JP2000290831A - Fluorescent coloring polyvinyl alcohol fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber and a fiber structure having high fluorescence coloring luminance and feeling and excellent in visibility and decorativeness. The present invention provides a fluorescent color-forming polyvinyl alcohol-based fiber containing at least one inorganic compound having a fluorescent color-forming property.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent color-forming polyvinyl alcohol (PVA) fiber, a fiber structure using the fiber, and a method for producing the fiber. The present invention relates to a fiber having excellent decorativeness.

[0002]

2. Description of the Related Art Conventionally, countermeasures for preventing forgery of securities paper,
It is known to use fluorescent coloring fibers for interior decoration such as wallpaper and carpet. The fiber does not emit light when exposed to visible light such as in sunlight or in a room with ordinary lighting, but emits light when irradiated with ultraviolet light in a dark place. , Figures, patterns, shapes, and the like can be raised and visually recognized. As a method of obtaining a fluorescent coloring fiber,
A method of applying and impregnating fibers with an inorganic fluorescent agent or an organic fluorescent agent having a fluorescent color under ultraviolet irradiation (Japanese Patent Application Laid-Open No.
No. 67764) and a method of adding a fluorescent agent to a thermoplastic resin and performing melt spinning (Japanese Patent Application Laid-Open No. 6-128807).
It has been known.

[0003]

However, the former method has a problem that the feeling of the fibers and the fiber structure is poor, and the fluorescent agent peels off due to long-term use or friction.
Further, in the latter method, since the fiber is spun by the melt spinning method, the fiber is likely to be broken, and there is a limit to the amount of the fluorescent color former that can be blended from the viewpoint of spinnability. For this reason, the emission luminance of the fluorescent color is lowered, the coloring is likely to be unclear, and the visibility is insufficient. From the above, the above-mentioned Japanese Patent Application Laid-Open No.
No. 28807 proposes a core-sheath composite fiber having a resin containing a fluorescent agent as a core component and a resin not containing a fluorescent agent as a sheath component in order to increase the content of a luminescent colorant. Have been shown to improve. However, in the melt spinning, since the yarn breakage is likely to occur, the amount of the fluorescent agent cannot be increased so much.
In addition, since the fluorescent agent is present only in the core component, the fluorescent coloring luminance and coloring properties are low. SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber having a good feel and a high fluorescent coloring luminance and coloring property, and a fiber structure comprising the fiber.

[0004]

SUMMARY OF THE INVENTION The present invention provides (1) a fluorescent coloring polyvinyl alcohol fiber containing at least one inorganic compound having a fluorescent coloring property, and (2) a fluorescent coloring polyvinyl alcohol-based fiber. (3) a fluorescent-color-forming polyvinyl alcohol-based fiber containing the above-mentioned inorganic compound, (3) a fluorescent-color-forming polyvinyl alcohol-based fiber containing one or more kinds of inorganic compounds and pigments that emit fluorescence under ultraviolet irradiation, (4) (1) To (3) a fiber structure using the fluorescent color-forming polyvinyl alcohol-based fiber described in any one of (1) to (3); Paper.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The PVA constituting the PVA fiber of the present invention is not particularly limited, and a modified PVA modified by another unit may be used. The average degree of polymerization of PVA is preferably 300 or more and 5,000 or less, particularly preferably 500 or more and 3,000 or less, from the viewpoint of handling properties and fiber properties of a spinning dope for wet or dry-wet spinning. The degree of saponification is preferably 96% or more and more preferably 99% or more from the viewpoint of water resistance and the like.

[0006] PVA fibers can be spun by a wet spinning method, a dry-wet spinning method, or a dry spinning method, so that breakage or the like hardly occurs, and thus a fiber having a large amount of an inorganic compound and excellent fluorescent coloring property can be obtained. In the case of melt spinning, the fiber constituent resin is easily affected by hard inorganic fine particles because it is melted during spinning, and easily breaks and breaks, resulting in impaired spinnability and the mechanical properties of the resulting fiber. The quality is low. Also in the case of performing wet spinning or the like, it is difficult to produce a spinning dope in which the inorganic compound is easily aggregated and uniformly dispersed, so that thread breakage is likely to occur and fiber quality is likely to be impaired. However, in the present invention, since PVA is used as a fiber constituent resin,
Micellization by PVA is performed, whereby the uniform dispersibility of the inorganic compound and the stability of the stock solution for spinning are remarkably improved, and a desired fiber can be obtained.

