JP2000282389A - Antibacterial and mold-resistant glass fiber sheet - Google Patents

Abstract

(57) [Problem] To provide an antibacterial / mold-resistant glass fiber sheet having good antibacterial / antifungal properties and a good appearance of flooring and wall materials. The antibacterial and fungicidal glass fiber sheet of the present invention is a sheet in which a polymer compound layer is provided on a nonwoven fabric containing glass fibers as a main component, and a fibrous substance containing a metal salt of a specific organic compound. Alternatively, an antibacterial and fungicide composition containing a metal salt of a specific organic compound and a water-insoluble polymer compound is contained. In particular, the metal salt is preferably one or more of silver, copper, and zinc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber sheet used for building materials such as flooring material, wall material, ceiling material and the like.
Particularly, the present invention relates to a glass fiber sheet having good antibacterial and antifungal properties when used for flooring and wall materials.

[0002]

2. Description of the Related Art Conventionally, asbestos paper has been used for building materials such as flooring materials, wall materials, ceiling materials, etc. However, cracks are liable to occur, fine dust is generated, and there is a problem in safety. For this reason, glass fiber sheets are used as an alternative due to dimensional stability, but due to the low density, the resin applied to the sheets penetrates and penetrates to the back surface, causing problems in process and surface smoothness. There has occurred.

[0003] In order to solve this problem, improvements have been made by using organic fine fibers such as pulp or treating with an organic binder.

However, depending on the application, there is a use in places where bacteria and mold are likely to occur, and even if pulp, organic fibers, binders and the like are used, antibacterial glass fibers which do not produce bacteria and mold are used. A seat was requested.

In particular, when a polymer compound layer was provided on the surface of the sheet in order to improve the surface smoothness and enhance the barrier property, the occurrence of mold was remarkable.

[0006] For example, Ag-containing glass fibers having antibacterial properties have good drawbacks in that they have good solubility in water and thus lose weight when dispersed in an aqueous system.

[0007] When the Ag-containing glass fine powder is used, it falls off during papermaking, and has a disadvantage of low yield.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the conventional problems, has almost no problem of yield during production, has good antibacterial and antifungal properties over a long period of time, has good surface smoothness, and has good decoration. The purpose is to develop a glass fiber sheet that provides flooring, wall material, etc., which have excellent properties.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the antibacterial and mold-resistant glass fiber sheet of the present invention is a glass fiber sheet in which a polymer compound layer is provided on a nonwoven fabric containing glass fibers as a main component, wherein the nonwoven fabric contains at least one of a nitrogen-containing heterocycle and a sulfur atom. An antibacterial and fungicidal fibrous substance A containing a metal salt of a compound.

[0010] The antibacterial and fungicidal glass fiber sheet of the present invention is characterized in that the fibrous substance used for the antibacterial and fungicidal fibrous substance is:
It is at least one selected from polystyrene, polyacryl, polyamide, polyester, polyethylene, and cellulose, and has at least one of a sulfonic acid group, a phosphonic acid group, and a carboxylic acid group.

The antibacterial and antifungal glass fiber sheet of the present invention is a glass fiber sheet comprising a nonwoven fabric mainly composed of glass fibers and a polymer compound layer provided on at least one surface of the nonwoven fabric. An antibacterial fungicide composition B containing a metal salt of an organic compound containing an antibacterial fungicide B and a water-insoluble polymer compound C is applied or impregnated.

The antibacterial and fungicidal glass fiber sheet of the present invention is characterized in that the organic compound containing at least one of a nitrogen-containing heterocyclic ring and a sulfur atom is a benzimidazole compound, a mercaptopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole. It is a compound or at least one compound selected from benzothiazolone compounds.

[0013] In the antibacterial and fungicidal glass fiber sheet of the present invention, the metal salt is at least one of a silver salt, a copper salt and a zinc salt.

The antibacterial and antifungal glass fiber sheet of the present invention is a sheet in which a metal salt is a composite of three kinds of silver salt, copper salt and zinc salt.

The antibacterial and mold-resistant glass fiber sheet of the present invention is obtained by laminating a polymer compound layer on a nonwoven fabric by a hot-melt extrusion lamination method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antibacterial and mold-resistant glass fiber sheet of the present invention will be described in detail. The present invention is an antibacterial and fungicidal glass fiber sheet in which a synthetic resin layer is provided on a nonwoven fabric mainly containing glass fibers containing an antibacterial and fungicidal fibrous substance. Here, “mainly composed of glass fibers” means that 30% by weight or more of the fibers of the nonwoven fabric are glass fibers, and the same applies to the following “main components”.

The reason why the non-woven fabric containing glass fiber as a main component is preferable is because the dimensional stability is improved. Preferably, the glass fiber content is at least 40% by weight.

