JP2003088755A - Antibacterial deodorization material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial deodorization material for adsorbing harmful substances from a gas or a liquid and its production method, more particularly, an antibacterial deodorization material usable in fields relevant to improvement of living environments and industrial work environments, for example, for adsorbing harmful substances for toilets, garbage, bedding, residences, hospitals, automotive and chemical-related facilities and the like, and its production method. SOLUTION: The antibacterial deodorization material is obtained by introducing an antibacterial deodorization function or a functional group changeable to have an antibacterial deodorization function into a substrate, which is soluble in water or a hydrated alcohol, by radiation graft polymerization of a polymerizable monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial deodorant material for adsorbing harmful substances from a gas or a liquid and a method for producing the same. More specifically, the present invention is used in fields related to the living environment, for example, an antibacterial deodorant material for adsorbing harmful substances in toilets, kitchen garbage, bedding, houses, hospitals, automobiles, etc. Regarding the manufacturing method.

[0002]

2. Description of the Related Art With the recent improvement of living standards, in addition to harmful substances emitted from factories, bad odors generated from daily life, such as toilet odors, kitchen odors, sewage odors, pet odors, etc. have become a problem. Has become. Causes of these malodors are ammonia, amines, hydrogen sulfide, mercaptans, lower fatty acids, aldehydes and the like. As a method of removing the malodor generated from these daily lives, for example, a method of spraying or volatilizing a fragrance substance, a chemical cleaning method using an acid / alkali, activated carbon, zeolite, bentonite, etc. There are a method of adsorption, an oxidation method using a catalyst and an oxidizing agent, and a method of neutralizing harmful substances by using an ion exchanger.

Japanese Unexamined Patent Publication (Kokai) No. 2-69123 discloses a medicine for disposing of excretions of pets. The chemical is obtained by adding a water-absorbing polymer powder to a main powder composed of a non-metallic mineral having an ion exchange property and an adsorptive power.

Japanese Examined Patent Publication No. 3-8738 discloses a dry granular material for treating excrement of livestock, pet animals and the like, which contains chemical pulp, mechanical pulp or semi-chemical pulp and an inorganic filler.

However, in these conventional methods,
It has drawbacks such as insufficient removal of harmful substances and the ability to remove only specific substances, and never achieved satisfactory effects.

[0006]

In view of the above prior art,
The present invention can adsorb a wide range of harmful substances, and
It is an object of the present invention to provide an antibacterial deodorant material having improved adsorption rate, adsorption efficiency and adsorption amount.

[0007]

[Means for Solving the Problems] In order to solve the above problems,
According to the present invention, there is provided an antibacterial deodorant material comprising a substrate to which a polymerizable monomer having a functional group having adsorptivity is bound.

The substrate used as the antibacterial deodorant material of the present invention is not particularly limited, and any material can be used as long as it can bond the polymerizable monomer. In the present invention, for example, aldohexose, sugars such as glucose, vitamins such as ascorbic acid, starch, water-soluble substances such as carboxymethyl cellulose, cotton, rayon, cellulose such as hemp, polyethylene, polyolefins such as polypropylene, or these Can be used.

The role of the substrate in the adsorbent material of the present invention is:
Supports a polymerizable monomer containing a functional group having adsorption performance,
Increase the adsorption area. Thus, in general, the substrate itself is in principle a material that is non-reactive, i.e. inert to the adsorbent material. In contrast to the role of the substrate, the polymerizable monomer plays a role of adsorbing the adsorbed substance. In this way, one of the major features of the present invention is that the substrate and the polymerizable monomer share the role of the adsorbent material. As a result, the adsorbed area increases and the material can be a physically and chemically stable antibacterial deodorant material. Unlike the adsorbent material of the present invention, the conventional ion-exchange resin polymerizes a polymerizable monomer having an ion-exchange group to form a polymer, so that there is no role sharing between the substrate and the functional group. Of.

