hexane diol; and (4) 20 parts of hexamethylene diisocyanate.
The isocyanate group and oxyethylene group contents in the resultant urethane pre-polymer were 5.02% and 10.2% by wei~ht respectively.
After cooling to 40C, 20 parts of dioxane was added to the resultant urethane pre-polymer to form a solution of the pre~polymer. The obtained solution was mixed thoroughly with 65 parts of an aqueous solution of sodium bisulfite having z concentration of 25% by weight at a temperature of 40C for 30 minutes. There-after, 202 parts of water was added to the reaction mixture to obtain an aqueous solution of the urethane prepolymer having a concentration of about 30% by weight.
LPreparation of a leatherlike sheet material]
The raised and dyed woven fabric as obtained in Example 1 was immersed in an 8% by weight aqueous solution of the abovementioned urethane pre-polymer, and then squeezed to a pick-up ratio of 70~ based on the weight of the fabric. The squeezed fabric was dried at a temperature of 100C for 3 minutes and heat-treated at a temperature of 140C for 30 seconds to obtain a leatherlike sheet material. The raised surface of the leatherlike sheet material was then buffed one time by a roller sander machine with sand paper of 100 mesh size, followed by brushing.
The obtained leatherlike sheet material ~-d fine touch, excellent repulsive elasticity, excellent wrinkle recovery and excellent writing effect similar to natural suede.
Example 3 [Preparation of a non-woven fabric]
After forming a fiber bundle consisting of the undrawn hollow composite yarns as obtained in Experi-ment No. 3 of Example 1 using a creel stand~ the fiber bundle was drawn at a temperature of 60C in a water bath at the drawing ratio of 3.75~ and bestowed 15 crimps/inch using a stuf.in~, box and cut into length of ~8 m~ -to make staple fibers.
The staple fibers were fed to a cross-wrapper to make webs. Two of the webs were laid one over the other and needlepunched with a needlepunching density of 800 needles/em2 to obtain a felty product having a weight of 200 g/m .
[Preparation of a lea-therlike shee-t material]
The obtained felty ?roduct - non-woven fabric -was immersed in a 20% by weight dimethylformamide solution of polyurethane (reaction product of methylene-diphenyl-diisocyanate a polyethylene glycol a and 1,4-butane diol). The fabric wcaS then squeezed to a solution pick~up ratio of 100% based on the weight of the fabric~ and thereafter immersed in water *o coagulate the polyurethane in the fabric. After drying, q~ 7Lr, c ~, / o ro ~ ; /e r~ c ~-~ the fabric was immersed in tric]loroet~lene at room temperature for 3 hours to substantially remove all the polystyrene segments in the hollow composite fibers. The surface of the obtained leatherlike sheet material was buffed one time by sand paper.
The resultant leatherlike sheet material, which was made from a non-woven fabric~ had fine touch and excellent repulsive elasticity similar to natural suede.
Example 4 [Preparation of hollow composite fibers]
r~_ 7~3 ~o Hollow composite filaments were prepared from poly-~-caproamide (nylon 6) having an intrinsic viscosity of 1.10 ~at 35C in m-cresol) as the po]ymer for the first melted polymer and polystyrene having a melt index of 30 as the polymer for the second melted polymer by using the spinneret as shown in Figure 2 (The number of spinning orifices was twenty and the number of small oridices 19 formed in the bottom of each guide holc 15 for the first melted polymer was sixteen).
The first and second melted polymers were supplied to the respective guide holes at a feeding speed of 10.8 g/min and 1.2 g/min respectively 9 and hollow composite filaments were spun at a temperature of 2S5C at a take-up speed of 1000 m/min. The obtained undrawn filaments were drawn at a temperature ; of 110C at a draw ratio of 3.0 to obtain hollow composite filaments 9 each having a denier of 2.6 and a hollow ratio of 6.5%. Each polyamide and polystyrene segment had a denier of 0.10 and 0.06 respectively.
The physical properties of the obtained hollow composite i filaments are shown in Table 2~ Experiment No. 6.
On the other hand~ two kind of hollow composite ' filaments were prepared by the same procedure as the abovementioned process, except that the feeding speed of the first and second melted polymers were 13.5 g/
min and 4.5 g/min respectively for one l~ind and the feeding speed of the first and second melted pGlymers ~ lB~ ~
were B.l g/min and 9.9 g/min respectively fGr the other. l'he former hollow composite filament had a denier of22.6 and a hollow ratio of 8.5~. Each poly-arnide and polystyrene segment in the former ilad a denier of 0.13 and 0.04 respectively. The latter hollow composite filament had a denier of 2.G and a hollow ratio of 3.0%. Each polyamide and polystyrene segment in the latter had a denier of 0.08 and 0.0~
respectively. The physical properties of the obtained hollow composite filaments are shown in Table 2, Experiment Nos. 7 (the former) and 8 (the latter).