Fibers other than glass fibers constituting the non-woven fabric of the present invention may be any fibers, and examples thereof include polyacryl, polyester, polyethylene, polypropylene, polyamide, vinylon, and nylon, and pulp, cotton, hemp and the like. Regenerated fibers such as natural fibers, rayon and cupra, and semi-synthetic fibers such as acetate and triacetate are appropriately used in combination.

The average diameter of the glass fibers constituting the nonwoven fabric of the present invention is generally 4 to 15 μm, and the average diameter is 5 μm.
m or more, and is preferably 13 μm or less from the viewpoint of workability because the fiber spacing becomes dense. Average length is 3-25mm
Is common, the strength is weak at less than 6 mm, 25 mm
Above is unfavorable because formation becomes worse.

As for synthetic fibers other than glass fibers, those having a large diameter are not preferred because of the role of filling the gap between the glass fibers. Preferably, the average diameter is 10 μm or less, and the average fiber length is 3 to 15 mm.

In the nonwoven fabric of the present invention containing glass fiber as a main component,
Preferably, the heat-fusible fiber is used in an amount of 5% by weight or more of the nonwoven fabric, so that the tensile strength of the nonwoven fabric and the adhesion to the synthetic resin layer can be improved. The heat-fusible fiber is a fiber which is partially or entirely softened or melted by heat and fused with an adjacent fiber, and is preferably softened or melted at about 200 ° C. or lower.

If the ratio of the heat-fusible fibers contained in the nonwoven fabric mainly composed of glass fibers is too large, the ratio of the glass fibers is reduced, which causes a problem in dimensional stability. Preferably 30 of non-woven fabric
% By weight or less.

The heat-fusible fiber used in the present invention may be a single fiber such as polyvinyl alcohol fiber, viscose fiber, polyolefin fiber such as polyethylene or polypropylene, or a low-melting polyester fiber, or a core-sheath type (consistent with a core-shell type). ) And side-by-side (same as side-by-side) composite fibers. For example, a combination of a polypropylene core and a polyethylene sheath, a combination of a high-melting polyester core and a low-melting polyester sheath, and further, a parallel type fiber can be used in those combinations.

When a heat-fusible fiber is used for a nonwoven fabric mainly composed of glass fiber, a high-molecular-weight compound layer that is hot-melted at a temperature higher than the softening temperature or the melting temperature is provided on the nonwoven fabric for strong adhesion. Property is obtained.

For example, a nonwoven fabric mainly composed of glass fiber has a melting point of 1
When 5% by weight or more of polyethylene-based heat-fusible fiber at 30 ° C. is used, and polyethylene resin is hot-melt extruded and laminated at 280 ° C., the heat-fusible fiber and polyethylene are fused and strong adhesion is obtained. Is obtained.

In the present invention, the nonwoven fabric mainly composed of glass fiber is produced by a wet papermaking method. The preferred reason is that a dense shape with few voids can be obtained.

The wet papermaking method is a method in which fibers are dispersed at a low concentration in water, and a dispersing agent, a cohesive agent, a coagulant, a paper strength enhancer, a sizing agent, and the like are added as necessary. It refers to a method of producing a nonwoven fabric using a fourdrinier paper machine, an inclined paper machine, or a combination paper machine combining two or more paper machines.

The basis weight of the nonwoven fabric mainly composed of glass fiber is selected depending on the application, such as strength and tactile sensation.
300 g / m ² , preferably 30 to 100 g / m ²
It is.

In the polymer compound layer provided on the nonwoven fabric mainly composed of glass fiber by coating or impregnation or the like, a pigment, a surfactant, an antifoaming agent, etc. are appropriately used with the polymer compound as a main component.

Examples of the polymer compound include a urethane polymer compound, a styrene-butadiene polymer compound, an acrylic polymer compound, an acrylonitrile-butadiene polymer compound, an ester polymer compound, a styrene polymer compound, and an amide polymer. Olefin-based polymer compounds such as a polymer compound, a vinyl chloride compound, a vinyl acetate compound, a fluorine compound, a silicon compound, an ethylene polymer compound and a propylene polymer compound.
In the case of applying a foaming resin paste, for example, a polyvinyl chloride paste in the post-processing, the surface smoothness is appropriately selected depending on the interlayer strength, but from the surface smoothness, a plasticizer such as dioctyl phthalate is contained. It is preferable to have resistance or to suppress penetration of the plasticizer by swelling.

As the pigment, kaolin, clay, calcium carbonate, aluminum silicate and the like can be used, and as the additives such as surfactants, those used in general coated papers such as art paper and coated paper can be used. .

