JP2005170015A - Fibrous laminated board with antibacterial activity, mildew resistance and deodorant effect - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fibrous laminated board in which an inorganic silver-based antibacterial agent is added and thus, antibacterial activity, mildew resistance and deodorization are effective for a long period. <P>SOLUTION: In this fibrous laminated board, the inorganic silver-based antibacterial agent carried by zeolite or zirconium phosphate is not added, but a silver chlorocomplex salt is added to fibers. Accordingly, antibacterial activity, mildew resistance and deodorizing effect are sustained for a long period. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

Detailed Description of the Invention

  The present invention relates to an antibacterial, anti-bacterial and deodorant fibrous laminated board obtained by adding a silver antibacterial agent to a fibrous board. More particularly, the present invention relates to an antibacterial, anti-bacterial and deodorant laminated board obtained by adding a silver chloro complex salt to a fibrous laminated board.

  In recent years, the contamination of the living environment has been highlighted as a major social problem due to formaldehyde generated from building materials using wooden boards obtained by applying formalin adhesives such as fiberboard and particleboard and hot pressing. Therefore, there is a strong demand for wooden boards that generate as little formaldehyde as possible. On the other hand, wooden board construction materials that generate little formaldehyde and boards that do not generate at all solve the problem of the living environment, but have a problem that the antibacterial and antifungal performance deteriorates.

  A method of adding an antifungal agent for the production of the above-mentioned wood board is also conceivable, but many organic antifungal agents currently in general use are highly toxic. In addition, it has the property of decomposing and reducing the effect in the process of heat-clamping during the production of wooden boards, and there is also the possibility of generating harmful substances such as dioxins due to halogen compounds contained in organic antifungal agents during incineration.

  Therefore, a method using a borax or boric acid type antifungal agent (Japanese Patent Laid-Open No. 10-278013), silver is supported on a support such as zeolite, or silver, copper, zinc or the like is supported on zirconium phosphate. A method using an inorganic antibacterial agent (JP-A-10-286807), a method using an organic iodine antifungal agent (JP-A 2002-36215), and the like have been reported. For rice husk boards, there is a report on the use of antifungal agents in JP-A-63-118203.

Problems to be solved by the invention

  However, it is also true that there are some points that cannot be solved by conventional methods. Organochlorine antifungal agents are generally used as organic antifungal agents, but organochlorine antifungal agents have poor heat resistance and are volatile, so they retain long-term effects. There's a problem. In addition, borax, boric acid-based antifungal agents, and methods using inorganic antibacterial agents in which silver, copper, zinc, etc. are supported on inorganic zeolite or zirconium phosphate, have long-term effect retention and safety, and are suitable for incineration. There is no problem, but the problem is that it is less effective than organic antifungal agents. Furthermore, the current board is focused on antibacterial and antifungal treatment only on the board itself, and the problem is that the emphasis is not on the living environment where the boards are attached. By adding silver-based antibacterial agents to the boards, not only the boards themselves, but also the long-term effects of antibacterial, anti-fouling and deodorizing in the living environment where the boards are attached, safety, and incineration It provides boards for the purpose of solving problems. Further, the present invention provides a board for improving various physical properties of the board itself by using a fiber laminated board.

Means for solving the problem

  As a result of diligent research, the present inventors have found that in a fiber laminated board, when a silver antibacterial agent is added and dispersed in the fiber, unlike the conventional inorganic-supported silver antibacterial agent and organic antifungal agent, The present invention was completed by finding that it adheres firmly and adheres and exhibits antibacterial, antifungal and deodorant properties for a long time. The present invention relates to adding a silver-based antibacterial agent to a fiber to obtain a fiber laminated board. As a special feature, the antibacterial agent uses a silver chloro complex salt.

The present invention is an antibacterial, anti-deodorizing and deodorizing fiber laminated board characterized in that an inorganic antibacterial agent is added to the fiber laminated board. The antibacterial agent used in the present invention is a silver antibacterial agent, and specific examples of the antibacterial agent include those containing a silver chloro complex salt. The antibacterial agent containing a silver chloro complex salt also has an action as an antifungal agent and a deodorant. The silver chloro complex salt is not particularly limited as long as it is a salt having a complex ion structure represented by the structural formula “[AgCl ₄ ] ³⁻ ”. Further, the counter ion (cation) in the silver chloro complex salt is not particularly limited. In addition, the manufacturing method of the antibacterial agent containing a silver chloro complex salt is not specifically limited.

