JP7614238B2 - Textile products and their manufacturing methods - Google Patents

Description

The present invention relates to a functional textile product and a method for producing the textile product. More specifically, the present invention relates to a textile product having antiallergenic and antiviral properties and a method for producing the textile product.

In recent years, interest has been growing in measures to combat allergies caused by pollen and dust mites, as well as viral infections caused by influenza viruses and the like, and in the textile industry, there is also an increasing demand for functional textile products with anti-allergenic and anti-viral properties.

For this reason, the applicant has previously developed a textile product with anti-allergenic and anti-viral properties (Patent Document 1). The textile product in Patent Document 1 is suitable for use in automobile seats and the like, and exhibits excellent anti-allergenic and anti-viral properties, but its washing durability has not been examined. Textile products that are washed by users are required to maintain a high level of anti-viral and anti-allergenic properties even after washing, so there is a demand for textile products with high washing durability.

WO2016/157942

Therefore, the objective of the present invention is to provide a textile product that can maintain high antiviral and antiallergenic properties even after washing, and a method for producing the textile product.

As a result of repeated investigations to solve the above problems, the inventors of the present invention have succeeded in developing a textile product that exhibits high antiviral and antiallergenic properties even after repeated washing by immersing a textile substrate such as a fabric in a dispersion liquid containing zirconium phosphate and a specific antiviral component to adhere the zirconium phosphate and the antiviral component to the textile substrate, and then forming a resin layer containing zirconium phosphate and the specific antiviral component on at least a portion of the surface of the textile substrate.

The present invention, which can solve the above problems, has the following configuration.
[1]
A textile product,
The present invention includes a fiber substrate and a resin layer present on at least a portion of a surface of the substrate,
The zirconium phosphate (A) and the antiviral component (B) are adhered to the substrate in amounts of 1.0 to 3.0 g/m ² and 2.0 to 5.0 g/m ² per unit area of the substrate, respectively;
the resin layer contains zirconium phosphate (A) and an antiviral component (B) in amounts of 1.2 to 4.0 g/m ² and 2.9 to 3.9 g/m ² , respectively, per unit area of the substrate;
The textile product, wherein the antiviral component (B) contains a compound (b1) having a salt of a sulfonic acid group and an organic acid (b2) having a carboxy group.
[2]
the compound having a salt of a sulfonic acid group comprises a linear polymer, an aromatic ring bonded to the linear polymer, and a sulfonic acid group bonded directly or indirectly to the aromatic ring,
The textile product according to [1], wherein the organic acid having a carboxy group has a plurality of carboxy groups in the molecule.
[3]
The substrate is in a sheet form,
The resin layers are disposed on one surface of the sheet-like substrate at intervals,
The textile product according to [1] or [2], wherein a ratio of a total area of the resin layer to a total area of one side of the substrate is 10% or more and 60% or less.
[4]
1. A method for producing a textile product, comprising:
(I) a step of immersing a fiber substrate in a dispersion containing zirconium phosphate (A), an antiviral component (B), and a resin (C1), and then removing the fiber substrate from the dispersion and drying it;
(II) forming a resin layer on at least a portion of the surface of the substrate by printing using a composition containing zirconium phosphate (A), an antiviral component (B), and a resin (C2), wherein
the antiviral component (B) in the steps I and II contains a compound (b1) having a salt of a sulfonic acid group and an organic acid (b2) having a carboxy group,
the amounts of zirconium phosphate (A) and antiviral component (B) attached to the substrate by step I are 1.0 to 3.0 g/m ² and 2.0 to 5.0 g/m ² per unit area of the substrate, respectively;
the amounts of zirconium phosphate (A) and the antiviral component (B) contained in the resin layer formed by the step II are 1.2 to 4.0 g/m ² and 2.9 to 3.9 g/m ² , respectively, per unit area of the substrate;
method.
[5]
The method according to [4], further comprising the step of washing the substrate with hot water after step II.

The present invention provides a textile product that can maintain high antiviral and antiallergenic properties even after washing.

The textile product according to the present invention comprises a textile substrate and a resin layer present on at least a portion of the surface thereof, zirconium phosphate (A) and an antiviral component (B) are attached to the textile substrate, and the resin layer also contains zirconium phosphate (A) and an antiviral component (B).

