CA2087793A1 - Socks and stockings comprising fiber containing metal - Google Patents
Socks and stockings comprising fiber containing metalInfo
- Publication number
- CA2087793A1 CA2087793A1 CA002087793A CA2087793A CA2087793A1 CA 2087793 A1 CA2087793 A1 CA 2087793A1 CA 002087793 A CA002087793 A CA 002087793A CA 2087793 A CA2087793 A CA 2087793A CA 2087793 A1 CA2087793 A1 CA 2087793A1
- Authority
- CA
- Canada
- Prior art keywords
- socks
- stockings
- fiber
- mixed
- metal oxides
- 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.)
- Abandoned
Links
- 239000000835 fiber Substances 0.000 title description 25
- 229910052751 metal Inorganic materials 0.000 title description 8
- 239000002184 metal Substances 0.000 title description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 35
- 150000004706 metal oxides Chemical class 0.000 description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 32
- 210000004177 elastic tissue Anatomy 0.000 description 29
- 239000004814 polyurethane Substances 0.000 description 29
- 229920002635 polyurethane Polymers 0.000 description 29
- 229910044991 metal oxide Inorganic materials 0.000 description 27
- 230000000694 effects Effects 0.000 description 20
- 230000005855 radiation Effects 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 239000002657 fibrous material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 14
- 230000005670 electromagnetic radiation Effects 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000017531 blood circulation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229920006307 urethane fiber Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B11/00—Hosiery; Panti-hose
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
- A41B17/00—Selection of special materials for underwear
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
- D10B2501/021—Hosiery; Panti-hose
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Socks And Pantyhose (AREA)
- Artificial Filaments (AREA)
- Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)
- Radiation-Therapy Devices (AREA)
Abstract
Abstract SOCKS AND STOCKINGS COMPRISING FIBER CONTAINING METAL
This invention relates to socks and stockings comprising the fiber containing metal which comprises fiber materials mixed-spun with at least 2% polyurethane elastic fiber to which at least one of metal oxides selected from alumina, silica, and titania, as well as platinum are mixed as essential components, wherein, because metal oxides are mixed in the polyurethane elastic fiber with expandability, electromagnetic radiation (far infrared radiation) liberated from the metal oxides are emitted nearly in close contact with the human body, permitting electromagnetic radiation (far infrared radiation) to work effectively on the contact feeling at the wearing portion as well as when the socks and stockings are put on and thermal conductivity while they are worn, and enabling manifestation of an extremely excellent heat-retaining effect.
This invention relates to socks and stockings comprising the fiber containing metal which comprises fiber materials mixed-spun with at least 2% polyurethane elastic fiber to which at least one of metal oxides selected from alumina, silica, and titania, as well as platinum are mixed as essential components, wherein, because metal oxides are mixed in the polyurethane elastic fiber with expandability, electromagnetic radiation (far infrared radiation) liberated from the metal oxides are emitted nearly in close contact with the human body, permitting electromagnetic radiation (far infrared radiation) to work effectively on the contact feeling at the wearing portion as well as when the socks and stockings are put on and thermal conductivity while they are worn, and enabling manifestation of an extremely excellent heat-retaining effect.
Description
2~;~7~g,~
SOCKS AND STOCKINGS COMPRISING FIBER CONTAINING METAL
Field of the Invention This invention relates to socks and stockings comprising fiber containing metal and the object of the present invention is to provide socks and stockings comprising fiber containing metal which not only provides agreeable wear comfort while they are worn but also emitts electro magnetic radiation liberated from the metal oxides nearly in close with the body of wearer to work effectively on contact feeling at the wearing portion as same as when they are put on and thermal conductivity while they are worn, enabling manifestation of an extremely good heat-retaining effect.
Description of Prior Art In general, for fiber materials forming socks and stockings, cotton, nylon, polyester, acrylic, and urethane fiber are well-known, and these fiber materials are properly selected according to wearing seasons, such as for summer or for winter and mixed-spun at an optional ratio to form socks and stockings.
For example, socks and stockings for summer are formed with fiber materials primarily comprising cotton in view of permeability and absorbency, while socks and stockings for winter, in addition to said fiber materials, wool is rrequently mixed to improve heat-retaining property.
Recently, in anticipation of heat-retaining property of far infrared radiation, socks and stockings using fiber mixed with far infrared irradiating ceramics as a component material have been known.
This socks and stockings use fiber having far infrared . ~
.
208779~
irradiating material.s like alumina, girconia, or magne~ia conta.ined in polyethylene- and polyamide-based fiber materials which show high permeability to far infrared radiation and the fiber material containing this far infrared irradiating material futher covered with a protection layer as part of the component fiber, and are formed in anticipaction of the heat-retaining effect by wearing.
Problems to be Solved b~ this Invention However, it is difficult that the socks and stockings mixed-spun with the wool manifest sufficient heat-retaining effect at soles of wearer, but mixed-spinning wool at high ratio to increase a heat-retaining effect causes bulkiness of the socks and stockings themselves, producing a problem that the socks and stockings are not worn readily.
On the other hand, the socks and stockings mixed with far infrared irradiating ceramics can eliminate the bulkiness as compared with said socks and stockings mixed-spun with wool but they have a problem that the intended effect is difficult to be achieved unless a large area is covered with the fiber material containing far infrared irradiating substance over the whole socks and stockings.