  The antibacterial agent containing the silver chloro complex salt further contains a chloride that supplies chloride ions for stabilizing the silver chloro complex salt. Specific examples of the chloride include chlorides containing alkali metal ions such as lithium ions, sodium ions and potassium ions as counter ions (alkali metal chlorides); alkaline earth metal ions such as magnesium ions and calcium ions. Chloride as a counter ion; polyaluminum chloride; ammonium chloride; trioctylmethylammonium chloride, aliphatic quaternary ammonium chloride having one or two long-chain alkyl groups having 12 to 18 carbon atoms, tetramethylammonium chloride, Aliphatic quaternary ammonium salts such as tetraethylammonium chloride; choline chloride; polyamine hydrochlorides such as ethylenediamine hydrochloride, hexamethylenediamine hydrochloride and hexamethylenetriamine hydrochloride; 1 such as methylamine hydrochloride and methylamine hydrochloride Amine hydrochlorides; tertiary amine hydrochlorides such as trimethylamine hydrochloride and triethylamine hydrochloride; aromatic amine hydrochlorides such as pyridine hydrochloride and aniline hydrochloride; trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, chloride Examples thereof include aromatic quaternary ammonium salts such as benzalkonium, benzethonium chloride, imidazolinium chloride, and N-laurylpyridinium chloride.

The ratio of the silver chloro complex salt and chloride is not particularly limited as long as it is within a predetermined range in which the antibacterial agent can exhibit antibacterial properties, but is in a mass ratio of 1: 100 to 20: 100. Is more preferable, and it is most preferable that it is in the range of 3: 100 to 15: 100. In addition, the antibacterial agent containing silver chloro complex salt may further contain oxidizing agents, such as sodium chlorite and sodium hypochlorite.
The amount of silver chloro complex antibacterial agent to be used is not particularly limited, but is preferably such that the amount of fibrous silver ions is 0.01 ppm or more, and is about 0.05 ppm or more. The amount is optimal.

  Generally, a silver chloro complex salt is stable in a water-soluble or readily water-soluble state without causing precipitation of silver chloride because it is excellent in stability at a high chloride ion concentration. Further, the silver chloro complex salt has a property that silver chloride or silver metal is likely to be precipitated when the surrounding chloride ion concentration is lowered by dilution with water or the like. This is because the amount of chloride ions that directly contributes to the stabilization of the silver chloro complex salt is reduced when the chloride ion concentration is low. The silver chloro complex salt exhibits antibacterial properties when silver chloride or silver metal deposited in such a low chloride ion concentration adheres to the fiber. That is, the antibacterial property produced by the adhesion of the silver chloride to the fiber is more specifically, in a state where the chloride ion concentration is low, the silver chloro complex salt becomes unstable and precipitates as silver chloride fine particles. It is demonstrated by doing. Therefore, when an antibacterial agent is included in the fiber, the concentration of the solution or emulsion of the antibacterial agent may be set to a chloride ion concentration such that the silver chloride fine particles are generated. Thereby, the silver chloride fine particles can be fixed or fixed on the fiber, and a stable antibacterial property can be imparted. Unlike other silver antibacterial agent-supporting fiber boards, fiber laminated boards containing silver chloro complex salts as antibacterial agents exhibit antibacterial, antifungal and deodorant properties over a long period of time. As a method for adding the silver antibacterial agent used in the present invention, ordinary methods are used and there is no limitation. However, a method of applying to the surface of the obtained boards, an adhesive is mixed with the raw wood fiber or wood powder. There are a method of spraying before, a method of mixing in an adhesive, and the like.

  Since the silver chloro complex salt used in the present invention is stable, it can be used in combination with other silver antibacterial agents, organic iodine antifungal agents, organic antibacterial agents, and organic antifungal agents.

  In general, the fiber boards targeted by the present invention include the following. Wood board, such as fiber board, particle board, wood flour board, waste paper board, rice husk, etc., and also part of straw board with barley, buckwheat husk, tea leaves, rice straw, wheat straw, stalk or leaf cuts The board etc. which replaced.

  In the present invention, as the fiber board, a commonly used material such as a wood fiber is used, and as the particle board, a wood chip, a wood chip, a wood fiber or the like is used. The raw materials are coniferous trees such as spruce, pine, pine, cedar, firewood and spruce, maple, hardwood such as beech, birch, etc. It can be obtained by defibrating with a disc refiner.

  The wood flour board uses wood powder or wood powder. The raw material used for the wood flour board is mainly wood waste. Wood waste such as thinned wood, sawmill waste, wood industry waste, wood industry waste, roadside tree pruning material, building waste, cedar, firewood, Hiba, white birch, pine, and baran (mainly bark) is there. These waste materials are made into chips by an existing apparatus, and if necessary, further refined and dried before use. A tree obtained by adding an adhesive to the wood thus obtained is used. Furthermore, in order to maintain strength, the wood powder and the sheet may be pre-pressed to form a board. In that case, the sheet uses one kind of paper, non-woven fabric, woven fabric, glass fiber, carbon fiber and the like.