Since the ratio of the feeding speed of polyamide to that of polystyrene was 75 : 25 in Experiment No. 7 and 45 : 55 in Experiment No. 8, which were out of the preferred scope of the present invention 9 the hollow composite fibers had poor workability in melt-spinning and drawing.
~lilLB~L~
_ ~
~ 0 ~C o\ -x o o o V~ O
_ _ _ _ _____ ~1 bO
. ,~ ~ W ~ O
~ 4~ o ,1 O bO O ~ ~ h .. .. ..
.t:l ~ C~
E~ ~ ~ o _ ~ ~ C~
,1 ~
~ tn 0 4~
O
_ _ __ ~D t- ao o z æ
~ =
. ____ I
- 33 ~
~Preparation of a knitted fabric]
A tricot having a weight of 250 g/m was prepared by using as a front yarn~ a single twist filament yarn (S 150 T/m) of the ho'low composite multifilaments (600 deniers/260 fila~ents) as obtained in Experiment No. 6, and as a back yarn~ a filament yarn (150 deniers/
48 filaments) of nylon 6.
The -tricot was relaxed in a hot water bath at a temperature of 80C for 20 minutes, and dried at a temperature of 120C for 3 minutes. Thereafter, the tricot was washed 5 times with trichloroethylene to substantially remove a]l the polystyrene segments in the hollow composite fibers. The tricot was then dyed at a temperature of 100C for 40 minutes in an aqueous dyeing bath containing 4% (based on the weight of the tricot~ of Suminol Milling Brilliant Red B (C.I. No.
18134~ trademark for an acid dye produced by Sumitomo Chemical Co.) and 2 mQ/Q of acetic acid. Ihe tricot was then washed with an aqueous solution containing a nonionic detergent at a temperature of 70C for 20 minutes, and dried at a temperature of 120C ~or 3 minutes.
[Preparation of a leatherlike sheet material]
The dyed tricot was immersed in a 2.4~ by weight aqueous emulsion of a mixture of 102% by weight of an ethylene-vinyl acetate copolymer (a copolymer of equivalent moles of each component), 0.9% by weight polybutyl acrylate, and 0.3% by weight of a polyester-~"
lllB170 ~ 34 -polyether block copolymer as used in Example 1, and was squeezed to an emulsion pick-up ratio of 70% based on the weight of the tricot and dried at a temperature of 120C for 3 minutes, and then heat-set at ~ temperature of 150C for 30 seconds~ The resultant leatherlike sheet material was buffed one time by a roller sander machine with sand paper of 100 mesh size, followed by brushing.
The leatherlike sheet material had fine touch and excellent suppleness.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of leatherlike sheet materials which comprises the steps of:
(1) preparing hollow composite fibers 3 each composed of 16 to 96 alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, said hollow composite fiber having a denier of 1 to 20 9 and said each segment having a denier of 0.01 to 0.5 9 (2) forming a fabric using thus prepared hollow composite fibers;
(3) removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and (4) applying an elastic polymer to the fabric.
(1) preparing hollow composite fibers 3 each composed of 16 to 96 alternately arranged segments of polyester or polyamide and polystyrene which are mutually adhered side-by-side and encompass a hollow space, and which extend along the longitudinal axis of the fiber to form a tubular body, said hollow composite fiber having a denier of 1 to 20 9 and said each segment having a denier of 0.01 to 0.5 9 (2) forming a fabric using thus prepared hollow composite fibers;
(3) removing the polystyrene segments with a solvent thereof from the hollow composite fibers; and (4) applying an elastic polymer to the fabric.
2. The process according to Claim 13 wherein the ratio of the total weight of the polyester or polyamide segments to that of the polystyrene segments in the hollow composite fiber is in a range of between 50 : 50 and 70 30.
3. The process according to Claim 13 wherein the hollow ratio of the hollow composite fiber is between 1 and 30% by volume.
4. The process according to Claim 1, wherein the polyester is polyethylene terephthalate.
5. The process according to Claim 1, wherein the polyamide is nylon 6 or nylon 66.
6. The process according to Claim 1, wherein the fabric is a woven fabric.
7. The process according to Claim 1, wherein the fabric is a knitted fabric.
8. The process according to Claim 1, wherein the fabric is a non-woven fabric.
9. The process according to Claim 19 wherein the step of applying an elastic polymer to the fabric comprises applying an aqueous solution or emulsion of hydroscopic and heat-active urethane pre-polymer having an isocyanate group blocked by bisulfites to the fabric, and then heat-treating the fabric at a tempera-ture of 100 to 180°C to form polyurethane in the fabric.