The metal salt used in the antibacterial and fungicidal fibrous substance A and the antibacterial and fungicide B of the present invention is selected from silver, copper, zinc, tin, manganese, cobalt and iron salts. From the viewpoint of effect, it is preferably selected from silver, copper, and zinc salts, and is further formed of two or more composite salts, and more preferably a composite of three silver, copper, and zinc salts. The reason is that the water solubility of each metal salt is different, the zinc salt dissolves quickly, and the silver salt is slow. As described above, particularly, three kinds of composite salts of silver, copper, and zinc are preferable.

Examples of the organic compound containing at least one of a nitrogen-containing heterocyclic ring and a sulfur atom used in the antibacterial and fungicidal fibrous substance A and the antibacterial and fungicide B of the present invention include:
Pyrrole, pyridine, pyrimidine, pyrazole, imidazole, benzimidazole, 1,3,5
-Triazine, hexahydro-1,3,5-triazine, triazole, isoxazole, thiazole, benzothiazole, thiazolone, benzothiazolone, isothiazolone, benzoisothiazolone,
Examples thereof include those having a tetrahydrothiadiazinethione-based skeleton as a basic skeleton, and further include their alkylallyl derivatives and mercapto derivatives. Among them, benzimidazole compounds and mercaltopyridine-
At least one compound selected from N-oxide compounds, isothiazolone compounds, benzothiazole compounds and benzothiazolone compounds is particularly preferred. Specific examples of these include, for example, 2- (4-thiazolyl) -benzimidazole, 2- (carbomethoxyamino) -benzimidazole, 2-mercartopyridine-N-oxide, 1,2-benzoisothiazolin-3-one , 5-chloro-2-methyl-4-isothiazolin-3-one, 2
-Methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzothiazolone, 2- (4-thiocyanomethylthio) benzothiazole and the like.

In particular, at least one of a benzimidazole compound, a mercaptopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole compound and a benzothiazolone compound is preferred from the viewpoint of the effect.

As the fibrous substance used in the antibacterial and fungicidal fibrous substance of the present invention, a so-called ion exchange fiber is used. For example, a sulfonic acid group, a base polymer such as polystyrene, polyacryl, polyamide, polyethylene, cellulose, etc. It can be obtained by appropriately introducing a phosphonic acid group, a carboxylic acid group and the like.

Further, natural cellulose fibers usually called pulp can be preferably used by partially chemically modifying them. Examples of the chemical denaturation treatment include sulfation, phosphorylation, nitration, carboxymethylation, carboxyethylation, and carboxypropylation. Among them,
The carboxymethylation process is easy, economical,
It is excellent in safety, excellent in swelling property, ion permeability and the like, and is extremely suitable for the practice of the present invention.

As the fibrous substance in the present invention, suitably carboxymethylated wood pulp (softwood pulp, hardwood pulp, etc.) is suitable for the practice of the present invention. In addition, regenerated cellulose such as rayon is also used. It can be used as well. Further, a synthetic fiber, an alginic acid fiber, or a wet-spun fiber of a soluble polymer, which is appropriately modified according to the above-mentioned purpose and has ion exchange ability, may be used. Further, a wet-spun fiber produced from a polymer solution containing an organic metal complex salt having antibacterial and antifungal properties according to the present invention may be used.

A preferred specific example of the fibrous substance in the present invention is achieved by carboxymethylation of a natural cellulosic fiber.

To obtain a fibrous substance having a desired degree of carboxymethyl group substitution, basically, it is possible to adjust the amount of sodium monochloroacetate, the amount of alkali and water, and other reaction conditions with respect to the cellulosic fiber. It is.

In general, the degree of carboxymethyl group substitution is
It is defined as the degree of substitution of carboxymethyl groups per glucose unit (DS). The degree of substitution is to convert to acid-type carboxymethylcellulose, neutralize it by adding an excess amount of alkali, and then back titrate with acid. Required by

The fibrous substances having various degrees of carboxymethyl group substitution used in the present invention have a higher metal ion-capturing ability as the degree of substitution increases, and therefore, the organic metal having antibacterial and antifungal properties according to the present invention. Although the packing density of the composite salt increases, the swelling proceeds excessively at a high degree of substitution, leading to a decrease in fiber strength and, consequently, to solubilization. Generally, the degree of substitution becomes soluble at around 0.6. Although the strength is reduced, the degree of substitution is about 0.5, which is the upper limit level at which the fiber shape can be maintained.

Next, the antibacterial and antifungal fibrous substance A of the present invention
As an example of the preparation, an example using Na-type carboxymethylcellulose having a substitution degree of 0.4 will be described. 1) Add water to an amount equivalent to 100 g of the above pulp solid content to such an extent that stirring is possible. 2) Add 100 mmol / equivalent (17 g) of silver nitrate. 3) Add alkali so that the pH of the system is 5.5 to 6.0. 4) Stir at room temperature for 30 minutes to allow sufficient displacement (adsorption). 5) 1000 ml of a 0.1 M / l solution of sodium 2-mercaptopyridine-N-oxide is added little by little with stirring. When the potential is measured using a silver electrode or a platinum electrode, the reaction end point can be detected. 6) After completion of the addition, the mixture is stirred for 30 minutes to allow a sufficient reaction. 7) The pH of the system is lowered to about 4 by adding a 0.1 M / l sulfuric acid solution, and then the system is dehydrated by a dehydration press.