Such textile products can be produced, as described above, by a process comprising the steps of:
(I) immersing a fiber substrate in a dispersion containing zirconium phosphate (A), an antiviral component (B), and a resin (C1), and then removing the fiber substrate from the dispersion and drying it; and
(II) A step of forming a resin layer on at least a portion of the surface of the substrate by printing using a composition containing zirconium phosphate (A), an antiviral component (B), and a resin (C2).

Process I is a process known as DIP-NIP processing, in which, for example, the fiber substrate is immersed in a dispersion liquid, then removed from the dispersion liquid, and the water is squeezed out of the fiber substrate using a mangle roller or the like, and the fiber substrate is then dried (for example, at a temperature of 120 to 170°C), thereby adhering the zirconium phosphate (A) and the antiviral component (B) to the fiber substrate.

The amount of zirconium phosphate (A) attached to the substrate in step I is 1.0 to 3.0 g/ ^m2 per unit area of the substrate. If the amount of zirconium phosphate is too small, the anti-allergenicity becomes insufficient, and if the amount is too large, chalk marks are likely to occur. The amount of zirconium phosphate (A) attached is more preferably 1.5 to 2.5 g/ ^m2 , and particularly preferably 1.7 to 2.3 g/ ^m2 .

The amount of the antiviral component (B) adhered to the substrate in step I is preferably 2.0 to 5.0 g/ ^m2 per unit area of the substrate. The amount of the antiviral component (B) adhered is more preferably 2.4 to 4.0 g/ ^m2 , and particularly preferably 2.9 to 3.6 g/ ^m2 .

The resin (C1) used in step I serves to adhere the zirconium phosphate (A) and the antiviral component (B) to the substrate. As the resin, polyester-based resins, acrylic-based resins, urethane-based resins, etc. can be used. Polyester-based resins and urethane-based resins are more preferred, and polyester-based resins are particularly preferred. The amount of resin adhered to the substrate in step I is preferably 0.4 to 1.5 g/ ^m2 in the case of polyester-based resins, more preferably 0.5 to 1.0 g/ ^m2 . In the case of urethane-based resins and acrylic-based resins, it is preferably 0.05 to 1.5 g/ ^m2 , and particularly preferably 0.1 to 0.8 g/ ^m2 .

Step II is a process known as resin printing, in which, for example, zirconium phosphate (A), antiviral component (B), and resin (C2) are mixed and, if necessary, thickened to an appropriate viscosity with a thickener (e.g., a cellulose-based thickener such as carboxymethyl cellulose) to prepare a composition, and the composition is applied to at least a portion of the substrate surface by screen printing (e.g., a rotary screen, etc.) to form a resin layer containing (A) and (B) on at least a portion of the substrate surface. If only step I is performed without step II, the antiallergenic and antiviral properties of the textile product decrease after washing, and the desired properties cannot be maintained, so step II is essential for producing a textile product with washing durability.

The resin layers are preferably arranged on the substrate at intervals. For example, resin layers of a predetermined shape may be repeatedly arranged at intervals on the substrate surface to form a repeating pattern (pattern pattern) made of the resin layers on the substrate surface. For example, when the substrate is in the form of a sheet such as a fabric, the resin layer may be in the form of a pattern pattern formed on the entire surface of one side of the sheet-like substrate. The ratio of the total area of the resin layers to the total area of one side of the substrate is preferably 10% to 60%, more preferably 10% to 40%, and particularly preferably 10% to 20%. By partially forming a resin layer on the substrate surface, the texture of the fabric can be kept softer than when the entire substrate surface is coated with a resin layer. In addition, since the stretch of the fabric itself is less restricted, the fabric can be made into a sheet with improved tailoring properties, and improved appearance quality such as wrinkles and horns and sewability can be expected.