10. The process according to Claim 1, wherein the step of forming the fabric using the hollow composite fibers is followed by the step of applying the elastic polymer to the fabric and thereafter the step of removing the polystyrene segments with the solvent thereof from the hollow composite fibers in the fabric.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP106292/77 | 1977-09-06 | ||
| JP52106292A JPS5928670B2 (en) | 1977-09-06 | 1977-09-06 | Method for manufacturing leather-like structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118170A true CA1118170A (en) | 1982-02-16 |
Family
ID=14429968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000308728A Expired CA1118170A (en) | 1977-09-06 | 1978-08-03 | Process for the preparation of leatherlike sheet materials |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5928670B2 (en) |
| BE (1) | BE870167A (en) |
| CA (1) | CA1118170A (en) |
| CH (1) | CH639158A5 (en) |
| DE (1) | DE2835293C3 (en) |
| ES (1) | ES473105A1 (en) |
| FR (1) | FR2401766A1 (en) |
| GB (1) | GB2004496B (en) |
| IT (1) | IT1106627B (en) |
| NL (1) | NL176483C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2951307A1 (en) * | 1979-12-20 | 1981-07-02 | Akzo Gmbh, 5600 Wuppertal | SUEDE-LIKE AREA |
| EP0305596B1 (en) * | 1983-02-10 | 1992-01-15 | Toray Industries, Inc. | Process for dyeing ultrafine polyamide fibers |
| JPS59150133A (en) * | 1983-02-10 | 1984-08-28 | 東レ株式会社 | Leather-like yarn |
| JPS6021980A (en) * | 1983-07-12 | 1985-02-04 | Toray Ind Inc | Composite material |
| DE102013200696A1 (en) | 2013-01-17 | 2014-07-17 | Würth Elektronik eiSos Gmbh & Co. KG | inductance component |
| CN115716360B (en) * | 2022-03-30 | 2023-10-27 | 长春工业大学 | High sound insulation polymer composite material and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1218191A (en) * | 1966-10-17 | 1971-01-06 | Toray Industries | Improvements relating to non-woven fibrous felt and methods of manufacturing such felt |
| US3705226A (en) * | 1969-07-09 | 1972-12-05 | Toray Industries | Artificial leather and a method of manufacturing the same |
| JPS5329198B2 (en) * | 1974-01-31 | 1978-08-18 | ||
| JPS5132681A (en) * | 1974-09-13 | 1976-03-19 | Fujikura Ltd | NETSUDENTSUINOSEIZOSOCHI |
| JPS5148402A (en) * | 1974-10-18 | 1976-04-26 | Mitsubishi Rayon Co | Hikakuyokozobutsuno seizoho |
| JPS581221B2 (en) * | 1974-12-12 | 1983-01-10 | 帝人株式会社 | Shikagawa henshiyokubutsuno |
| DE2543093A1 (en) * | 1975-09-26 | 1977-04-07 | Bayer Ag | PROCESS FOR THE PREPARATION OF BISULFITE ADDITION PRODUCTS FROM POLYISOCYANATE PREPOLYMERS IN WATER |
-
1977
- 1977-09-06 JP JP52106292A patent/JPS5928670B2/en not_active Expired
-
1978
- 1978-08-03 CA CA000308728A patent/CA1118170A/en not_active Expired
- 1978-08-11 DE DE2835293A patent/DE2835293C3/en not_active Expired
- 1978-08-24 NL NLAANVRAGE7808751,A patent/NL176483C/en not_active IP Right Cessation
- 1978-09-01 BE BE190224A patent/BE870167A/en not_active IP Right Cessation
- 1978-09-01 GB GB7835248A patent/GB2004496B/en not_active Expired
- 1978-09-04 IT IT50958/78A patent/IT1106627B/en active
- 1978-09-05 ES ES473105A patent/ES473105A1/en not_active Expired
- 1978-09-06 CH CH934578A patent/CH639158A5/en not_active IP Right Cessation
- 1978-09-06 FR FR7825669A patent/FR2401766A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5441302A (en) | 1979-04-02 |
| ES473105A1 (en) | 1979-04-01 |
| JPS5928670B2 (en) | 1984-07-14 |
| FR2401766B1 (en) | 1981-09-11 |
| NL7808751A (en) | 1979-03-08 |
| GB2004496B (en) | 1982-02-17 |
| BE870167A (en) | 1979-01-02 |
| CH639158A5 (en) | 1983-10-31 |
| DE2835293B2 (en) | 1981-02-19 |
| FR2401766A1 (en) | 1979-03-30 |
| DE2835293C3 (en) | 1981-10-01 |
| IT1106627B (en) | 1985-11-11 |
| GB2004496A (en) | 1979-04-04 |
| IT7850958A0 (en) | 1978-09-04 |
| DE2835293A1 (en) | 1979-03-08 |
| NL176483B (en) | 1984-11-16 |
| NL176483C (en) | 1985-04-16 |
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