In some cases, conjugate spun fibers (core-sheath type,
It may be a side-by-side type, a laminated type or the like, or a mixed spun fiber (sea-island structure fiber) or the like, but it is preferable to contain a color-forming inorganic compound in the vicinity of the fiber surface from the viewpoint of obtaining high color development. It is preferable that a part of the color-forming inorganic compound exists in the surface layer within 1 μm from the fiber surface.

The fluorescent chromogenic inorganic compound (hereinafter sometimes simply referred to as “fluorescent inorganic compound”) used in the present invention is not particularly limited. For example, an inorganic compound that fluoresces under ultraviolet irradiation (a luminous compound). ) Or inorganic compounds that emit luminous fluorescence by visible light, and specific examples thereof include those that emit fluorescent colors such as white, blue, red, and green. It is preferable to use an inorganic compound that emits fluorescence under ultraviolet irradiation from the viewpoints of a camouflage prevention effect, ease of color control, and the like. From the viewpoint of the human body environment and the ease of developing the coloring effect, the wavelength is 1 nm or more and less than 400 nm, particularly 200 nm.
Inorganic compounds that emit fluorescence when irradiated with ultraviolet light having a wavelength of 380 nm or less are preferred.

For example, as the inorganic compound which develops a red color, europium-activated Y ₂ O ₃ : Eu, YV
O ₄ : Eu, Y ₂ O ₂ S: Eu, and the inorganic compound that emits green color are ZnS: Cu, AI, and Zu.
S: Cu, Zn ₂ GeO ₄ : Mn, Zn ₂ GeO ₂ : Mn. As an inorganic compound that develops a blue color, Z
nS: Ag, CaWO ₄ , Sr ₅ (PO ₄ ) ₃ Cl: Eu,
Sr ₅ (PO ₂ ) ₃ Cl: Eu, (Ba, Sr, Eu)
(Mg, Mn) Al ₁₀ O _{17 and the} like.

Among them, Y ₂ O ₃ : Eu which emits a clear fluorescent red when irradiated with ultraviolet rays having a wavelength of 254 nm, and which emits a clear blue fluorescent light when irradiated with ultraviolet rays having a wavelength of 365 nm, from the viewpoints of uniform dispersibility and fluorescence coloring property. (Ba, Sr, Eu) (Mg,
Mn) Al ₁₀ O ₁₇ , which emits a clear fluorescent blue-violet color when irradiated with 365 nm ultraviolet rays (Zn, Cd) S: Cu, 365 n
m to emit a clear fluorescent white color by ultraviolet irradiation (ZnS: A
It is preferable to use one or more inorganic compounds selected from g + (Zn, Cd) S: Cu, Al), and particularly Y.
₂ O ₃ : Eu and / or (ZnS: Ag + (Zn, Cd)
S: Cu, Al) is preferably used.

Two or more fluorescent inorganic compounds may be used in combination as a fluorescent coloring agent. From the viewpoint of the forgery prevention effect, it is preferable to use a fiber which emits fluorescence with respect to ultraviolet rays having two or more different wavelengths. It is preferable to use two or more kinds of fluorescent inorganic compounds having different wavelengths of ultraviolet rays emitting fluorescence. Specifically, Y ₂ O ₃ : Eu which expresses a fluorescent red color under irradiation of ultraviolet light with a wavelength of 254 nm, and a fluorescent white color expresses under irradiation of ultraviolet light with a wavelength of 365 nm (ZnS: Ag + (Zn,
A combination of Cd) S: Cu, Al) is preferably exemplified. Also, an anthraquinone-based or acetophenone-based whitening agent can be used in combination.

The larger the particle size of the fluorescent inorganic compound is, the higher the brightness of the fluorescent color becomes, but the sedimentation stability and spinnability in the spinning dope are likely to decrease. From the above, the average particle size is preferably 20 μm or less, particularly preferably 5 μm or less, and from the viewpoint of emission luminance, it is preferably 0.5 μm or more. In general, those having a small average particle size are not commercially available, and in some cases, it is preferable to reduce the average particle size by pulverizing an inorganic compound. The pulverization method is not particularly limited, and a suitable example is a method in which the inorganic compound is dispersed in water and then wet pulverized using a wet pulverizer (such as an attritor) having ceramic balls.