In addition, they have another problem that since in this socks and stockings a covered layer is provided to protect the far infrared irradiating layer but this covered layer absorbs far infrared radiation, the far infrared radiation emitted from the ceramics is unable to be effectively used.
Consequently, this socks and stockings have a problem that effect by the far infrared radiation is unable to work most effectively on the contact feeling when the socks and stockings are put on, thermal conductivity while they are .
:
SOCKS AND STOCKINGS COMPRISING FIBER CONTAINING METAL
Field of the Invention This invention relates to socks and stockings comprising fiber containing metal and the object of the present invention is to provide socks and stockings comprising fiber containing metal which not only provides agreeable wear comfort while they are worn but also emitts electro magnetic radiation liberated from the metal oxides nearly in close with the body of wearer to work effectively on contact feeling at the wearing portion as same as when they are put on and thermal conductivity while they are worn, enabling manifestation of an extremely good heat-retaining effect.
Description of Prior Art In general, for fiber materials forming socks and stockings, cotton, nylon, polyester, acrylic, and urethane fiber are well-known, and these fiber materials are properly selected according to wearing seasons, such as for summer or for winter and mixed-spun at an optional ratio to form socks and stockings.
For example, socks and stockings for summer are formed with fiber materials primarily comprising cotton in view of permeability and absorbency, while socks and stockings for winter, in addition to said fiber materials, wool is rrequently mixed to improve heat-retaining property.
Recently, in anticipation of heat-retaining property of far infrared radiation, socks and stockings using fiber mixed with far infrared irradiating ceramics as a component material have been known.
This socks and stockings use fiber having far infrared . ~
.
208779~
irradiating material.s like alumina, girconia, or magne~ia conta.ined in polyethylene- and polyamide-based fiber materials which show high permeability to far infrared radiation and the fiber material containing this far infrared irradiating material futher covered with a protection layer as part of the component fiber, and are formed in anticipaction of the heat-retaining effect by wearing.
Problems to be Solved b~ this Invention However, it is difficult that the socks and stockings mixed-spun with the wool manifest sufficient heat-retaining effect at soles of wearer, but mixed-spinning wool at high ratio to increase a heat-retaining effect causes bulkiness of the socks and stockings themselves, producing a problem that the socks and stockings are not worn readily.
On the other hand, the socks and stockings mixed with far infrared irradiating ceramics can eliminate the bulkiness as compared with said socks and stockings mixed-spun with wool but they have a problem that the intended effect is difficult to be achieved unless a large area is covered with the fiber material containing far infrared irradiating substance over the whole socks and stockings.
In addition, they have another problem that since in this socks and stockings a covered layer is provided to protect the far infrared irradiating layer but this covered layer absorbs far infrared radiation, the far infrared radiation emitted from the ceramics is unable to be effectively used.
Consequently, this socks and stockings have a problem that effect by the far infrared radiation is unable to work most effectively on the contact feeling when the socks and stockings are put on, thermal conductivity while they are .
:
- 3 - 2~8779~
worn, and skin temperature after they are worn, so that the excellent heat-retaining effects cannot be expected.
Therefore, in the industry, invention of socks and stockings which effects successfully on contact feeling when they are put on, thermal conductivity while they are worn, and the wearing temparature, with an extremely excellent heat-retaining property, has been required.
Means to Solve the Problems A11 of the above-mentioned prior problems are solved by providing socks and stockings comprising fiber containing metal which comprises fiber materials mixed-spun with at least 2% polyurethane elastic fiber, to which at least one of metal oxides selected from alumina, silica, and titania as well as platinum are mixed as essential components.
Detailed Description of the Invention The construction Or socks and stockings comprising fiber containing metal relating to the present invention will be described in detail hereinafter.
In this invention, the fiber material mixed-spun with at least 2% polyurethane elastic fiber mixed with at least one of metal oxides selected from alumina (Al203), silica (SiOz), and titania (TiO2) as well as platinum (Pt) as essential components is designated as component fiber.
As alumina (Alz03), silia (SiO2), and titania (TiO2) used in 2~ the present invention, those in the powder form with grain size of 1 ~ or smaller are favorably used, but there is no restriction.
As platinum (Pt), that with grain size as fine as 7-40~ and - ~ - 2~8779~
in a colloidal form is preferably used.
This is based on the experimental knowledge of the inventor that the use of colloidal-form platinum can yield the satisfactory heat-retaining property.
The mix ratio o~ these metal oxides and platinum is about 9-45% alumina (Al203), 50-80% silica (SiO2), 8-15% each titania (TiO2) and/or platinum (Pt), but there is no restriction.
To these metal oxides, oxides of calcium, zinc, and copper may be mixed by about 2-10%.
From the metal oxides comprised as above, electromagnetic radiation (far infrared radiation) with a 5-12 micron wavelength range to be effective for human bodies are stably and sufficiently emitted even at the tempeature range of' around 30 C , as clear from the following tests.
Polyurethane elastic fiber to which metal oxides and platinum are mixed is not particularly specified but SPANDEX
which comprises a noncrystalline segments including either polyester or polyether portions and crystalline segment with urethane bonds and is popularly used in regular textile products is favorably used.