The functional group having an adsorptive property in the present invention includes, for example, a hydrophilic group, a cationic dissociative group and an anionic dissociative group. Preferably, the functional group comprises a hydrophilic group and a cationic dissociative group and / or an anionic dissociative group. That is, the reactive monomer contains a hydrophilic group and a cationic dissociative group, a hydrophilic group and an anionic dissociative group, or a hydrophilic group and a cationic and anionic dissociative group. As described above, in the adsorption material of the present invention, the hydrophilic (nonionic) group and the ionic (cation and / or
Coexistence with the (or anion) group is one of the major characteristics.

As the graft polymerization method, for example, a reaction initiator polymerization method, a thermal polymerization method or an ionizing radiation polymerization method can be used. In this case, the desired degree of polymerization can be obtained by appropriately controlling the reaction conditions. When using ionizing radiation, ultraviolet rays, electron beams, X
Rays, α rays, β rays, γ rays and the like can be used. Therefore, the resulting polymerizable monomer is a polymerizable monomer having a hydrophilic group and a polymerizable monomer having a cationic dissociative group and / or a polymerizable monomer having an anionic dissociative group. Will consist of In this case, in the preparation of the polymerizable monomer, a mixture of the polymerizable monomer having a hydrophilic group, the polymerizable monomer body having a cationic dissociative group, and the polymerizable monomer having an anionic dissociative group The molar ratio can be appropriately selected depending on the intended use and performance of the adsorbent material. For example, the polymerizable monomer having a hydrophilic group is about 5 to about 20 mol%, the polymerizable monomer having a cationic dissociating group is about 30 to about 50 mol%, and the polymerization having an anionic dissociating group. The antibacterial deodorant material can be obtained by polymerizing a mixed solution of the functional monomer of about 30 to about 50 mol%.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic group includes, for example, a hydroxyl group,
There are hydroxyalkyl groups (wherein the alkyl groups are preferably lower alkyl groups), diol groups, amino groups or pyrrolidonyl groups. Preferred hydrophilic groups include hydroxyl groups and hydroxyalkyl groups. One or more hydrophilic groups may be introduced into the antibacterial deodorant material. And, as the polymerizable monomer having such a hydrophilic group, those useful in the present invention include, for example, hydroxyethyl methacrylate, hydroxypropyl acrylate, vinylpyrrolidone, dimethylacrylamide, ethylene glycol monomethacrylate, ethylene glycol monoacrylate. , Ethylene glycol monomethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate and triethylene glycol methacrylate. Among these, particularly useful polymerizable monomers include hydroxyethyl methacrylate and vinylpyrrolidone.

In the present invention, the "cationic dissociative group" means an ion exchange group whose counter ion is a cation. A typical cationic dissociative group is an acid group. The cationic dissociative group has the ability to adsorb a polar substance and can release a proton (hydrogen ion) to neutralize with a basic substance such as ammonia or amines. As a result, the basic substance is removed. In the reactive monomer,
One or two or more kinds of cationic dissociative groups may be introduced.

Examples of such a cationic dissociative group include a carboxyl group, a sulfone group, a phosphoric acid group, a sulfoethyl group, a phosphomethyl group and a carbomethyl group. Preferred cationic dissociative groups include sulfone groups and carboxyl groups. And, those useful in the present invention as the polymerizable monomer having such a cationic dissociative group,
For example, acrylic acid, methacrylic acid, allyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid and salts thereof, and 2-acrylamido-2-methylpropane sulfonic acid. Further, a polymerizable monomer having a group capable of being converted into a cationic dissociative group is also useful in the present invention. Examples of such reactive monomers include glycidyl methacrylate and glycidyl acrylate.

In the present invention, the "anionic dissociative group" means an ion exchange group whose counter ion is an anion. Therefore, the anionic dissociative group has the ability to adsorb polar substances,
In addition, it can neutralize with acidic substances such as hydrogen sulfide and mercaptans. As a result, the acidic substances are removed. One or more anionic dissociative groups may be introduced into the polymerizable monomer.