The proportion of the inorganic compound is 10 to 50% by weight /
It is preferable to use PVA, particularly 15 to 45% by weight / PVA. From the viewpoint of emission luminance, it is preferable to increase the amount of the inorganic compound. However, since the sedimentation and spinnability in the spinning dope are reduced, it is preferable to appropriately examine the amount according to the purpose. When the melt spinning method is employed, the amount of the inorganic compound can be reduced to at most about 8% by weight from the viewpoint of spinnability and the like, but in the present invention, a spinning method other than the melt spinning method can be employed. Since PVA having an excellent effect of uniformly dispersing the inorganic compound is used, even if the amount of the inorganic compound is large, spinnability is hardly impaired, and a fiber having high emission luminance and excellent quality can be obtained.

A PVA-based resin and an inorganic compound are blended to prepare a spinning dope, and the fibers may be produced by a wet spinning method, a dry-wet spinning method or a dry spinning method. P in spinning dope
The mixing ratio of the VA resin is 8 to 30% by weight, particularly 10 to 2% by weight.
It is preferably 0% by weight. If the PVA concentration is too low, the fluorescent fiber will settle out, making it difficult to obtain desired fibers. Although it is preferable to use water as the solvent, an organic solvent such as dimethyl sulfoxide may be used in some cases.

In order to suppress the sedimentation of the inorganic compound in the spinning dope and to remarkably enhance the uniform dispersibility, a dispersion water containing the inorganic compound is injected into the PVA aqueous solution immediately before the spinning nozzle, and the mixture is immediately stirred and stirred. It is preferable to employ a method of uniformly mixing and then discharging from the nozzle. By employing this method, fibers in which the inorganic compound is uniformly dispersed can be produced more efficiently. It is preferable that the dispersion water is always settled by a stirrer until it is poured into the spinning solution. At this time, it is more preferable to add a dispersant for improving the uniform dispersibility of the inorganic compound to the dispersion water containing the inorganic compound. The concentration of the inorganic compound in the dispersion water is preferably 20 to 40% by weight from the viewpoint of uniform dispersibility and the like. The addition of the dispersion water reduces the PVA concentration of the aqueous PVA solution. Is preferably set to be about 3 to 5% higher than the concentration of

From the viewpoint of suppressing aggregation of the inorganic compound and improving dispersibility in water, it is preferable to add various surfactants to the spinning dope. In addition, by adding a surfactant, excellent effects such as prolongation of die life and improvement of stretchability of fiber can be obtained. The addition amount of the surfactant is preferably 20% by weight or less / spinning solution, particularly preferably 0.1 to 5% by weight.

Further, a pigment may be added to the spinning dope to color the fibers in the visible light region. In particular, by adding a pigment having a color different from the emission color of the fluorescent coloring agent, the color developed under visible light irradiation and the fluorescent color generated under ultraviolet irradiation can be changed, which is more excellent in terms of decoration effect and disguise prevention effect. The effect is obtained. The pigment is not particularly limited as long as it can be stably dispersed in a spinning solution containing PVA and a fluorescent coloring agent and can be stably spun. The amount of the pigment added is from 0.01 to 5% by weight / P from the viewpoint of spinning stability and coloring property.
VA, particularly preferably 0.1 to 3% by weight. As the pigment, those which develop color under visible light having a wavelength of 400 nm or more and 780 nm or less are preferable.

By spinning the spinning stock solution by a wet spinning method, a dry spinning method, or a dry-wet spinning method having an air gap filled with air or an inert gas between a spinning nozzle and a coagulation bath, the desired fluorescent coloring property is obtained. A PVA-based fiber is obtained. From the viewpoint of spinning stability, it is more preferable to employ a wet spinning method. When performing wet spinning or dry-wet spinning, it is only necessary to immerse the yarn discharged from the nozzle in a coagulation bath. As the substance having a solidifying ability, salts having a dehydrating ability such as sodium sulfate (Glauber's salt), ammonium sulfate and sodium carbonate can be preferably used. The concentration of the coagulating liquid can be selected from 100 g / liter to a saturated concentration, but those having a concentration close to the saturated concentration can be suitably used because of their high dehydrating and coagulating ability. Coagulation bath concentration is 20
The temperature is preferably from 70 to 70C, particularly preferably from 30 to 50C.

After the shinoshi is separated from the coagulation bath, it may be drawn to a predetermined fiber thickness according to a standard method. As a preferred method, after the bath is separated, the roller is stretched about 1 to 4 times, and then the same dehydration and coagulation capacity as the coagulation bath is obtained.
After performing wet heat stretching at a low temperature of 1 to 4 times in a bath of 0 to 100 ° C., drying, and stretching and heat treatment are performed as desired. If necessary, a formalization treatment or the like for improving water resistance can be performed.