According to the above procedure, mercaptopyridine-
A pulp containing a silver N-oxide salt is obtained. If necessary, the fallout can be removed in advance by dispersing in water again and washing with water. According to the results of the experiment, it was confirmed that salts were formed in the form of in-fiber and surface fixation at a high yield of 90% or more, although they were partially removed.

In order to form a mercaptopyridine-N-oxide silver salt inside or on the surface of a fiber with a high yield, it is necessary to optimize pH control, stirring, concentration and rate of chemical addition.

The water-insoluble polymer compound C used in the antibacterial and fungicide composition D of the present invention includes a urethane polymer compound, a styrene-butadiene polymer compound, an acrylic polymer compound, and acrylonitrile-butadiene compound. Polymer compound, ester polymer compound, styrene polymer compound, amide polymer compound, vinyl chloride compound, vinyl acetate compound, fluorine compound, silicon compound, ethylene polymer compound and propylene polymer compound. And olefin-based high molecular compounds such as molecular compounds.

The reason that the water-insoluble polymer compound C is preferred is that the antibacterial and fungicidal composition containing it is applied or impregnated on various materials and dried at a temperature not lower than the minimum film-forming temperature to obtain a particularly high water resistance. This is because a material having good antibacterial and antifungal properties can be obtained. Furthermore, when a water-insoluble polymer compound is imparted with self-emulsifying properties, or when dried in water with an emulsifier, a discontinuous portion of the film is liable to occur, and different types of materials such as an antibacterial and fungicide are used. Is particularly remarkable when the compound is added, the components of the antibacterial and antifungal agent are easily transferred from the discontinuous portion, and it is expected that good antibacterial and antifungal properties will be exhibited.

In the present invention, the weight ratio B / C of the antibacterial fungicide B to the water-insoluble polymer compound C is preferably 0.05 to 5. If it is larger than 5, water resistance and durability tend to be poor,
If the value is smaller than 0.05, the water-insoluble polymer compound C covers the antibacterial fungicide B, so that it is difficult to obtain the effect of the antibacterial fungicide B on the inner side. This is because the mold effect tends to be inferior.

In the present invention, the water-insoluble polymer compound C is coated or impregnated with the antibacterial fungicide composition D and dried.
The film has water resistance, is stable even when moisture is added,
It is expected that a good antibacterial and antifungal effect will be continuously obtained by appropriately moving the antibacterial and fungicide components to the surface together with water and releasing them gradually.

In order to further improve the water resistance, it is possible to add a crosslinking agent to the water-insoluble polymer compound C so as to crosslink appropriately.

From the characteristics such as durability, light resistance and friction strength,
Preferably, a urethane polymer, a styrene-butadiene polymer, or an acrylic polymer is used as the water-insoluble polymer C.

Preferably, the water-insoluble polymer compound C is a self-emulsifying type. The reason is that it is not necessary to add various emulsifiers when dispersing in water, so apply or impregnate each article,
This is because the adhesion between the antibacterial fungicide B and the water-insoluble polymer compound C after drying becomes good, and the water resistance and durability are excellent.

More specifically, water-insoluble polymer compounds such as urethane, styrene-butadiene, and acryl are used in an amount of a specified amount or more such as anions such as carboxyl groups, amino groups, hydroxyl groups and esters, nonions, and cationic hydrophilicity. , So that it can be stably dispersed in water. Hydran HW350 manufactured by Dainippon Ink and Chemicals, Luck Star DS-405, Luck Star DS-407, Patera Coat SB-301, and the like.

Preferably, the water-insoluble polymer compound C is a self-crosslinking type. The reason is that the self-crosslinking strengthens the film and improves water resistance and durability. When a cross-linking agent is added to the water-insoluble polymer compound C which is not a self-cross-linking type, the liquid stability of the antibacterial fungicide composition is inferior, and the antibacterial fungicides are easily aggregated with each other. Choosing the quantity is difficult.

Specifically, a water-insoluble polymer compound C such as a urethane type, styrene-butadiene type or acrylic type has a highly reactive portion such as a vinyl group, an aldehyde group, an epoxy group, etc. And self-crosslinking by addition reaction, ring opening reaction and the like. Examples include Bonncoat 3256 and Luckstar DS-407 manufactured by Dainippon Ink and Chemicals, Inc.