A method to mix metal oxides and platinum to said polyurethane elastic fiber is not particularly specified but any of the optional methods can be adopted as required, such as the method to mix the polymerized fiber material solution dispersedly in the solution before dry spinning or mix into the dry-spun yarns.
The blending ratio of metal oxides mixed in polyurethane elastic fiber is not particularly specified but any of the -5- 2~87793 blending ratio can be favorably adopted if it is the blending ratio which emitts electromagnetic radiation (far infrared radiation) with a wavelength range of about 5-12 microns to be effective for human bodies at the temperature around 30 C , successfully effects contact feeling and thermal conductivity during wearing and manifests an satisfactory heat-retaining effect and is within the range that enables to spin and that does not impair wear comfort as component fiber material of socks and stockings.
Furthermore, in the present invention, the reason why polyurethane elastic fiber is particularly used is that mixed-spinning polyurethane elastic fiber with generous expandability results in improved wear comfort of socks and stockings and at the same time mixing the above-mentioned metal oxides and platinum to this polyurethane elastic fiber enables emission of electromagnetic radiation (far infrared radiation) from the metal oxides into the body with the socks and stockings closely in contact with the body of the wearer, makes the best use of the effect of emitted electromagnetic radiation (far infrared radiation), and allows the electromagnetic radiation (far infrared radiation ) to work effectively on the contact feeling when the socks and stockings are put on and the thermal conductivity, there by temperature variation in the body increases after the socks and stockings are worn and the blood flow rate at the wearing portion is easy to increase, as a result, a superior heat-retaining effect can be manifested.
The polyurethane elastic fiber mixed with at least one of metal oxides selected from the above-mentioned alumina (Al203), silica (SiOz), and titania (TiO2) as well as platinum (Pt) as essential components is mixed-spun with other regular f`iber materials into socks and stockings through a regular method. In this event, polyurethane elastic fiber must be mixed-spun with metal oxides by at - 6 - ~Q87793 least 2%.
This is because in case that the mixed-spinning ratio of polyurethane elastic fiber containing metal oxides is less than 2%, emission of electromagnetic radiation from metal oxides using expandability of the above-mentioned polyurethane elastic fiber does not take place effectively and the superior heat-retaining property is not manifested.
As other fiber materials to be mixed-spun with polyurethane elastic fiber, ordinary natural and artificial fiber materials such as cotton, hemp, wool, acrylic, polyester, and nylon are favorably used and these fiber materials may be optimally mixed-spun to make socks and stockings at an optional ratio, and are not particularly specified.
Effects of the Invention As described above in detail, because the present invention relates to socks and stockings comprising the fiber containing metal which are characterized in comprising fiber material mixed-spun with at least 2% polyurethane elastic fiber, to which at least one of metal oxides selected from alumina, silica, and titania as well as platinum are mixed as essential components, bulkiness of the socks and stockings themselves hardly exist and agreeable wear comfort is ensured when the socks and stockings are put on, and at the same time because electromagnetic radiation (far infrared radiation) by metal oxides is emitted nearly in close contact with the wearer by making use of expandability of polyurethane elastic fiber, as clear from the results of said tests, electromagnetic radiation (far infrared radiation) is permitted to work effectively on contact 3U feeling of the wearing portion as well as when the socks and stockings are put on and thermal conductivity while they are worn, enabling manifeststion of an extremely excellent heat-:
retaining effect.
Brief Description of the Drawings J
Figure 1 is a spectral emissivity chart for the fiber obtained in Example 2.
Figure 2 is a spectral emissivity chart for the fiber obtained in Example 3.
Figure 3 is a spectral emissivity chart for the fiber obtained in Example 4.
Figure 4 is a spectral emissivity chart for the fiber obtained in Example 5.
Figure 5 is a spectral emissivity chart for the fiber obtained in Example 6.
Examples -The effects of socks and stockings comprising fiber containing metal relating to the pressent invention will become more apparent from the following examples.
(Example 1) The 6.4% polyurethane elastic fiber mixed with metal oxides comprising a]umina (Al203), silica (SiO2), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 was mixed-spun with 56% cotton, 24.1% acrylic, and 13.5% nylon, and made into ladies' socks by an ordinary method.
(Conlparison 1) Ladies' socks were made in the same manner of Example 1 -8- ~0877~3 except using polyurethane elastic fiber not mixed with metal oxides.
(Comparison 2) The 1.7% polyurethane elastic fiber mixed with metal oxides comprising alumina (Al203), silica (SiO2), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 was mixed-spun with 64.7% cotton, 27.6% acrylic, and 5.2% nylon, and made into men's socks by an ordinary method.
(Comparison 3) Men's socks were made in the same manner of Comparison 2 except using polyurethane elastic fiber not mixed with metal oxides.
(Test 1) The ladies' and men's socks obtained in said Example 1 and Comparisons 1 through 3 were measured for various properties including density (g/m2), thickness (cm), contact feeling (Q
max), steady thermal conductivity (W/cm C x 10-~), and heat-retaining ratio (%) with THERMOLABO 2-KES7 (KATOHTEC: heat property measuring equipment).
Table 1 shows the results.
[A ] [B ] [C ] = ~ [~ ]
EXAMPLE 1 286 0.102 0.083 3.52542.3 COMPARISON 1 287 0.111 0.089 4.71935.2 _ ____ . _ _ _ __ COMPARISON 2 438 0.221 0.064 8.49539.7 _ _ COMPARISON 3 4380.236 0.068 8.873 45.4 .