The visibility of the fluorescent fiber is greatly affected by the amount of the fluorescent inorganic compound added, but is also greatly affected by the thickness of the fiber. The diameter of the fiber may be set as appropriate, but it is preferable to increase the diameter from the viewpoint of visibility. Specifically, the diameter is preferably about 20 to 30 μm or more, that is, 5 d or more. When the dry spinning method is adopted, not only fibers having a diameter of 25 μm or more can be produced, but also monofilaments having a diameter of 1 mm or more can be produced.
Further, when thin fibers are preferable, as in the case where the obtained fibers are made into paper, a wet spinning method or a dry-wet spinning method is preferably employed, and fibers having a diameter of about 5 to 60 μm are efficiently used. Can be manufactured A fiber having an excessively large fiber diameter is not preferable as a stock because of poor papermaking properties. In the melt spinning method, it is difficult to produce fibers with such fineness because the yarn is apt to break.

According to the present invention, there can be obtained a fiber which emits vivid fluorescent light at a high luminance, is excellent in quality and feeling and does not cause sticking or the like, and can be used for all purposes. For example, there are industrial materials, clothing, medical materials, agricultural materials, living materials, miscellaneous goods, and the like, and more specifically, they can be used as forgery prevention papers such as curtains, banners, wallpapers, and security papers.

Although the fiber of the present invention may be used as it is, it can be processed into any fiber structure. Specifically, cut fiber, yarn (spun yarn, filament yarn),
It can be processed into strings, ropes, fabrics (woven or knitted fabrics, nonwoven fabrics, etc.). At this time, it may be used in combination with fibers other than the PVA-based fibers of the present invention. The fibers that can be used in combination are not particularly limited, but may be other PVA fibers containing no dyeable fine particles, polyester fibers (including wholly aromatic polyester fibers), polyamide fibers, polyvinyl alcohol-ethylene copolymer. Fiber, cellulose fiber, cotton, hemp, and the like.

Among them, the fiber of the present invention is excellent in water dispersibility since it has high hydrophilicity and does not cause agglutination, and has a high adhesive effect, and thus is suitable as a stock. The fiber may be used as a stock to make a desired paper. At this time, it can be used in combination with general paper materials such as pulp, binder fibers, etc., and the resulting paper has the ability to develop high brightness under UV irradiation without damaging the characteristics of conventional paper. A remarkable effect is obtained from what can be done. The obtained paper is suitable as, for example, anti-counterfeit paper, decorative paper such as wallpaper, etc., and is particularly excellent as anti-counterfeit paper such as security paper.

[0024]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. [Average particle size μm] 5,000 to 20,000 under electron microscope
Regarding the fine particles observed in the cross section of the fiber magnified 00 times, the diameter is measured when the fine particle shape is a perfect circle or a substantially circular shape, and the long diameter is measured when the fine particle shape is non-circular, and the average value of the diameter of the fine particles present in one cross section is calculated This is performed in five or more cross sections, and the average value is obtained. In the case of the fine particle dispersion, the particle size distribution is measured using a Microtrac particle size distribution measuring device, and the highest peak point particle size (MV value) is defined as the average particle size. [Content of inorganic compound (vs. PVA added) wt%] The PVA-based fiber weighed in advance is dissolved in hot water, and the solution is filtered through a Teflon membrane filter or ultrafiltration membrane to separate the inorganic compound. After drying, the content was determined.

Example 1 30 parts by weight of a fluorescent inorganic compound having a structural formula of Y ₂ O ₃ : Eu (“P22-RE1” manufactured by Kasei Optonics Co., Ltd.) that emits fluorescence under ultraviolet irradiation, and a water dispersant (Kao Corporation) Was added to 62.5 parts by weight of water to prepare an aqueous dispersion of 30% by weight of a fluorescent inorganic compound. Next, the aqueous dispersion was wet-pulverized in a wet ball mill equipped with ceramic balls until the average particle size of the inorganic compound became about 1 μm.