Such anionic dissociative groups include, for example, quaternary ammonium groups, 1-groups such as amino groups, methylamino groups, dimethylamino groups and diethylamino groups.
There are primary to quaternary amine groups. Preferred anionic dissociative groups are quaternary ammonium groups and amino groups. And as a reactive monomer having such an anionic dissociative group, those useful in the present invention include, for example, vinylbenzyltrimethylammonium salt, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl. Acrylate, diethylaminomethyl methacrylate, tertiary butylaminoethyl acrylate, tertiary butylaminoethyl methacrylate and dimethylaminopropyl acrylamide, acrylamide,
There are allylamine, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylamide. Of these, particularly useful polymerizable monomers are vinylbenzyl trimethyl ammonium salt, diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylamide, acrylamide,
It is allylamine. A polymerizable monomer having a group that can be converted into an anionic dissociative group is also useful in the present invention. Such polymerizable monomers include, for example, chloromethylstyrene.

In the present invention, one or more hydrophilic groups may be present in the polymerizable monomer. Similarly, the cationic dissociative group and the anionic dissociative group may be respectively present in the polymerizable monomer in one or more kinds.

The preferred combination of functional groups in the present invention is, specifically, a sulfone group and a carboxyl group, 4
There are such as primary ammonium group, and hydroxyethyl group. Further, another preferable combination of the functional groups in the present invention specifically includes a sulfone group, a carboxyl group, a quaternary ammonium group, and a pyrrolidonyl group.

It is of course possible to use the antibacterial deodorant material having a functional group capable of adsorbing a polar substance thus obtained alone. That is, the antibacterial deodorant material may be diluted and filled in a spray can to be used as a spray type deodorant spray. However, in the present invention, an antibacterial deodorant material is bonded to a substrate in view of widening its application as an adsorbent material by immobilizing a reactive monomer chemically and physically stably on an existing shape substrate. To do.

In the adsorbent material of the present invention, the antibacterial deodorant material is chemically bonded to the substrate. As a binding method, any known method can be used. As described above, the antibacterial deodorant material of the present invention can remove various substances with high efficiency, and thus, for example, antibacterial deodorant spray, garbage deodorant, toilet deodorant, diaper deodorant, It can be used in a wide range of applications such as improving the living environment such as deodorizing refrigerators, deodorizing perm liquid, deodorizing hospitals, deodorizing industrial waste, and industrial fields such as industrial raw materials.

The present invention will be described in more detail below with reference to examples.

[0022]

Example 1 Sodium allyl sulfonate 3 parts, acrylic acid 1.5 parts, aldohexose 0.5 part, trimethyl borate
Mixed solution 1 containing 0.1 part and 1 part isopropyl alcohol
1 liter was placed in a polyethylene container. Next, this aqueous solution was irradiated with γ-rays from cobalt 60 at a dose rate of 5 KGy / hr for 2 hours at room temperature to polymerize the solution to obtain a graft-polymerized deodorant material of the present invention. As a result of measuring the ion exchange capacity, 2.0 mmol of the cation exchange group was introduced per gram of the deodorant material.

Next, the adsorption performance of the deodorant material thus obtained was tested. A 100 ml beaker was placed in the center of the bottom of a 5 liter glass desiccator, and 3 g of deodorant material was placed therein. Add 100% 28% ammonia water to the beaker.
1 g of the double diluted solution was added and 1 minute later, the concentration of ammonia in the container was measured with a Gastec detector tube. As a result, ammonia gas was not detected. Add 100% 28% ammonia water to a beaker
In a blank test in which 1 g of a double-diluted solution was added and 1 minute later, the ammonia concentration in the container was measured with a Gastec detector tube, the ammonia concentration was 450 ppm. Similarly, when measured with a typical commercially available deodorant, the result was that the ammonia concentration in the container was 100 ppm. It was found that the deodorant material of the present invention has an extremely large adsorption capacity and is immediately effective.