: ~ :
.
.
- 9 ~~ 2 0 8 77 9 3 [A] ~ENSITY (g/m2) [B] THICKNESS (cm) [C] C~NTACT FEELING (Q max) [D] STEADY THERMAL CONDUCTIVETY (W/cm~C x 10 1) ~ 2 [E] HEAT-RETAINING RATIO (%) ~ 3 1 : The coldness felt by wearer in putting on;
The bigger value indicates the more coldness.
2: The facility of thermal conduction of cloth;
The bigger value indicates the more facility.
~ 3 : The ability of heat-retaining of cloth;
The bigger value indicates the better ability.
(Test 2) Using the ladies' and men's socks obtained in said Example 1 and Comparsions 1 through 3, tests were carried out on the living body.
First of all, skin temparature of right and left soles of a paneler were masured as the skin temparature before putting on socks, after adjusting on the living body for a specified period to harmonize the skin temparature of the right and left soles.
After the measure, the sock of Example 1 was put on the left foot, the sock of Comparison 1 was put on the right foot, and skin temperature (average, maximum) of the soles were measured in the situation after putting on and retaining heat for 900 seconds.
Then, the right and le~t socks was taken off, skin temperature (average, maximum) of the right and left soles were measured immediately after and about 61 seconds after the socks was taken off.
The overall temperature variation in skin temperature at the right and left soles while wearin6 the socks was calculated.
, . . . :
- lo- 2Q~7793 Next, using the same paneler, skin temparature of right and left soles was adjusted on the living body for a speciried period in the same manner, then the sock of Comparison 2 was put on the left foot, the sock of Comparison 3 was put on the right foot, and skin temperature (average, maximum) of the soles and the overall temperature variation in skin temperature were measured in the same manner.
The measured skin temperatures in this test were calculated from average and maximum values of the picture analysis temperature distribution of a specific region ~f the thermogram obtained from thermo analysis by thermograph (NEC
San-Ei 6T/62 type (HgCdTe sensor, 8-13 u m): infrared radiation thermometer - 50- 2000~C ).
Table 2 shows the results.
_ __ _ [A ] _ _ [C ] ~C] [D]
EXAMPLE 1 29. 3 29 . 1 31 . 1 ( 1 . O ) 31 . 1 1 . 8 _ _ 31.5 31.5 33.8 (2.3) 33.8 2.3 COMPARISON 1 31.2 30.2 32.8 (0-5) 32.8 1.6 33.5 32.3 34.7 (1.2) 34.7 1.2 ______ COMPARISON 2 32.6 32.1 33.1 (0.5) 32.8 0.2 34.3 34.0 35.2 (0.9) 34.6 0.3 _ COMPARISON 3 31.6 32.0 32.6 (1.0) 32.6 1.0 ~
33.7 34.0 34.2 (0.5) 34.2 0.5 l_ [A] PEFORE PUTTING ON
[B] WEARING AND HEAT-RETAINING
/ HEAT-RETAINING FOR 900 SEC.
[C] RIGHT AF'TER TAKING OFF
[D] RADIATION OF HEAT / RADIATION FOR 66 SEC.
[E] OVERALL TEMPERATURE VARIATION
THE UPPER ROW : AVERAGE TEMPARATURE (C ) THE LOWER ROW : MAXIMUM TEMPARATURE (C ) ( ~ indicate~ temparature of heat-retaining effect.
-. - - . . .
, . ~ ~
.
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(Test 3) The ladies' socks of said Example 1 and Comparison 1 were respectively worn by the same paneler on the hand, and the blood flow rate (ml/min/100g) was measured by the laser Doppler method (Journal of the Laser Medical Society of Japan Vol. 12, No. 1, 7. 1988) using the laser Doppler rheometer (ADVANST: ALF-21) in both cases of retaining heat and heating by irradiation from a lamp.
Table 3 shows the results.
_ BLOOD FLOW OF FINGER
(ml/min/100g) EXAMPLE 1 24.0 COMPARISON 1 22.0 _ _ _ _ 24.0 ~
~ THE LOWER ROW CASE OF HEATING BY IRRADIATION FROM LAMP
As clear from TABLE 1, in case that mixed-spinning ratio of polyurethane elastic fiber is 6.4%, comparing ladies' socks mixed with metal oxide (Example 1) with that not mixed with metal oxide (Comparison 1) shows that the density and thickness are small, however small contact feeling results in small coldness when they are put on and small steady thermal conductivity results in small -temperature variation due to the coldness of open-air, proving a high heat-retaining ratio.
In case that polyurethane elastic fiber is mixed-spun as low as 1.7% (Comparison 2), the effect is similar to that using polyurethane elastic fiber not containing metal oxides (Comparison 3), showing that heat-retaining effect is not sufficiently manifested.
-,:
- , - .: , ' , ~; ' ' ', ~
.
- . .
2 ~ ~3 rt r~ ~ 3 As clear from TABLE 2, in case of mixed-spinning ratio of polyurethane elastic fiber is 6.4%, in the balance of heat-retaining and heat-radiation a~ter puttting on the socks, the socks containing metal oxides (Example l) provides overall temperature variation difference 0.2C higher on average and 1.1 ~C higher on maximum than that of socks not containing metal oxides (Comparison l), showing higher heat-retaining effect.