In the present invention, various adhesives, pigments, dyes, and the like can be mixed with the antibacterial fungicide composition D, if necessary.

Next, as an example of the preparation of the antibacterial fungicide B of the present invention, an example of silver mercaptopyridine-N-oxide will be described. 1) Prepare 1000 g of water. 2) Add 100 mmol / equivalent (17 g) of silver nitrate. 3) Stir at room temperature for 30 minutes to fully dissolve. 4) 1000 ml of a 0.1 M / l solution of 2-mercaptopyridine-N-oxide sodium salt is added little by little with stirring. 5) After completion of the addition, the mixture is stirred for 30 minutes to allow a sufficient reaction.

According to the above procedure, mercaptopyridine-
A silver N-oxide is obtained.

In the present invention, a complex salt of an organic compound exhibiting the most effective antibacterial and antifungal function can be prepared in the same manner.

The antibacterial and fungicidal composition D of the present invention is preferably stabilized by adding a water-insoluble polymer compound immediately after the completion of the complex salt of the organic compound.

It is to be noted that silver nitrate is first added to the aqueous dispersion of the water-insoluble polymer compound, and 2-mercaptopyridine-N-oxide sodium salt is added.
Although it is possible to synthesize an N-oxide silver salt, the particle size tends to be non-uniform.

[0061] content per nonwoven unit area of the glass fibers mainly antibacterial and antifungal fibrous material A of the present invention is generally at 0.5 g / m ² or more, 1 g / m ² or more is preferable .

The content of the antibacterial fungicide B of the present invention per unit area of the nonwoven fabric mainly composed of glass fiber is generally 0.0
It is 5 g / m ² or more, preferably 0.1 g / m ² or more.

When the amount of the antibacterial and antifungal agent B is less than 0.05 g / m ² , it is difficult to obtain sufficient antibacterial and antifungal properties from the beginning of use. The content can be appropriately selected depending on the required duration of the antibacterial and antifungal properties, but for long-term use, 0.2 g / m ² or more is required.

The antibacterial and fungicidal composition D of the present invention may be directly applied or impregnated on a nonwoven fabric or the like, but in order to improve the stability and adhesion of the antibacterial and fungicidal composition. It is also possible to apply various adhesives before application and to apply a small amount of pigment or dye for coloring.

The antibacterial and fungicide composition D of the present invention includes various water-soluble polymer compounds other than the water-insoluble polymer compound C, for example, polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, starch and the like. It can be used alone or in combination with a crosslinking agent.

The amount of the water-soluble polymer compound to be imparted to the antibacterial fungicide composition D is preferably less than 50% by weight based on the solid content of the antibacterial fungicide composition of the present invention. If it exceeds 50% by weight, the adhesiveness is increased, but the antibacterial and antifungal properties are reduced.

[0067]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
In addition, "%, part" means "% by weight" and "part by weight".

Example 1 A nonwoven fabric mainly composed of glass fiber was formed into a sheet by a square-shaped hand-made box with the following fiber composition, appropriately added with polyacrylamide to a concentration of about 0.05%, and then pressed. ,
After drying, a nonwoven fabric having a basis weight of 50 g / m ² was prepared. Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 60 parts Pulp fiber (NBKP, csf450 ml) 25 parts CP22AgMP (created in Production Example A) 5 parts Vinylon fiber (1d × 3 mm) 10 parts

Production Example A Modified NBK having a carboxymethyl group substitution degree of 0.22 (DS = 0.22) according to the description of the above embodiment of the invention.
A fibrous substance containing an antibacterial and fungicide composed of a metal salt of an organic compound having silver / 2-mercaptopyridine-N-oxide adsorbed on P was prepared (hereinafter abbreviated as CP22AgMP). Silver nitrate is added to the modified NBKP dispersion to adjust the pH to 5.5, and then the mixture is stirred for 30 minutes.
A 0.1 M / l sodium 2-mercaptopyridine-N-oxide solution was added in an equimolar amount to the silver nitrate added to the modified NBKP dispersion. After stirring for 30 minutes,
After the pH was lowered to 4 with sulfuric acid, it was dehydrated. To the dehydrated pulp, 500 ml of water was again added, and the mixture was washed with stirring and dehydrated. This was replaced with a carboxymethyl group substitution degree of 0.22 (DS = DS) containing an antibacterial and antifungal agent comprising a metal salt of an organic compound adsorbed with silver / 2-mercaptopyridine-N-oxide.
0.22).