[0024]

Example 2 1 liter of a mixed aqueous solution containing 2 parts of N, N-dimethylaminopropyl acrylamide, 1 part of hydroxyethyl methacrylate and 0.5 part of aldohexose was placed in a polyethylene container. Next, this aqueous solution was irradiated with γ-rays from cobalt 60 at a dose rate of 5 KGy / hr for 2 hours at room temperature to polymerize the solution to obtain a graft-polymerized deodorant material of the present invention. As a result of measuring the ion exchange capacity, 1.5 mmol of anion exchange groups were introduced per gram of the deodorant material.

Then, the adsorption performance of the deodorant material thus obtained was tested in the same procedure as in Example 1. However, a solution prepared by diluting acetic acid by 15 times was used instead of ammonia. As a result, the acetic acid concentration of the deodorant material of the present invention was 0 p
In the pm blank test, the acetic acid concentration was 30 ppm. Similarly, when measured with a typical commercial deodorant, the acetic acid concentration in the container was 20 ppm. It was found that the deodorant material of the present invention has an extremely large adsorption capacity and is immediately effective.

[0026]

Example 3 1 liter of a mixed aqueous solution containing 2 parts of sodium vinyl sulfonate, 1 part of methacrylic acid, 1 part of vinylpyrrolidone and 0.5 part of carboxymethyl cellulose was placed in a polyethylene container. Next, cobalt 6 is added to this aqueous solution.
Graft polymerization was carried out by irradiating γ rays from 0 at a dose rate of 5 KGy / hr at room temperature for 2 hours to polymerize. Copper was adsorbed on the sulfone group and the carboxyl group of this deodorant solution to form an antibacterial deodorant material.

As a result of measuring the ion exchange capacity, 1.0 mmol of the cation exchange group was introduced per gram of the deodorant material.
The antibacterial deodorant material thus obtained was then tested for adsorption performance. 1 g of a non-woven fabric impregnated with 23 g / m 2 of antibacterial deodorant was put in a 1 liter Tedlar bag, and 60 ppm of methyl mercaptan gas was put therein, and after 60 minutes, the methyl mercaptan concentration was measured with a Gastec detector tube. As a result, methyl mercaptan gas was not detected. In the blank test, the methyl mercaptan concentration was 60 ppm. Similarly, when measured with a typical commercial deodorant, the concentration of methyl mercaptan in the Tedlar bag was 55 ppm. The deodorant material of the present invention has an extremely large adsorption capacity,
It was found to have immediate effect.

[0028]

Example 4 Allylamine 1 part, vinylbenzyltrimethylammonium salt 1 part, vinylpyrrolidone 1 part, starch
1 liter of a mixed aqueous solution containing 0.5 part was placed in a polyethylene container. Next, γ from cobalt 60 was added to this aqueous solution.
The deodorizing material of the present invention was obtained by graft-polymerizing the wire by irradiating it with a dose rate of 5 KGy / hr for 2 hours at room temperature for polymerization. As a result of measuring the ion exchange capacity, 2.0 mmol of the cation exchange group was introduced per gram of the deodorant material.

Next, the adsorption performance of the deodorant material thus obtained was tested by the same procedure as in Example 1. However, instead of ammonia, a 36% formaldehyde solution diluted 5 times was used. As a result, the formaldehyde concentration was 0 ppm in the deodorant material of the present invention, and the formaldehyde concentration was 50 ppm in the blank test. Also,
Similarly, when measured with a typical commercially available deodorant, the formaldehyde concentration in the container was 24 ppm. It was found that the deodorant material of the present invention has an extremely large adsorption capacity and is immediately effective.