On the contrary, in case that the mixed-spinning ratio of polyurethane elastic fiber is low (Comparisons 2 and 3), heat-retaining effect by wearing socks is not manifested.
As clear from TABLE 3, the socks of Example l tend to increase the blood flow rate by heat-retaining as compared to the socks of Comparison l.
(Example 2) The 15% polyurethane elastic fiber containing metal oxides comprising alumina (Al203), silica (sio2 ), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 is mixed-spun with 85% cotton to make fiber.
(Example 3) The 18% polyurethane elastic fiber same as said Example 2 are mixed-spun with 82% cotton to make fiber.
(Example 4) The 28% polyurethane elastic fiber same as said Example 2 are mixed-spun with 72% cotton into fiber.
:
. , (Example 5) The 50% polyurethane elastic fiber same as said Example 2 are mixed-splln with 50% staple fiber to make fiber.
(Example 6) The 17% polyurethane elastic fiber same said above Example 2 are mixed-spun with 83% nylon to make fiber.
(Test 4) For the fiber obtained by Examples 2 through 6, spectral emissivity was measured.
Measuring conditions are the wavelength range: 4.5-20.0 ~ m;
resolution: 16cm-' ; detector: wide-range MCT; measuring temperature: 33 C for surface temperature of texture;
measuring position and time: four tlmes in total, each once at two different positions and twice at the same position.
~igures 1 through 5 show the obtained relevant spectral emissivity.
Qs clear from the obtained spectral emissivity, in the fiber obtained in Examples 2 through 6, electromagnetic radiation (far infrared radiation) with wavelengths about 5-12 microns to be effective for human bodies is emitted even at the comparatively low temperature range of 33C .
worn, and skin temperature after they are worn, so that the excellent heat-retaining effects cannot be expected.
Therefore, in the industry, invention of socks and stockings which effects successfully on contact feeling when they are put on, thermal conductivity while they are worn, and the wearing temparature, with an extremely excellent heat-retaining property, has been required.
Means to Solve the Problems A11 of the above-mentioned prior problems are solved by providing socks and stockings comprising fiber containing metal which comprises fiber materials mixed-spun with at least 2% polyurethane elastic fiber, to which at least one of metal oxides selected from alumina, silica, and titania as well as platinum are mixed as essential components.
Detailed Description of the Invention The construction Or socks and stockings comprising fiber containing metal relating to the present invention will be described in detail hereinafter.
In this invention, the fiber material mixed-spun with at least 2% polyurethane elastic fiber mixed with at least one of metal oxides selected from alumina (Al203), silica (SiOz), and titania (TiO2) as well as platinum (Pt) as essential components is designated as component fiber.
As alumina (Alz03), silia (SiO2), and titania (TiO2) used in 2~ the present invention, those in the powder form with grain size of 1 ~ or smaller are favorably used, but there is no restriction.
As platinum (Pt), that with grain size as fine as 7-40~ and - ~ - 2~8779~
in a colloidal form is preferably used.
This is based on the experimental knowledge of the inventor that the use of colloidal-form platinum can yield the satisfactory heat-retaining property.
The mix ratio o~ these metal oxides and platinum is about 9-45% alumina (Al203), 50-80% silica (SiO2), 8-15% each titania (TiO2) and/or platinum (Pt), but there is no restriction.
To these metal oxides, oxides of calcium, zinc, and copper may be mixed by about 2-10%.
From the metal oxides comprised as above, electromagnetic radiation (far infrared radiation) with a 5-12 micron wavelength range to be effective for human bodies are stably and sufficiently emitted even at the tempeature range of' around 30 C , as clear from the following tests.
Polyurethane elastic fiber to which metal oxides and platinum are mixed is not particularly specified but SPANDEX
which comprises a noncrystalline segments including either polyester or polyether portions and crystalline segment with urethane bonds and is popularly used in regular textile products is favorably used.
A method to mix metal oxides and platinum to said polyurethane elastic fiber is not particularly specified but any of the optional methods can be adopted as required, such as the method to mix the polymerized fiber material solution dispersedly in the solution before dry spinning or mix into the dry-spun yarns.
The blending ratio of metal oxides mixed in polyurethane elastic fiber is not particularly specified but any of the -5- 2~87793 blending ratio can be favorably adopted if it is the blending ratio which emitts electromagnetic radiation (far infrared radiation) with a wavelength range of about 5-12 microns to be effective for human bodies at the temperature around 30 C , successfully effects contact feeling and thermal conductivity during wearing and manifests an satisfactory heat-retaining effect and is within the range that enables to spin and that does not impair wear comfort as component fiber material of socks and stockings.
Furthermore, in the present invention, the reason why polyurethane elastic fiber is particularly used is that mixed-spinning polyurethane elastic fiber with generous expandability results in improved wear comfort of socks and stockings and at the same time mixing the above-mentioned metal oxides and platinum to this polyurethane elastic fiber enables emission of electromagnetic radiation (far infrared radiation) from the metal oxides into the body with the socks and stockings closely in contact with the body of the wearer, makes the best use of the effect of emitted electromagnetic radiation (far infrared radiation), and allows the electromagnetic radiation (far infrared radiation ) to work effectively on the contact feeling when the socks and stockings are put on and the thermal conductivity, there by temperature variation in the body increases after the socks and stockings are worn and the blood flow rate at the wearing portion is easy to increase, as a result, a superior heat-retaining effect can be manifested.