On the surface of the obtained nonwoven fabric, a coating solution having the following composition was applied with a coating rod to obtain a solid content of 40 g / m ^2.
And dried at 120 ° C. to obtain an antibacterial and mold-resistant glass fiber sheet. Styrene-butadiene latex (620 from Asahi Kasei) 60 parts Polyvinyl alcohol (117 from Kuraray) 25 parts Kaolin (Ultra White 90 from EMC) 15 parts

Examples 2 to 5 An antibacterial and fungicidal glass fiber sheet was prepared in the same manner as in Example 1 except that the fiber composition of the nonwoven fabric mainly composed of glass fiber was changed as shown in Table 1. Obtained. In addition, Production Example B in the table is CP40Ag25 produced in Production Example B.
This shows Cu25Zn50MP. Similarly, Production Example A is CP
22AgMP is shown.

Preparation Example B The same as Preparation Example A, but according to the description of the embodiment of the present invention, a modified compound having a carboxymethyl group substitution degree of 0.40 (DS = 0.40) instead of CP22AgMP. NB
KP with (silver, copper, zinc) / 2-mercaptopyridine-N
-A fibrous substance containing an antibacterial and fungicide consisting of three metal salts of an organic compound to which an oxide was adsorbed was prepared (hereinafter abbreviated as CP40Ag25Cu25Zn50MP). In addition, the number following the metal atom in parenthesis represents a mol% ratio.

Example 6 A non-woven fabric mainly composed of glass fiber was formed into a sheet by a square hand-made box with the following fiber composition, suitably adding polyacrylamide to a concentration of about 0.05%, and then pressing. ,
After drying, a nonwoven fabric having a basis weight of 50 g / m ² was prepared. Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 50 parts Pulp fiber (NBKP, csf450 ml) 20 parts CP22AgMP (prepared in Production Example A) 5 parts Vinylon fiber (1d × 3 mm) 10 parts Heat-fusible fiber (Daiwa) 15 parts of NBF-E2d × 5 mm manufactured by Spinning Co., Ltd.
The polymer compound layer of 30 g / m ² was provided by hot-melt extrusion lamination at 0 ° C. to obtain an antibacterial and mold-resistant glass fiber sheet of Example 6.

Example 7 In Example 1, the fiber structure of the nonwoven fabric was changed to the following, and the antibacterial and fungicide composition AgMP-UA0. 3 to 10 solids
An antibacterial and fungicidal glass fiber sheet was obtained in the same manner except that the composition was applied so as to give g / m ² . Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 60 parts Pulp fiber (NBKP, csf450 ml) 30 parts Vinylon fiber (1d × 3 mm) 10 parts

Production Example C An antibacterial fungicide containing a metal salt of an organic compound and containing a silver / 2-mercaptopyridine-N-oxide and a urethane polymer according to the description of the above embodiment of the invention An antibacterial fungicide composition containing the compound and an acrylic polymer compound was prepared (hereinafter abbreviated as AgMP-UA0.3). That is, 0.1 mol of silver nitrate is added to water and stirred. 0.1 mol / l 2-mercaptopyridine-N-
A sodium oxide solution is added in an equimolar amount to the added silver nitrate and stirred for 30 minutes. To this was added an aqueous dispersion of a self-emulsifying urethane polymer compound (Hydran HW-350, manufactured by Dainippon Ink and Chemicals, Inc.), and the mixture was stirred for 5 minutes. An aqueous dispersion of Bon Coat 3256) manufactured by Nippon Ink Chemical Industry Co., Ltd. was added, and the weight ratio of the antibacterial fungicide of silver / 2-mercaptopyridine-N-oxide to the urethane polymer compound was 0.3. The number following the metal atom in the parenthesis indicates the mole% ratio, and the last number indicates the weight ratio of the antibacterial and fungicide to the water-insoluble polymer compound.

Examples 8 to 11 Antibacterial and fungicidal glass fiber sheets were obtained in the same manner as in Example 7 except that the antibacterial and fungicide compositions in Example 7 were changed to the compositions shown in Table 2. Production Example C in the table indicates AgMP-UA0.3 obtained in Production Example C, and Production Example D was Ag25-Ag25.
This shows Cu25Zn50MP-UA0.3.

Production Example D The same as Production Example C, but according to the description of the above embodiment of the present invention, instead of AgMP-UA0.3, (silver,
Water of self-emulsifying urethane polymer compound (Hydran HW-350) and self-crosslinking acrylic polymer compound (Boncoat 3256) containing an antibacterial fungicide of (copper, zinc) / 2-mercaptopyridine-N-oxide A dispersion was prepared. That is, 0.25 mol of silver nitrate, 0.25 mol of copper sulfate
mol, 0.5 mol of zinc nitrate and 1.75 mol of 2-mercaptopyridine-N, which is the total molar equivalent thereof.
-Add sodium hydroxide aqueous solution, stir, add self-emulsifying urethane polymer compound aqueous dispersion, after stirring, add self-crosslinking acrylic compound aqueous dispersion, stir,
The weight ratio of the antibacterial fungicide (silver, copper, zinc) / 2-mercaptopyridine-N-oxide, the self-emulsifying urethane polymer and the self-crosslinking acrylic polymer was 0.3 ( Hereinafter, Ag25Cu25Zn50MP-
UA0.3). The number following the metal atom in the parenthesis indicates the mole% ratio, and the last number indicates the weight ratio of the antibacterial fungicide to the water-insoluble polymer compound.