  The waste paper board of the present invention mainly uses waste paper such as newspapers, magazines, cardboard, and high-quality paper (OA paper, etc.). As a method for producing a paper by defibrating the waste paper, a conventionally known method may be used. For example, the waste paper is put into a beater, a pulper or the like and pulped to make paper.

  Ingredients used for the boards of rice husks and the like of the present invention include rice husks, wheat husks, buckwheat husks, and tea leaves. In some cases, these coarsely pulverized products, wood chips and wood flour are used. . In addition, rice straw, wheat straw, stalks or leaves of those cut out, and rice husks etc. are used. In some cases, rice husk is bleached and decolorized.

  In the present invention, an adhesive is used to improve the bending strength and tensile strength of the fiber laminated board. The adhesive used for the wooden board is urea resin, urea melamine condensation resin, urea phenol copolymer resin, amino acid. A water-based adhesive such as a resin is used, but ammonium chloride, ammonium nitrate, ammonium sulfate or lower fatty acid ester may be used as a curing accelerator. A phenol resin, a urea resin, an isocyanate resin, or an epoxy resin may be used. The adhesive used for waste paper boards is mainly polyvinyl alcohol. Phenol formaldehyde resin, urethane resin, synthetic rubber latex or the like is used as an adhesive used for a board such as rice husk. The addition ratio of the adhesive used in the present invention is preferably 3 to 20 parts, more preferably 5 to 15 parts, with respect to 100 parts of the total dry weight of the fiber. The adhesive may be added in advance by kneading the adhesive into the fiber raw material or by applying it after forming.

  The board forming method used in the present invention varies depending on the type of board, and basically, the board manufacturing methods and conditions conventionally produced are applied as they are.

In addition, fiber, particles, wood powder, waste paper, rice husks, etc. are made into a laminated board, so that strength is increased and dimensional stability is improved by laminating due to differences in fiber orientation, fiber length, and fiber. , Improvement of warpage, improvement of air permeability, prevention of powder falling, improvement of antibacterial, antifungal and deodorizing properties and long-term sustainability can be obtained. We can expect weight reduction effect. Furthermore, it can be expected to repel mice and pests. Further reduction of various harmful substances of the NO _X such air can be expected.

  Boards manufactured in the present invention are cut into small pieces and attached to indoor walls, used as an arrangement for flower arrangements, decorated with a picture frame on the surface of the board, decorated in a frame, etc. It is thought to contribute to indoor antibacterial, antifungal and deodorant.

Examples In order to make the present invention easier to understand, examples are shown below, but the following examples do not limit the present invention.

  As shown below, an antibacterial agent containing silver chloro complex salt (hereinafter referred to as an antibacterial agent) was prepared and used in the examples. A salt solution in which 25 kg of sodium chloride was dissolved in 711 water was prepared, and 40 g of silver chloride corresponding to silver metal was dissolved as an antibacterial agent while stirring the salt solution.

Example 1
Rice husk and cedar bark (bark) treated with the above antibacterial agents were used. The antibacterial agent was treated by separately putting rice husk and cedar bark separately in a rotating mixing drum with a hole in the center of the top lid, mixing the antibacterial agent 5% by weight while spraying and rotating the drum. . Each husk and cedar bark was entangled with a urethane-based water-dispersed adhesive using a gray blender. The amount of adhesive used was 10% by weight. The total weight of rice husk and cedar bark is 560 g, forming in the order of rice husk / cedar bark / rice husk, heat-pressed at 160 ° C. and 30 kg / cm ² for 5 minutes, 40 × 40 × 1 cm, density 0.35 g An antibacterial, antifungal and deodorant fiber floor board of / cm ³ was obtained. When exhalation was blown from one side of the obtained board, the exhalation was blown from the other side, and the cedar bark did not fall off.

Example 2
The cocoons and wood fibers treated with the above antibacterial agents were used. Each of the rice husks and wood fibers was entangled with a urethane-based water-dispersed adhesive using a gray blender. The amount of adhesive used was 8% by weight. The total weight of rice husk and wood fiber was formed in the order of rice husk / wood fiber / cocoon using 630 g, and pressure-clamped at 160 ° C. and 30 kg / cm ² for 10 minutes in the same manner as in Example 1. 40 × 40 A 1 cm density 0.38 g / cm ³ antibacterial, antifungal and deodorant fibrous laminate board was obtained.