The amount of zirconium phosphate (A) in the resin layer formed in step II is preferably 1.2 to 4.0 g/ ^m2 per unit area of the substrate. If the amount of zirconium phosphate is too small, the anti-allergenicity becomes insufficient. In consideration of chalk marks, the amount of zirconium phosphate in the resin layer is preferably 3.8 g/m2 or ^less . The amount of zirconium phosphate (A) in the resin layer is more preferably 2.0 to 3.7 g/ ^m2 , and particularly preferably 2.2 to 3.5 g/ ^m2 .

The amount of the antiviral component (B) in the resin layer formed in step II is preferably 2.9 to 3.9 g/ ^m2 per unit area of the substrate. If it is less than 2.9 g/ ^m2 or more than 3.9 g/ ^m2 , the antiviral properties of the textile product after washing will be insufficient. The amount of the antiviral component (B) in the resin layer is more preferably 3.0 to 3.8 g/ ^m2 , and particularly preferably 3.2 to 3.6 g/ ^m2 .

As the resin (C2) used in step II, polyester resin, acrylic resin, urethane resin, etc. can be used. From the viewpoint of flame retardancy, polyester resin and urethane resin are more preferable (when acrylic resin is used, it is preferable to use it in combination with a flame retardant). In consideration of texture, friction fastness, washing durability, etc., urethane resin is particularly preferable. In the case of urethane resin, the amount of resin in the resin layer is preferably 2.0 to 5.0 g/m ² , and particularly preferably 2.5 to 4.0 g/m ² , per unit area of the substrate. In the case of polyester resin, it is preferably 1.5 to 4.0 g/m ² , and particularly preferably 2.0 to 3.0 g/m ^2. In the case of acrylic resin, it is preferably 2.0 to 2.8 g/m ^2. If the amount of resin is too small or too large, the antiallergenicity and/or antiviral property of the textile product tends to decrease after washing.

The resin (C1) in step I and the resin (C2) in step II may be the same or different, but taking into consideration not only the antiallergenic and antiviral properties but also other properties such as the texture of the fabric, flame retardancy, and chalk marks, it is preferable to use a polyester resin in step I and a urethane resin in step II, each in the amounts described above.

After step II, washing with hot water (step III) may be performed as an option. In step III, the fiber substrate on which the resin layer has been formed is washed with hot water at 65 to 90°C (more preferably 70 to 90°C, and particularly preferably 75 to 85°C). This step makes it possible to remove excess surfactants, thickeners, etc., and improve the edge appearance of the fiber product. After washing with hot water, the fabric is dried. Appropriate drying conditions are, for example, 110 to 170°C, particularly 120 to 160°C, for about 1 to 5 minutes.

The textile product of the present invention has excellent antiallergenic and antiviral properties even after washing, and is therefore particularly suitable for textile products that may be washed, such as seat covers for vehicles (cars, trains, airplanes, etc.) and interior items (e.g. furniture covers, curtains, etc.).

The fiber base material, zirconium phosphate, and antiviral component used in the present invention will be described in more detail below.
Fiber Base Material
The fiber substrate of the present invention may be one or more fibers selected from natural fibers (cotton, hemp, wool, silk, etc.), regenerated fibers (rayon, etc.), semi-synthetic fibers (acetate, etc.), and synthetic fibers (polyester, polyamide, polyacrylonitrile). The fiber substrate may be in the form of a sheet, and for example, a fabric (woven fabric, knitted fabric, felt, nonwoven fabric, etc.) can be used. In particular, a fabric made of polyester-based fibers is preferred.

(A) Zirconium Phosphate The zirconium phosphate (A) used in steps I and II is preferably α-zirconium phosphate, the crystal of which has a layered structure. As the zirconium phosphate (A), for example, Allerimub (registered trademark) ZK-200 sold by Toagosei Co., Ltd. can be used. The average particle size of zirconium phosphate is preferably 0.5 to 1.5 μm, and more preferably 0.8 to 1.3 μm. If the average particle size is less than 0.5 μm, it will recondense and it will be difficult to prepare a stable paste or dispersion, and if it exceeds 1.5 μm, chalk marks will easily occur. The average particle size can be measured using a scattering type particle size distribution measuring device (for example, scattering type particle size distribution measuring device LA-950 [manufactured by Horiba, Ltd.]).