PVA aqueous solution having a PVA (degree of saponification: 99.9 mol%, viscosity average degree of polymerization: 1700) concentration of 18% by weight
Into 0 parts by weight, 18 parts by weight of the dispersion of the pulverized fluorescent inorganic compound having a concentration of 30% by weight was injected and stirred to obtain a PVA concentration of 16% by weight.
Immediately after the spinning stock solution was prepared, it was discharged from a nozzle having 2000 holes into a coagulating solution having a temperature of 40 ° C. and a sodium sulfate concentration of 420 g / liter to form a shinoshino. Next, the obtained Itoshino is
La-stretching (drawing ratio 2 times), then 1.5-fold wet heat stretching in a saturated sodium sulfate bath at 95 ° C, and then drying at 160 ° C,
Further, it was heat-treated at 220 ° C. and wound up. The spinning property is good, and the yarn can be efficiently spun without substantially causing breakage,
The fluorescent inorganic compound was uniformly dispersed in the fiber.
Next, the Glauber's salt contained was washed in running water at 25 ° C. for 1 hour with the ligament, and dried in a dryer to produce a fiber having a single fiber fineness of 10d. The obtained fiber contains a fluorescent inorganic compound in an amount of 30% by weight / PVA, has no sticking or the like, has a good feeling, and is white under visible light.
Under the ultraviolet irradiation of m, a clear fluorescent red color was generated.

Example 2 (Ba, S)
r, Eu) (Mg, Mn) Al 3 O ₁₇ , except that an inorganic compound represented by Al ₁₀ O ₁₇ (“LP-B2” manufactured by Kasei Optonics Co., Ltd.) was used. A liquid was prepared and wet-pulverized PVA (degree of saponification: 99.9 mol%, viscosity average degree of polymerization: 17)
00) 100 parts by weight of a PVA aqueous solution having a concentration of 18% by weight
12 parts by weight of the obtained dispersion of the fluorescent inorganic compound having a concentration of 30% by weight was injected and stirred to prepare a spinning solution having a PVA concentration of 16% by weight. Thereafter, a 10d fiber was produced in the same manner as in Example 1. . The spinnability was good, the yarn could be efficiently spun without substantial breakage or the like, and the fluorescent inorganic compound was uniformly dispersed in the fiber. The obtained fiber contains 20 fluorescent coloring agents.
% By weight / PVA, no sticking, etc., good feeling, and white under visible light, 365
Under ultraviolet irradiation of nm, a clear fluorescent blue color was generated.

[Example 3] (Zn, C
d) Using an inorganic compound represented by S: Cu (“P7-Y1” manufactured by Kasei Optonics Co., Ltd.), a 30% by weight aqueous dispersion of a fluorescent color former was prepared in the same manner as in Example 1 and wet-ground PVA ( Degree of saponification 99.9 mol%, viscosity average degree of polymerization 17
00) 100 parts by weight of a PVA aqueous solution having a concentration of 18% by weight
A 10 d fiber was produced in the same manner as in Example 1 except that 24 parts by weight of the obtained dispersion of the crushed fluorescent inorganic compound having a concentration of 30% by weight was injected and stirred to prepare a spinning solution having a PVA concentration of 16% by weight. The spinnability was good, the yarn could be efficiently spun without substantial breakage or the like, and the fluorescent inorganic compound was uniformly dispersed in the fiber. The obtained fiber contains 40% by weight of a fluorescent coloring agent / PVA, has no sticking or the like, has a good feeling, is white under visible light, and has a clear fluorescent blue under irradiation with ultraviolet light of 365 nm. A purple color developed.

Example 4 As a fluorescent color former (ZnS:
An aqueous dispersion of 30% by weight of a fluorescent color former in the same manner as in Example 1 except that an inorganic compound represented by Ag + (Zn, Cd) S: Cu, Al) (“P4-K” manufactured by Kasei Optonics Co., Ltd.) was used. Was prepared and pulverized. PVA (degree of saponification: 99.9 mol%, viscosity average degree of polymerization: 1700) PVA having a concentration of 18% by weight
To 100 parts by weight of the aqueous solution, the pulverized fluorescent inorganic compound concentration of 3
18 parts by weight of a 0% by weight dispersion and 0.5 parts by weight of an orange pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) are added, and the mixture is stirred.
A spinning stock solution having a VA concentration of 16% by weight was prepared, and a fiber having a single fiber fineness of 10d was produced in the same manner as in Example 1. The spinnability was good, the yarn could be efficiently spun without substantial breakage or the like, and the fluorescent inorganic compound was uniformly dispersed in the fiber. The obtained fiber contains a fluorescent coloring agent in an amount of 30% by weight / PVA, has no sticking or the like, has a good feeling, and has an orange color under visible light and a clear fluorescent light under irradiation with 365 nm ultraviolet rays. A white color developed.