[0030]

[Example 5] An antibacterial deodorant solution was subjected to an antibacterial test using a sample obtained by impregnating a non-woven fabric with the antibacterial deodorant material obtained in Example 3 at 23 g / m2. An unprocessed nonwoven fabric was used as a comparative sample. Antibacterial test is JIS L 190
2 (textile product antibacterial test method). Staphylococcus aureus ATCC 6538P was used as the test bacterium. As a result, the antibacterial activity (bacteriostatic activity value) was 4.9 or more when the antibacterial deodorant material was impregnated into the nonwoven fabric, and 0.1 when the unprocessed nonwoven fabric was obtained. The excellent antibacterial property of the odorous material was confirmed.

[0031]

The antibacterial deodorant material of the present invention comprises a hydrophilic group, a cation dissociative group and / or an anion dissociable group and / or
Or, since it contains a complex-forming group, it can adsorb various harmful components in the environment at the same time in addition to acidic substances and basic substances. Is easy to process. In addition, a deodorant material having an extremely high adsorption efficiency, a large adsorption capacity and an antibacterial effect can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01D 53/02 B01D 53/02 Z B01J 20/30 B01J 20/30 C08F 291/00 C08F 291/00 F term (reference) 4C080 AA05 BB02 BB05 CC02 CC04 CC05 CC08 CC12 CC13 CC15 HH09 JJ05 KK06 KK08 LL02 LL09 LL12 MM02 MM12 MM22 MM23 MM26 MM28 NN22 NN23 NN24 NN26 NN28 QQ03 4D012 BA01 CA09 CA20 CB01 CG01 CG03 4G066 AC01C AD01B AD09B AD10B AD13B AD20B AE05B AE10B AE20C CA02 CA29 CA56 DA03 DA07 FA07 FA31 4J026 AA02 AA03 AA04 AA08 AA12 AA13 BA08 BA25 BA28 BA29 BA30 BA32 BA39 BA40 BA50 DB36 EA08 EA09 GA02 GA08

Claims (8)

[Claims] 1. An antibacterial deodorant function or a functional group capable of being converted into an antibacterial deodorant function is introduced into a base material soluble in water or alcohol hydrate by radiation graft polymerization of a polymerizable monomer. Antibacterial deodorant material characterized by 2. An antibacterial deodorant is formed by introducing a polymerizable monomer into a substrate having solubility in water or alcohol hydrate by a radiation graft polymerization method to form a graft side chain. A method for producing a radiation antibacterial deodorant material, which comprises introducing a functional group capable of converting into a function or an antibacterial deodorant function. 3. An antibacterial deodorant liquid and an antibacterial deodorant liquid comprising the antibacterial deodorant material or the deodorant material according to claim 1. 4. An antibacterial deodorant material whose base material having solubility in water or alcohol hydrate is composed of synthetic and natural materials. 5. A hydrophilic group, for example, a hydroxyl group or a hydroxyalkyl group, which is a functional group introduced by radiation-polymerizing a polymerizable monomer onto a substrate having solubility in water or alcohol hydrate. An antibacterial deodorant material comprising one or a combination of a diol group, an amino group or a pyrrolidonyl group. 6. A functional group introduced by radiation-induced graft polymerization of a polymerizable monomer onto a base material soluble in water or alcohol hydrate, wherein the functional group is a sulfone group, an oxosulfone group, a methylsulfone group, Ethyl sulfone group, phosphoric acid group,
Phosphonic acid group, carboxyl group, primary amino group, secondary amino group, tertiary amino group, quaternary amino group, quaternary ammonium group, trimethyl ammonium group, amidoxime group, iminodiacetic acid group, alkyl group, alkylene group, alkylene An antibacterial deodorant material composed of one or a combination of an oxymethylene group, an alkanol group, an alkoxymethylene group, a diol group. 7. An antibacterial deodorant material comprising one or several functional groups according to claim 5 or 6. 8. A part of the functional group introduced by the radiation graft polymerization comprises one of hydrogen, halogen, silver, copper, cobalt, nickel, zinc, manganese, iron, iodine, bromine and a combination thereof. Antibacterial deodorant material.