(B) Antiviral Component The antiviral component (B) used in steps I and II has a viral infection inhibitory effect (meaning an effect of eliminating or reducing the infectivity of a virus to a cell, or an effect of preventing the virus from proliferating in the cell even if the virus infects the cell). As such an antiviral component (B), a composition containing (b1) a compound having a salt of a sulfonic acid group and (b2) an organic acid having a carboxy group can be used.

The compound (b1) having a salt of a sulfonic acid group contains a salt of a sulfonic acid group (--SO ₃ X: X is a metal element or NH ⁴⁺ ) in the molecule. The compound having a salt of a sulfonic acid group has an excellent viral infection inhibitory effect, particularly against enveloped viruses. The salt of a sulfonic acid group is not particularly limited and examples thereof include sodium salts, calcium salts, and ammonium salts, with sodium salts being particularly preferred.

An example of the compound (b1) having a salt of a sulfonic acid group is a compound containing a linear polymer (e.g., a carbon chain), an aromatic ring bonded to the linear polymer, and a sulfonic acid group bonded directly or indirectly to the aromatic ring. The aromatic ring may be a monocyclic aromatic ring or a condensed aromatic ring (a ring in which multiple monocyclic aromatic rings are condensed). The aromatic ring is not particularly limited, and examples include a benzene ring and a naphthalene ring, with a benzene ring being particularly preferred. It is more preferred that the sulfonic acid group is directly bonded to the aromatic ring. When the sulfonic acid group is indirectly bonded to the aromatic ring, it is preferred that the salt of the sulfonic acid group is bonded to the aromatic ring via an alkylene group having 1 to 4 carbon atoms (preferably a methylene group or an ethylene group).

Another example of a compound (b1) having a salt of a sulfonic acid group is a compound that contains a linear polymer (e.g., a carbon chain) and a sulfonic acid group bonded to the end of the polymer.

Examples of linear polymers include carbon chains, polyester chains, and polyurethane chains, with carbon chains being particularly preferred.

Preferred examples of the compound (b1) having a salt of a sulfonic acid group include linear alkylbenzene sulfonate, alkyldiphenylether sulfonate, polymers having a salt of a sulfonic acid group in the side chain of a linear polymer (main chain), and α-olefin sulfonate.

The number of carbon atoms in the alkyl group of the linear alkylbenzene sulfonate is preferably 10 to 25, more preferably 11 to 20, and even more preferably 12 to 18. Preferred examples of linear alkylbenzene sulfonate include dodecylbenzene sulfonate, tridecylbenzene sulfonate, and tetradecylbenzene sulfonate, and sodium dodecylbenzene sulfonate is particularly preferred.

Examples of alkyl diphenyl ether sulfonates include sodium salts and calcium salts of alkyl phenyl ethers whose alkyl group has carbon numbers of C6 to C18, with sodium dodecyl diphenyl ether sulfonate (C12) being particularly preferred.

As a polymer having a salt of a sulfonic acid group in the side chain of a linear polymer (main chain), a polymer having a main chain selected from a carbon chain, a polyester chain, and a polyurethane chain, and a side chain containing an aromatic ring to which a sulfonic acid group is directly or indirectly bonded, is particularly preferred. Such a polymer includes a polymer containing a styrene sulfonate component, such as a styrene sulfonate homopolymer, a styrene-styrene sulfonate copolymer, a sulfonate of a compound obtained by sulfonating the benzene ring of polystyrene, or a sulfonate of a compound obtained by sulfonating the benzene ring of a polymer containing a styrene component. A homopolymer of sodium styrene sulfonate (particularly sodium p-styrene sulfonate) or a copolymer of sodium styrene sulfonate (particularly sodium p-styrene sulfonate) and styrene is more preferred.

Examples of α-olefin sulfonates include sodium and calcium salts of C12 to C18 olefin sulfonic acids, with C14 sodium tetradecene sulfonate being particularly preferred.

The organic acid (b2) can improve the viral infection prevention effect against non-enveloped viruses by promoting the release of the salt of the sulfonic acid group in the compound (b1) having a salt of the sulfonic acid group. In addition, the compound (b1) having a salt of the sulfonic acid group can weaken the capsid (protein shell) of the non-enveloped virus, improving the viral infection prevention effect of the organic acid (b2) against non-enveloped viruses. In this way, the antiviral component (B) contains (b1) and (b2) and thereby exhibits an improved viral infection prevention effect against enveloped and non-enveloped viruses.