Example 5 30 parts by weight of a fluorescent coloring agent ("P22-RE1" manufactured by Kasei Optonics Co., Ltd.) comprising an inorganic compound represented by the structural formula Y ₂ O ₃ : Eu, and an aqueous dispersing agent (manufactured by Kao Corporation) 7.5 parts by weight of "Demol P" (pure content: 20% by weight) were added to 62.5 parts by weight of water to prepare an aqueous dispersion of 30% by weight of a fluorescent color former. Next, the aqueous dispersion was wet-pulverized in a wet ball mill equipped with ceramic balls until the average particle size of the fluorescent coloring agent became about 1 μm. In a similar manner, the structural formula (ZnS: Ag + (Zn, Cd) S:
An aqueous dispersion of an inorganic compound represented by the formula (Cu, Al) (“P4-K” manufactured by Kasei Optonics Co., Ltd.) is produced and has an average particle size of about 1
Wet pulverization was performed until the particle size reached μm.

PVA aqueous solution 10 having a PVA (degree of saponification of 99.9 mol%, viscosity average degree of polymerization of 1700) concentration of 18% by weight
0 parts by weight, 12 parts by weight of each of the dispersions having a concentration of the pulverized fluorescent inorganic compound of 30% by weight was added, and the mixture was stirred.
After adjusting the spinning solution of 6% by weight, a fiber having a single fiber fineness of 10d was produced in the same manner as in Example 1. The spinnability was good, the yarn could be efficiently spun without substantial breakage or the like, and the fluorescent inorganic compound was uniformly dispersed in the fiber. The obtained fiber contains each fluorescent inorganic compound in an amount of 20% by weight / PVA, and has good feeling without sticking or the like.
Under visible light, a bright fluorescent red color was developed under irradiation of ultraviolet light of 254 nm, and a clear fluorescent white color was formed under irradiation of ultraviolet light of 365 nm. The fiber emits different fluorescences with respect to ultraviolet rays having two different wavelengths, and is extremely excellent in forgery prevention effect and the like.

Comparative Example 1 A spinning dope was prepared and wet spinning was carried out in the same manner as in Example 4, except that the fluorescent coloring agent was not added to the spinning dope. The thickness of this shinoshino was 10 denier single yarn and orange under visible light, but did not emit fluorescence even when irradiated with 365 nm ultraviolet rays.

Examples 6 to 10 Papers were produced using the PVA fibers obtained in Examples 1 to 5. First, the sample fiber was cut to a fiber length of about
Dispersed in water at 8 ° C., and then PVA binder fiber (“VPB105-1 × 3” single fiber fineness 1 by Kuraray Co., Ltd.)
d, fiber length 3 mm) was added so as to be 15% by weight of the total weight of the stock, and uniformly stirred and mixed to prepare a slurry having a solids concentration of 0.4% by weight. Using such a slurry, T
After the paper was fed to an APPI type paper machine to form a paper, it was dried using a cylinder dryer at 120 ° C., and the basis weight was 30 g / m 2.
Manufactured paper. All of the fibers obtained in the examples had no sticking between the single fibers, and were excellent in water dispersibility, and high quality paper was obtained. All of them exhibited a fluorescent color with high brightness under ultraviolet irradiation, and were suitable as anti-counterfeiting treated paper such as decorative paper such as wallpaper and security paper.
In particular, the fiber using the fiber obtained in Example 5 emits different fluorescences with respect to the ultraviolet rays having two different wavelengths, and is more excellent in the forgery prevention effect and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) D21H 13/16 D21H 13/16 21/48 21/48 F term (Reference) 4J002 BE021 DA076 DA096 DA116 DE086 DE096 DE146 DG026 DH056 FD096 GK01 HA04 4L035 AA04 BB03 BB06 BB16 BB72 BB81 BB89 BB91 CC01 EE07 FF01 FF05 HH10 JJ01 JJ05 JJ10 KK01 KK06 KK08 4L055 AF21 AF43 AH02 FA12 GA23 GA37 GA45

Claims (5)

[Claims] 1. A fluorescent color-forming polyvinyl alcohol-based fiber containing at least one inorganic compound having a fluorescent color-forming property. 2. A fluorescing polyvinyl alcohol fiber containing at least one inorganic compound which fluoresces under ultraviolet irradiation. 3. A fluorescing polyvinyl alcohol fiber containing at least one inorganic compound which fluoresces under ultraviolet irradiation and a pigment. 4. A fiber structure comprising the fluorescent coloring polyvinyl alcohol-based fiber according to claim 1. 5. Paper comprising the fluorescent coloring polyvinyl alcohol-based fiber according to claim 1.