The polyurethane elastic fiber mixed with at least one of metal oxides selected from the above-mentioned alumina (Al203), silica (SiOz), and titania (TiO2) as well as platinum (Pt) as essential components is mixed-spun with other regular f`iber materials into socks and stockings through a regular method. In this event, polyurethane elastic fiber must be mixed-spun with metal oxides by at - 6 - ~Q87793 least 2%.
This is because in case that the mixed-spinning ratio of polyurethane elastic fiber containing metal oxides is less than 2%, emission of electromagnetic radiation from metal oxides using expandability of the above-mentioned polyurethane elastic fiber does not take place effectively and the superior heat-retaining property is not manifested.
As other fiber materials to be mixed-spun with polyurethane elastic fiber, ordinary natural and artificial fiber materials such as cotton, hemp, wool, acrylic, polyester, and nylon are favorably used and these fiber materials may be optimally mixed-spun to make socks and stockings at an optional ratio, and are not particularly specified.
Effects of the Invention As described above in detail, because the present invention relates to socks and stockings comprising the fiber containing metal which are characterized in comprising fiber material mixed-spun with at least 2% polyurethane elastic fiber, to which at least one of metal oxides selected from alumina, silica, and titania as well as platinum are mixed as essential components, bulkiness of the socks and stockings themselves hardly exist and agreeable wear comfort is ensured when the socks and stockings are put on, and at the same time because electromagnetic radiation (far infrared radiation) by metal oxides is emitted nearly in close contact with the wearer by making use of expandability of polyurethane elastic fiber, as clear from the results of said tests, electromagnetic radiation (far infrared radiation) is permitted to work effectively on contact 3U feeling of the wearing portion as well as when the socks and stockings are put on and thermal conductivity while they are worn, enabling manifeststion of an extremely excellent heat-:
retaining effect.
Brief Description of the Drawings J
Figure 1 is a spectral emissivity chart for the fiber obtained in Example 2.
Figure 2 is a spectral emissivity chart for the fiber obtained in Example 3.
Figure 3 is a spectral emissivity chart for the fiber obtained in Example 4.
Figure 4 is a spectral emissivity chart for the fiber obtained in Example 5.
Figure 5 is a spectral emissivity chart for the fiber obtained in Example 6.
Examples -The effects of socks and stockings comprising fiber containing metal relating to the pressent invention will become more apparent from the following examples.
(Example 1) The 6.4% polyurethane elastic fiber mixed with metal oxides comprising a]umina (Al203), silica (SiO2), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 was mixed-spun with 56% cotton, 24.1% acrylic, and 13.5% nylon, and made into ladies' socks by an ordinary method.
(Conlparison 1) Ladies' socks were made in the same manner of Example 1 -8- ~0877~3 except using polyurethane elastic fiber not mixed with metal oxides.
(Comparison 2) The 1.7% polyurethane elastic fiber mixed with metal oxides comprising alumina (Al203), silica (SiO2), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 was mixed-spun with 64.7% cotton, 27.6% acrylic, and 5.2% nylon, and made into men's socks by an ordinary method.
(Comparison 3) Men's socks were made in the same manner of Comparison 2 except using polyurethane elastic fiber not mixed with metal oxides.
(Test 1) The ladies' and men's socks obtained in said Example 1 and Comparisons 1 through 3 were measured for various properties including density (g/m2), thickness (cm), contact feeling (Q
max), steady thermal conductivity (W/cm C x 10-~), and heat-retaining ratio (%) with THERMOLABO 2-KES7 (KATOHTEC: heat property measuring equipment).
Table 1 shows the results.
[A ] [B ] [C ] = ~ [~ ]
EXAMPLE 1 286 0.102 0.083 3.52542.3 COMPARISON 1 287 0.111 0.089 4.71935.2 _ ____ . _ _ _ __ COMPARISON 2 438 0.221 0.064 8.49539.7 _ _ COMPARISON 3 4380.236 0.068 8.873 45.4 .
: ~ :
.
.
- 9 ~~ 2 0 8 77 9 3 [A] ~ENSITY (g/m2) [B] THICKNESS (cm) [C] C~NTACT FEELING (Q max) [D] STEADY THERMAL CONDUCTIVETY (W/cm~C x 10 1) ~ 2 [E] HEAT-RETAINING RATIO (%) ~ 3 1 : The coldness felt by wearer in putting on;
The bigger value indicates the more coldness.
2: The facility of thermal conduction of cloth;
The bigger value indicates the more facility.
~ 3 : The ability of heat-retaining of cloth;
The bigger value indicates the better ability.
(Test 2) Using the ladies' and men's socks obtained in said Example 1 and Comparsions 1 through 3, tests were carried out on the living body.
First of all, skin temparature of right and left soles of a paneler were masured as the skin temparature before putting on socks, after adjusting on the living body for a specified period to harmonize the skin temparature of the right and left soles.
After the measure, the sock of Example 1 was put on the left foot, the sock of Comparison 1 was put on the right foot, and skin temperature (average, maximum) of the soles were measured in the situation after putting on and retaining heat for 900 seconds.