The organic acid (b2) is an organic compound capable of promoting the release of some or all of the salts of sulfonic acid groups in a compound having a salt of a sulfonic acid group, and has a carboxy group (-COOH) in the molecule. The organic acid (b2) preferably has multiple carboxy groups (-COOH) in the molecule. When the organic acid (b2) has multiple carboxy groups (-COOH) in the molecule, the release of some or all of the salts of sulfonic acid groups in the compound (b1) having a salt of a sulfonic acid group can be more reliably maintained or promoted, and the viral infection prevention effect against enveloped viruses and non-enveloped viruses can be further improved. It is preferable that the organic acid does not contain a salt of a sulfonic acid group.

The organic acid (b2) preferably has a pKa of 5.5 or less at 25°C, more preferably 4.0 to 5.0, and particularly preferably 4.2 to 4.6. The pKa of an organic acid can be determined by titrating the organic acid and sodium hydroxide at 25°C and measuring the pH at the half-equivalent point (the point at which half the amount required for complete neutralization has been dropped) at 25°C.

The organic acid (b2) is preferably a polymer, for example, having a weight average molecular weight of 3,000 to 1,000,000, preferably 5,000 to 900,000, more preferably 10,000 to 800,000, and particularly preferably 100,000 to 500,000. In the present invention, the weight average molecular weight of the polymer means a value measured by GPC (gel permeation chromatography) in terms of polystyrene. Particularly preferred polymeric organic acids include polymers in which a carboxy group is bonded as a side chain to a linear polymer (main chain, for example, a carbon chain, a polyester chain, or a polyurethane chain, particularly a carbon chain). Such a polymer can be produced, for example, by polymerizing acrylic acid and an acrylic acid ester (for example, methyl acrylate, etc.). The mass ratio of acrylic acid to acrylic acid ester can be, for example, 90 to 99:10 to 1.

In the antiviral component (B), the mass ratio of the compound (b1) having a salt of a sulfonic acid group to the organic acid (b2) is preferably b1:b2=5-45:95-55, more preferably 5-30:95-70, and particularly preferably 7-15:93-85.

The above-mentioned antiviral component (B) is sold as an antiviral agent in a state where it is mixed with other components such as additives and solvents. Such antiviral agents can be purchased, for example, from Sekisui Material Solutions Co., Ltd.

Next, the present invention will be described in more detail with reference to comparative examples and examples, but the present invention is not limited to the examples.

The zirconium phosphate, antiviral agent, resin (binder), and thickener used are as follows.
Zirconium phosphate and antiviral agent used in step I and step II
・α-zirconium phosphate: Product name: Areri Remove ZK-200 (Toagosei Co., Ltd.)
Antiviral agent: Product name Wiltaker BAC (Sekisui Material Solutions Co., Ltd.) Contains, as the antiviral component (B), a polymer containing styrene sulfonate (a compound (b1) having a salt of a sulfonic acid group) and a polycarboxylic acid (an organic acid (b2) having a carboxy group) in a mass ratio of (b1):(b2) of approximately 1:10)

Resin used in Step I and Step II : Polyester resin: Pluscoat Z (Goo Chemical Co., Ltd.)
- Urethane resin: Evaphanol HA (Nicca Chemical Co., Ltd.)
・Acrylic resin: Newcoat ACR (Shin-Nakamura Chemical Co., Ltd.)
Thickener used in step II
・Cellulose-based thickener: SI-1314 (Shinyo Co., Ltd.)

Step I: DIP-NIP processed zirconium phosphate, antiviral agent, and resin were added to water and mixed to prepare an aqueous dispersion for DIP-NIP. A polyester fabric (100% polyester, basis weight 250 g/ ^m2 ) was immersed in the aqueous dispersion, then squeezed with a mangle at a roll pressure of 3.0 kgf/ ^cm2 , and then dried by heating.