Comparative Example 1 A glass fiber sheet was obtained in the same manner as in Example 1 except that the following composition was used without using an antibacterial and fungicidal fibrous substance. Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 60 parts Pulp fiber (NBKP, csf450 ml) 30 parts Vinylon fiber (1d × 3 mm) 10 parts

Comparative Example 2 A glass fiber sheet was obtained in the same manner as in Example 1 except that the following composition was used without using an antibacterial and fungicidal fibrous substance. Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 20 parts Pulp fiber (NBKP, csf450 ml) 60 parts Vinylon fiber (1d × 3 mm) 20 parts

Comparative Example 3 The urethane polymer (Hydran HW-35) used in Example 7 for producing the antibacterial fungicide composition of Production Example C
A glass fiber sheet was obtained in the same manner as in Example 8, except that only 0) was applied instead of the antibacterial fungicide composition.

Comparative Example 4 A glass fiber sheet was obtained in the same manner as in Example 6, except that the fiber structure of the nonwoven fabric containing glass fiber as a main component was changed as follows. Glass fiber (average fiber diameter 9 μm, average fiber length 10 mm) 50 parts Pulp fiber (NBKP, csf450 ml) 25 parts Vinylon fiber (1d × 3 mm) 10 parts Heat-fusible fiber (manufactured by Daiwa Spinning Co., Ltd., NBF-E2d × 5 mm) 15 parts 28 low-density polyethylene resin on one side of the obtained non-woven fabric
Laminating was performed by hot-melt extrusion lamination at 0 ° C. to provide a polymer compound layer of 30 g / m ^{2. Thus} , an antibacterial and mold-resistant glass fiber sheet of Comparative Example 4 was obtained.

Table 3 shows the evaluation results of the following antibacterial and antifungal properties of the glass fiber sheets obtained in Examples 1 to 11 and Comparative Examples 1 to 4. Examples 1 to 11 and Comparative Examples 1 to 4
Polyvinyl chloride resin (126, manufactured by Zeon Corporation) on the surface of the glass fiber sheet obtained in
A paste sol having a ratio of 60 of dioctyl phthalate to 0 was applied so as to be 100 g / m ^2.
After cooling for minutes, the surface properties were evaluated. Five was the best in five stages.

<Durable antibacterial property> E. coli I
FO3301) in a liquid medium (peptone yeast)
The cells were pre-cultured for 4 hours and diluted to prepare a test solution. The glass fiber sheet obtained by the above Examples and Comparative Examples was
It is left for one month under the environmental conditions of 90 ° C. and 90% RH. A test piece of 2 cm × 2 cm is cut out from the glass fiber sheet taken out, placed on a Petri dish with the polymer compound layer facing down, and 5 drops (about 0.1 ml) of the above test solution is dropped and not dried. For 24 hours at 25 ° C. After a lapse of time, each of the test pieces was Nutrien.
The strain was pressed onto a t-Broth agar medium to transfer the bacteria on the test piece, peeled off, cultured at 38 ° C. for 24 hours, and observed. The evaluation was as follows. Evaluation grade --- Almost completely sterilized, no growth of bacteria. --- Growth of 5 colonies or less on the 2cm x 2cm transfer surface, but almost completely sterilized. -Good anti-bacterial effect with less than 100 colonies on 2cm x 2cm transfer surface. + 2cm × 2cm Although the effect is recognized on the transfer surface, it is weak or small. ++ 2 cm x 2 cm No substantial effect on transfer surface.

<Durable fungicide resistance> As a test strain, black mold (Aspergillus niger) was used. The spores were collected from the slant medium, a small amount of a wetting agent (dioctyl sodium sulfosuccinate solution) was added, and the spores were dispersed by shaking vigorously, and filtered with gauze to adjust the total volume to 50 ml. GP medium supplemented with 1.5% agar (manufactured by Nippon Pharmaceutical Co., Ltd.)
And the bacterial solution was sprayed uniformly, and the surface was once dried. The glass fiber sheet obtained in each of Examples and Comparative Examples was cut into a test piece of 2 cm × 2 cm, placed thereon with the polymer compound layer placed down, pressed sufficiently, and sprayed again with the test bacteria on the entire surface. The cells were cultured over time at ℃ and observed over time up to one month. The evaluation was as follows. Evaluation grade -------- Completely inhibits mold growth. --- It is difficult to judge whether mold is growing or not. -Shows fairly good controllability, but shows mold growth on less than 1/5 of the surface area. + Mold growth is observed at about 1/3 of the surface area. ++ Mold grows on the entire surface.