Then, the right and le~t socks was taken off, skin temperature (average, maximum) of the right and left soles were measured immediately after and about 61 seconds after the socks was taken off.
The overall temperature variation in skin temperature at the right and left soles while wearin6 the socks was calculated.
, . . . :
- lo- 2Q~7793 Next, using the same paneler, skin temparature of right and left soles was adjusted on the living body for a speciried period in the same manner, then the sock of Comparison 2 was put on the left foot, the sock of Comparison 3 was put on the right foot, and skin temperature (average, maximum) of the soles and the overall temperature variation in skin temperature were measured in the same manner.
The measured skin temperatures in this test were calculated from average and maximum values of the picture analysis temperature distribution of a specific region ~f the thermogram obtained from thermo analysis by thermograph (NEC
San-Ei 6T/62 type (HgCdTe sensor, 8-13 u m): infrared radiation thermometer - 50- 2000~C ).
Table 2 shows the results.
_ __ _ [A ] _ _ [C ] ~C] [D]
EXAMPLE 1 29. 3 29 . 1 31 . 1 ( 1 . O ) 31 . 1 1 . 8 _ _ 31.5 31.5 33.8 (2.3) 33.8 2.3 COMPARISON 1 31.2 30.2 32.8 (0-5) 32.8 1.6 33.5 32.3 34.7 (1.2) 34.7 1.2 ______ COMPARISON 2 32.6 32.1 33.1 (0.5) 32.8 0.2 34.3 34.0 35.2 (0.9) 34.6 0.3 _ COMPARISON 3 31.6 32.0 32.6 (1.0) 32.6 1.0 ~
33.7 34.0 34.2 (0.5) 34.2 0.5 l_ [A] PEFORE PUTTING ON
[B] WEARING AND HEAT-RETAINING
/ HEAT-RETAINING FOR 900 SEC.
[C] RIGHT AF'TER TAKING OFF
[D] RADIATION OF HEAT / RADIATION FOR 66 SEC.
[E] OVERALL TEMPERATURE VARIATION
THE UPPER ROW : AVERAGE TEMPARATURE (C ) THE LOWER ROW : MAXIMUM TEMPARATURE (C ) ( ~ indicate~ temparature of heat-retaining effect.
-. - - . . .
, . ~ ~
.
20~779~
(Test 3) The ladies' socks of said Example 1 and Comparison 1 were respectively worn by the same paneler on the hand, and the blood flow rate (ml/min/100g) was measured by the laser Doppler method (Journal of the Laser Medical Society of Japan Vol. 12, No. 1, 7. 1988) using the laser Doppler rheometer (ADVANST: ALF-21) in both cases of retaining heat and heating by irradiation from a lamp.
Table 3 shows the results.
_ BLOOD FLOW OF FINGER
(ml/min/100g) EXAMPLE 1 24.0 COMPARISON 1 22.0 _ _ _ _ 24.0 ~
~ THE LOWER ROW CASE OF HEATING BY IRRADIATION FROM LAMP
As clear from TABLE 1, in case that mixed-spinning ratio of polyurethane elastic fiber is 6.4%, comparing ladies' socks mixed with metal oxide (Example 1) with that not mixed with metal oxide (Comparison 1) shows that the density and thickness are small, however small contact feeling results in small coldness when they are put on and small steady thermal conductivity results in small -temperature variation due to the coldness of open-air, proving a high heat-retaining ratio.
In case that polyurethane elastic fiber is mixed-spun as low as 1.7% (Comparison 2), the effect is similar to that using polyurethane elastic fiber not containing metal oxides (Comparison 3), showing that heat-retaining effect is not sufficiently manifested.
-,:
- , - .: , ' , ~; ' ' ', ~
.
- . .
2 ~ ~3 rt r~ ~ 3 As clear from TABLE 2, in case of mixed-spinning ratio of polyurethane elastic fiber is 6.4%, in the balance of heat-retaining and heat-radiation a~ter puttting on the socks, the socks containing metal oxides (Example l) provides overall temperature variation difference 0.2C higher on average and 1.1 ~C higher on maximum than that of socks not containing metal oxides (Comparison l), showing higher heat-retaining effect.
On the contrary, in case that the mixed-spinning ratio of polyurethane elastic fiber is low (Comparisons 2 and 3), heat-retaining effect by wearing socks is not manifested.
As clear from TABLE 3, the socks of Example l tend to increase the blood flow rate by heat-retaining as compared to the socks of Comparison l.
(Example 2) The 15% polyurethane elastic fiber containing metal oxides comprising alumina (Al203), silica (sio2 ), titania (TiO2), and platinum (Pt) in the ratio 10:82:3:5 is mixed-spun with 85% cotton to make fiber.
(Example 3) The 18% polyurethane elastic fiber same as said Example 2 are mixed-spun with 82% cotton to make fiber.
(Example 4) The 28% polyurethane elastic fiber same as said Example 2 are mixed-spun with 72% cotton into fiber.
:
. , (Example 5) The 50% polyurethane elastic fiber same as said Example 2 are mixed-splln with 50% staple fiber to make fiber.
(Example 6) The 17% polyurethane elastic fiber same said above Example 2 are mixed-spun with 83% nylon to make fiber.
(Test 4) For the fiber obtained by Examples 2 through 6, spectral emissivity was measured.