Step II Resin Printing Zirconium phosphate, antiviral agent, and resin were added to water, mixed, and thickened with a cellulose thickener to prepare a composition for resin printing. Using a rotary screen, the composition was screen printed on one side of the fabric after step I to form a pattern consisting of a resin layer. The ratio of the total area of the pattern (resin layer) to the total area of one side of the fabric was about 12%.

Step III: Washing with Hot Water The fabric after step II was washed with hot water at 80° C. and then dried.

[Test 1]
The fabric after step III (hereinafter, "processed fabric") was measured for its anti-cedar pollen allergenicity, anti-mite allergenicity, and antiviral activity.
Thereafter, the treated fabric was washed five times in accordance with JIS L 0217 103, Section 2 (normal) washing method (JAFET standard detergent was used), and the same test was carried out on the treated fabric after washing. The evaluation method is as follows.

<Anti-allergenic (cedar)>
A 5 cm x 2.5 cm piece of treated fabric was placed in a test tube, and 2.25 ml of a solution adjusted to 6.7 ng/ml of Japanese cedar allergen was dropped onto it, and the mixture was left to stand at 20°C for 24 hours. The amount of allergen in the solution was measured by ELISA, and the inactivation rate was calculated using the following formula. The amount of Japanese cedar pollen allergen refers to the total protein amount converted from the amount of Cryj I.
Inactivation rate = [(amount of allergen added - amount of allergen measured after curing) x 100] / amount of allergen added An inactivation rate (anti-allergenicity) of 70% or more is considered to be a pass.

The methods for evaluating the performance of textile products are as follows.
<Anti-allergenic (mites)>
A 5 cm x 2.5 cm piece of treated fabric was placed in a test tube, and 2.25 ml of a solution adjusted to 47 ng/ml mite allergen was dropped onto it, and the mixture was left to stand at 37°C for 8 hours. The amount of allergen in the solution was measured by ELISA, and the inactivation rate was calculated using the following formula. The amount of mite allergen refers to the total protein amount converted from the amount of Derf II.
Inactivation rate = [(amount of allergen added - amount of allergen measured after curing) x 100] / amount of allergen added An allergen inactivation rate (anti-allergenicity) of 91% or more is considered to be a pass.

<Antiviral>
1. Prepare a virus suspension (Influenza A virus [mouse H1N1] suspension).
0.2 mL of the virus suspension was dropped onto the treated fabric (0.4 g) cut into a 2.3 cm square, and the fabric was left to stand at 25°C for 2 hours.
3. Then, place the treated fabric in a centrifuge tube, add 1.8 ml of maintenance medium, centrifuge, and extract 1 ml of reaction liquid.
4. Dilute the extracted reaction solution with maintenance medium to prepare a dilution series (10-fold, 100-fold, 1,000-fold, 10,000-fold, 100,000-fold).
5. The dilution series is inoculated into host cells (MDBK cells: derived from bovine kidney cells), and the dilution ratio at which 50% of the cells are infected (TCID ₅₀ : Median tissue culture infectious dose) is determined (this value is the virus infectivity value _Vc ).
6. The virus infectivity of the untreated fabric is designated as _Vb , and the virus reduction rate is calculated by the following formula I.
Formula I: Virus reduction rate (%) = [(V _b - V _c ) x 100]/V _b
A virus reduction rate of 99.9% or more is considered a pass.

The results are shown in Table 1. The numerical value of each component in Table 1 is the mass (g) of the solid content of each component per unit area ( ^m2 ) of the fabric (the same applies to Table 2). If all of the anti-allergenic properties (cedar and mite) and anti-viral properties exceeded the target values after five washes, the overall evaluation was rated "good", and if any one of them fell below the target value, it was rated "poor".

As is clear from Table 1, the fabric that underwent only step I (No. 1) had low antiallergenic and antiviral properties after washing, and did not achieve the target values. Even when step II was performed in addition to step I, the fabric (No. 2) in which the amount of zirconium phosphate and antiviral component in step II was small did not reach the target values for antiallergenic and antiviral properties after washing. Furthermore, not only when the amount of antiviral component in step II was small (No. 6 and 7), but also when it was large (No. 10), the desired antiviral properties could not be maintained after washing. Furthermore, when the amount of antiviral component in step I was small (No. 11), the antimite allergenic properties did not reach the target values after washing.