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[Table 1]

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[Table 2]

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[Table 3]

Results: Of these glass fiber sheets,
Any of those included in the present invention have good long-term antibacterial properties, good antifungal properties, good surface quality of the surface coated with polyvinyl chloride paste, and excellent decorativeness, and are suitable for flooring and wall materials. It is a mold-resistant glass fiber sheet.

The glass fiber sheets of Examples 1 to 6 all have good antibacterial and antifungal properties. Particularly, the glass fiber using the antibacterial and antifungal fibrous substance containing Ag-Cu-Zn of Production Example B The sheet shows good antibacterial and antifungal properties even with a small amount of compounding. The glass fiber sheet containing no antibacterial and fungicidal fibrous substance of Comparative Examples 1 and 2 has no durable antibacterial and antifungal properties.

All of the glass fiber sheets of Examples 7 to 11 show good antibacterial and antibacterial properties. In particular, A of Production Example D
The glass fiber sheet using the g-Cu-Zn-containing antibacterial fungicide composition exhibits good durability and antibacterial fungicide with a small amount of application. In the case of the glass fiber sheet containing no antibacterial and fungicide composition of Comparative Example 3, there is no durable antibacterial and fungicide properties.

In Example 6, a high molecular compound layer was provided by laminating polyethylene, but the same antimicrobial and antifungal properties as those of Example 3 were obtained, and the polyvinyl chloride surface property was good. Was. However, in Comparative Example 4 in which the antibacterial and antifungal fibrous substance was removed from the nonwoven fabric structure of Example 6, the antibacterial and antifungal properties tended to be worse than in Comparative Examples 1 to 3.

In the evaluation of the surface where the polyvinyl chloride paste was applied to the glass fiber sheet, the sheets of Examples 1 to 11 obtained good appearance smoothness, but the glass fiber sheet of Comparative Example 2 had a small amount of glass fiber of 20%. Inferior results were obtained.

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As described above in detail with reference to Examples and Comparative Examples, according to the present invention, flooring materials, wall materials, etc., which have good antibacterial properties and mildewproofness and good visual smoothness. Can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L033 AA09 AB07 AC10 BA19 BA23 BA24 BA55 BA57 CA29 CA68 DA02 4L055 AF04 AF09 AF10 AF16 AF20 AF21 AF27 AF33 AF35 AF44 AG27 AG36 AG39 AG63 AG64 AG76 AG89 AG97 AH21 AJ02 BE08 BE10 BE13 FA30 GA21 GA23 GA27 GA38

Claims (7)

[Claims] 1. A glass fiber sheet comprising a nonwoven fabric mainly composed of glass fibers and a polymer compound layer provided on a nonwoven fabric, wherein the nonwoven fabric contains a metal salt of an organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom. An antibacterial and antifungal glass fiber sheet containing a moldy fibrous substance (A). 2. The fibrous substance used for the antibacterial and fungicidal fibrous substance (A) is at least one selected from polystyrene, polyacryl, polyamide, polyester, polyethylene and cellulose, and comprises a sulfonic acid group, The antibacterial and mold-resistant glass fiber sheet according to claim 1, wherein the sheet has at least one kind of an acid group and a carboxylic acid group. 3. A glass fiber sheet comprising a nonwoven fabric mainly composed of glass fibers and a polymer compound layer provided on a nonwoven fabric, wherein at least one surface of the nonwoven fabric is a metal salt of an organic compound containing at least one of a nitrogen-containing heterocycle and a sulfur atom. An antibacterial / mold-resistant glass fiber sheet obtained by applying or impregnating an antibacterial / fungicidal agent composition (D) containing an antibacterial / fungicidal agent (B) and a water-insoluble polymer compound (C). 4. The organic compound containing at least one of a nitrogen-containing heterocyclic ring and a sulfur atom is at least one selected from a benzimidazole compound, a mercaptopyridine-N-oxide compound, an isothiazolone compound, a benzothiazole compound and a benzothiazolone compound. The antibacterial and fungicidal glass fiber sheet according to claim 1 or 3, which is a compound of the formula (1). 5. The metal salt according to claim 1, wherein the metal salt is at least one of a silver salt, a copper salt, and a zinc salt.
The antibacterial and mold-resistant glass fiber sheet according to the above. 6. The antibacterial and antifungal glass fiber sheet according to claim 1, wherein the metal salt is a composite of a silver salt, a copper salt and a zinc salt. 7. The antibacterial and mold-resistant glass fiber sheet according to claim 1, wherein the polymer compound layer is provided so as to be laminated on the nonwoven fabric by a hot melt extrusion lamination method.