Measuring conditions are the wavelength range: 4.5-20.0 ~ m;
resolution: 16cm-' ; detector: wide-range MCT; measuring temperature: 33 C for surface temperature of texture;
measuring position and time: four tlmes in total, each once at two different positions and twice at the same position.
~igures 1 through 5 show the obtained relevant spectral emissivity.
Qs clear from the obtained spectral emissivity, in the fiber obtained in Examples 2 through 6, electromagnetic radiation (far infrared radiation) with wavelengths about 5-12 microns to be effective for human bodies is emitted even at the comparatively low temperature range of 33C .
Claims
1. Socks and stockings comprising fiber containing metal which are characterized in comprising fiber materials mixed-spun with at least 2% polyurethane elastic fiber, to which at least one of metal oxides selected from alumina, silica, and titania as well as platinum are mixed as essential components.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4-213557 | 1992-07-16 | ||
JP4213557A JP2585166B2 (en) | 1992-07-16 | 1992-07-16 | Socks made of metal-containing fibers |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2087793A1 true CA2087793A1 (en) | 1994-01-17 |
Family
ID=16641184
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002087793A Abandoned CA2087793A1 (en) | 1992-07-16 | 1993-01-21 | Socks and stockings comprising fiber containing metal |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0582769B1 (en) |
JP (1) | JP2585166B2 (en) |
KR (1) | KR100237718B1 (en) |
AT (1) | ATE138537T1 (en) |
CA (1) | CA2087793A1 (en) |
DE (1) | DE69302865T2 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2124649B1 (en) * | 1995-05-29 | 1999-11-16 | Pergo Nv | CLOTHING FOR MEN, ESPECIALLY BOXES WITH MAGNETIC ELEMENTS, ESPECIALLY TO INCREASE MALE SEXUAL POWER. |
KR0155608B1 (en) * | 1995-07-14 | 1998-12-01 | 박홍기 | Method for producing far-infrared radioactive polyester fiber |
DE19819900A1 (en) * | 1998-05-05 | 1999-11-11 | Thermal Quarz Schmelze Gmbh | Infrared radiator element |
EP1442168A1 (en) | 2001-11-09 | 2004-08-04 | Legend Care I.P. Limited | A sock |
DE202007001955U1 (en) * | 2007-02-06 | 2007-04-26 | X-Technology Swiss Gmbh | Sock for electrically heated footwear includes a zone incorporating thermally conducting thread aligned with the heating pad |
SI2072666T1 (en) | 2007-09-28 | 2012-01-31 | Venex Co Ltd | Fiber containing nano-sized diamond and platinum nanocolloid, and bedding product comprising the fiber |
ES2569657T3 (en) | 2007-12-14 | 2016-05-12 | Rhodia Poliamida E Especialidades Ltda | Polymeric composition, process for the manufacture of the polymeric composition, articles based on this polymeric composition and use of these articles |
GR1009117B (en) * | 2015-04-06 | 2017-09-18 | Γεωργιος Εμμανουηλ Ψιψικας | Skin-contacting garments produced from fabric coated with a synthetic material based on metal oxides and a non-organic material |
WO2018225464A1 (en) * | 2017-06-08 | 2018-12-13 | 岡本株式会社 | Clothing item |
JP6952956B2 (en) * | 2017-08-22 | 2021-10-27 | 株式会社エスティー | Heat storage socks |
KR101971849B1 (en) * | 2019-02-25 | 2019-04-23 | 박희대 | Thermoplastic Polyurethane Yarn |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63112701A (en) * | 1986-10-29 | 1988-05-17 | 株式会社 ア−スクリ−ン | Socks |
JP2577379B2 (en) * | 1987-04-07 | 1997-01-29 | 旭化成工業株式会社 | Antibacterial and deodorant socks |
JPH0473226A (en) * | 1989-07-25 | 1992-03-09 | J Pii U:Kk | Yarn for woven fabric containing far infrared radiation substance and production thereof |
JPH03190990A (en) * | 1989-12-20 | 1991-08-20 | Toshio Komuro | Powder for radiation of infrared ray-weak energy and synthetic fiber containing same powder |
JPH0434001A (en) * | 1990-05-30 | 1992-02-05 | Toray Ind Inc | Stocking |
-
1992
- 1992-07-16 JP JP4213557A patent/JP2585166B2/en not_active Expired - Lifetime
-
1993
- 1993-01-21 CA CA002087793A patent/CA2087793A1/en not_active Abandoned
- 1993-01-30 DE DE69302865T patent/DE69302865T2/en not_active Expired - Fee Related
- 1993-01-30 AT AT93101479T patent/ATE138537T1/en not_active IP Right Cessation
- 1993-01-30 EP EP93101479A patent/EP0582769B1/en not_active Expired - Lifetime
- 1993-03-15 KR KR1019930003877A patent/KR100237718B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE138537T1 (en) | 1996-06-15 |
KR100237718B1 (en) | 2000-01-15 |
KR940001831A (en) | 1994-02-16 |
EP0582769B1 (en) | 1996-05-29 |
DE69302865T2 (en) | 1996-09-26 |
JPH0641801A (en) | 1994-02-15 |
EP0582769A1 (en) | 1994-02-16 |
JP2585166B2 (en) | 1997-02-26 |
DE69302865D1 (en) | 1996-07-04 |
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