[Test 2]
Next, polyester fabric (100% polyester, basis weight 250 g/ ^m2 ) dyed black or gray was subjected to steps I to III in the same manner as described above. The resulting treated fabric was evaluated for one or more of whitening, chalk marks, friction fastness, bending resistance, abrasion resistance, and flame retardancy. The evaluation methods for each were as follows. In addition, the antiallergenicity and antiviral property after five washes were evaluated in the same manner as described above.

<Bleaching>
The color change (whitening) of each treated fabric was confirmed compared with the fabric before step I (hereinafter, untreated fabric), and the fabric was graded according to the following criteria. Grade 3 or higher was considered to be acceptable.
Judgment details
Grade 5: no color change at all; Grade 4: almost no color change; Grade 3: slight color change; Grade 2: easily noticeable color change; Grade 1: significant color change

<Chalk mark>
To check whether the chalk marks (whitening due to scratches) were worse than those of the untreated fabric, the surfaces of the treated and untreated fabrics were lightly rubbed with a fingernail, and the degree of whitening due to scratches was compared and judged according to the following criteria. Grade 3 or above is judged as passing.
Judgment details
Grade 5: no color change at all; Grade 4: almost no color change; Grade 3: slight color change; Grade 2: easily noticeable color change; Grade 1: significant color change

<Friction fastness>
In accordance with JIS L0849 (test method for color fastness to friction), dry and wet tests were conducted for each processed fabric. Staining was judged on a scale of 1 to 5 using the staining gray scale (JIS L0805). A grade of 4 or higher in the dry test and a grade of 3.5 (between grades 3 and 4) or higher in the wet test are judged as passing.

<Bending and softening properties>
The bending resistance was measured by the so-called cantilever method. Specifically, three test pieces each of 25 mm wide and 200 mm long were taken from the processed fabric in the vertical direction (longitudinal direction) and horizontal direction (direction perpendicular to the longitudinal direction), and placed along a smooth horizontal table with a 45-degree slope at one end, one end of the test piece was accurately aligned with one end of the horizontal table on the slope side, and the position (A) of the other end of the test piece was read on a scale. Next, the test piece was lightly held down by a presser plate of approximately the same size as the test piece, and slid in the direction of the slope at a speed of about 10 mm/s, and the position (B) of the other end when one end of the test piece contacted the slope was read on a scale. The bending resistance is expressed by the travel distance (A-B) of the test piece (the smaller the bending resistance value, the softer the fabric, and the higher the value, the harder the fabric). The table shows the average value (mm) of three measurements for each of the test pieces in the longitudinal and transverse directions. A value of 120 or less is considered to be acceptable.

<Wear resistance>
Each processed fabric was tested according to JIS L1096 (Fabric Testing Method for Woven and Knitted Fabrics). Specifically, a circular test piece with a diameter of 130 mm was taken from each processed fabric, a 6 mm hole was drilled in the center, and the test piece was attached to a sample holder with the surface facing up using a Taber abrasion tester. A CS-10 abrasion wheel was placed on the test piece, a load of 4.9 N was applied, and the test was performed at a rotation speed of 70 rpm to check the degree of wear on the test piece surface. The grade was determined according to the following criteria, and a grade of 3 or higher was determined as passing after 1000 tests, and a grade of 3 or higher was determined as passing after 3000 tests.
Judgment details
・Class 5: No change observed ・Class 4: Slight change observed ・Class 3: Clear change observed ・Class 2: Slight change observed ・Class 1: Significant change <Flame retardancy>
Tests were conducted in accordance with the "Flammability of Interior Materials" stipulated in the Federal Motor-Vehicle Safety Standard (FMVSS) to determine flame retardant performance.
"Self-extinguishing" indicates that the flame was extinguished within a burning distance of 50 mm and within a burning time of 60 seconds after the flame crossed the A mark. For treated fabrics that did not meet the above criteria for "self-extinguishing," the burning rate (mm/min) is recorded in the table, and a burning rate of 81 mm/min or less is judged to be acceptable.