Example 3
Particle chips and cedar barks were treated with the above antibacterial agent. Each particle chip and cedar bark were entangled with a urethane-based water-dispersed adhesive using a gray blender. The amount of adhesive used was 7% by weight. Particle chips / cedar bark / particle chips were formed in this order and heat-clamped at 150 ° C. and 30 kg / cm ² in the same manner as in Example 1 to obtain an antibacterial and antibacterial agent having a density of 40 × 40 × 1 cm and a density of 0.37 g / cm ³ .黴 Deodorized fibrous laminated board was obtained.

Example 4
Waste paper recycled pulp and buckwheat hulls treated with the above antibacterial agent were used. In addition, about the waste paper recycled pulp, after mixing with the said antibacterial agent, the mixed slurry which added polyvinyl alcohol 10weight% as an adhesive agent was put into the container of the net bottom, and it formed and used. The buckwheat husk was entangled with a phenol resin adhesive using a 10% by weight gray blender. Formed in the order of buckwheat husk / treated waste paper recycled pulp / buckwheat koji, carried out in the same manner as in Example 1 at 150 ° C., 20 kg / cm ^{2 with a} heating and pressing time of 10 minutes, and an antibacterial and antifungal agent with a density of 0.45 g / cm ² An odor fiber laminate board was obtained.

Example 5
Wood fiber and cedar bark were treated with the above antibacterial agent. A wood fiber and cedar bark were entangled with an adhesive urea phenol copolymer resin and ammonium chloride added as a curing accelerator using a 10 wt% gray blender. Formed in the order of wood fiber / cedar bark / wood fiber, and performed in the same manner as in Example 1 at 150 ° C. and 30 kg / cm ² with a heat-clamping time of 7 minutes, and an antibacterial and antifungal deodorant fiber having a density of 0.39 g / cm ³ A quality laminated board was obtained.

Comparative Examples 1-5
In Examples 1 to 5 except that the addition of the antibacterial agent was made as Comparative Examples 1 to 5.

Comparative Example 6
Comparative Example 6 was obtained by changing the total amount of the antibacterial agent of Example 1 to 1% by weight of Zeomic AC (a silver-supported silver antibacterial agent manufactured by Sinanen Zeomic Co., Ltd.).

Comparative Example 7
Comparative Example 7 was obtained by replacing 1% by weight of the antibacterial agent of Example 1 with 1% by weight of Novalon AG300 (zirconium phosphate-carrying silver antibacterial agent manufactured by Toagosei Co., Ltd.).

Example 6
The boards obtained in Examples 1 to 5 and Comparative Examples 6 and 7 were cut into 10 cm squares, placed in 20 cm square containers, then sealed with ammonia gas in a 30 ppm container, and measured with a detector tube after 7 days. . Although Examples 1-5 were 3-6 ppm, Comparative Examples 6 and 7 were 23-26 ppm.

Example 7
An antibacterial test was performed using the test pieces cut out from the boards obtained in Example 1 and Comparative Example 1 as specimens. After immersing the specimen in ordinary bouillon for 24 hours, E. coli, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, green bacterium, and Salmonella prepared with ordinary bouillon according to the “Film Contact Method” of the Antibacterial Product Technical Council The sample was covered with a plastic film, kept at 35 ° C. for 24 hours, and then the viable count on the specimen was measured.

Example 8
The boards obtained in Examples 1 to 5 and Comparative Examples 1 to 7 were tested by the “mold resistance test method” according to JISZ2911. The following 5 kinds of Aspergillus niger, Penicillium citrinum, Rhizopus stolonifer, Cladospodium cladosporoides, and Chaetomium globosum liquid mixture were prepared on three surfaces of each test piece (50 mm × 50 mm). After 1 ml was added and sealed, the cells were cultured at a temperature of 28 ° C. and a humidity of 95% for 4 weeks. The occurrence of mold was visually evaluated in the following five stages.
-: No mold on the sample +: Slight mold generation on the sample ++: Mold generation on 1/3 or less on the sample +++: Mold generation on 1/3 to 2/3 on the sample +++++: 2/3 or more on the sample Mold generation

The invention's effect

  The fibrous laminated board obtained by the present invention has antibacterial, antifungal and deodorizing performance and exhibits a long-term effect. It has been found that it is possible to provide fiber-laminated boards having a long lasting effect comparable to other silver antibacterial-added boards and organic anti-fungal additive-added boards.

Claims (3)

  A fibrous laminated board comprising an inorganic silver antibacterial agent added to a fibrous board.   The fibrous laminated board according to claim 1, wherein the antibacterial agent is a silver chloro complex salt.   2. The fiber laminate board according to claim 1, wherein the fiber laminate board is selected from wood boards such as fiber boards, particle boards, and wood flour boards, waste paper boards, and rice husks.