The results are shown in Table 2. Since the bending resistance, abrasion resistance, and flame retardancy do not change depending on the color tone of the fabric, when the test was performed on a gray fabric, the test was omitted for a black fabric.

As shown in Table 2, when the amount of α-zirconium phosphate in process II was large (No. 14), the chalk marks did not reach the target value for dark colored (black) fabrics. When the resin in process II was changed to an acrylic resin (No. 15-17), the flame retardancy did not reach the target value. When the amount of urethane resin used in process II was increased, the target value could be achieved, but the dark colored (black) fabrics tended to be more susceptible to whitening and chalk marks (comparison of No. 18 black and No. 19 black). When the resin in process I was changed to a urethane resin (No. 20) or an acrylic resin (No. 21), the target value could also be achieved, but the dark colored (black) fabrics tended to be more susceptible to chalk marks. When the resin in process II was changed to a polyester resin (No. 22), the target value could be achieved, but the anti-cedar allergenicity after washing was lower than that of the other processed fabrics (No. 3-No. 21). In addition, when the amount of zirconium phosphate in step I was small (less than 1.0 g/ ^m2 ), the allergenicity was reduced, and when it was large (more than 3.0 g/ ^m2 ), chalk marks were likely to occur (data not shown).

As is clear from the results of these tests, according to the present invention, by using a predetermined amount of zirconium phosphate (A) and antiviral component (B) per unit area of the fabric in steps I and II, it is possible to maintain the same antiallergenic and antiviral properties as before washing, even after five repeated washings. In addition to the amounts of (A) and (B), the type and amount of resin used in steps I and II can also be appropriately adjusted to achieve the target values for the other properties shown in Table 2. In order to obtain a textile product that is excellent not only in antiallergenic and antiviral properties but also in other properties, it is particularly preferable to use a polyester resin in step I and a urethane resin in step II.

Claims (5)

A textile product,
The present invention includes a fiber substrate and a resin layer present on at least a portion of a surface of the substrate,
The zirconium phosphate (A) and the antiviral component (B) are adhered to the substrate in amounts of 1.0 to 3.0 g/m ² and 2.0 to 5.0 g/m ² per unit area of the substrate, respectively;
the resin layer contains zirconium phosphate (A) and an antiviral component (B) in amounts of 1.2 to 4.0 g/m ² and 2.9 to 3.9 g/m ² , respectively, per unit area of the substrate;
The textile product, wherein the antiviral component (B) contains a compound (b1) having a salt of a sulfonic acid group and an organic acid (b2) having a carboxy group. the compound having a salt of a sulfonic acid group comprises a linear polymer, an aromatic ring bonded to the linear polymer, and a sulfonic acid group bonded directly or indirectly to the aromatic ring,
The organic acid having a carboxy group has a plurality of carboxy groups in the molecule.
The textile product according to claim 1. The substrate is in a sheet form,
The resin layers are disposed on one surface of the sheet-like substrate at intervals,
3. The textile product according to claim 1, wherein a ratio of a total area of the resin layers to a total area of one side of the substrate is 10% or more and 60% or less. 1. A method for producing a textile product, comprising:
(I) a step of immersing a fiber substrate in a dispersion containing zirconium phosphate (A), an antiviral component (B), and a resin (C1), and then removing the fiber substrate from the dispersion and drying it;
(II) forming a resin layer on at least a portion of the surface of the substrate by printing using a composition containing zirconium phosphate (A), an antiviral component (B), and a resin (C2), wherein
the antiviral component (B) in the steps I and II contains a compound (b1) having a salt of a sulfonic acid group and an organic acid (b2) having a carboxy group,
the amounts of zirconium phosphate (A) and antiviral component (B) attached to the substrate by step I are 1.0 to 3.0 g/m ² and 2.0 to 5.0 g/m ² per unit area of the substrate, respectively;
the amounts of zirconium phosphate (A) and the antiviral component (B) contained in the resin layer formed by the step II are 1.2 to 4.0 g/m ² and 2.9 to 3.9 g/m ² , respectively, per unit area of the substrate;
method. The method according to claim 4, further comprising the step of washing the substrate with hot water after step II.