KR20010103268A - Deodorant and antimicrobial compositions - Google Patents

Abstract

Deodorizing and antimicrobial compositions comprise oxides or hydroxides of alkaline earth metals, hydrous silicic acid and cationic surfactants. Deodorizing and antimicrobial resin compositions can be obtained using deodorizing and antimicrobial compositions and thermoplastic resins. This deodorant and antimicrobial resin composition may be molded or molded.

Description

Deodorant and antimicrobial compositions {DEODORANT AND ANTIMICROBIAL COMPOSITIONS}

The present invention relates to deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions using the deodorizing and antimicrobial compositions, and deodorizing and antimicrobial resin moldings obtained by molding or molding the resin composition. More specifically, the present invention is useful as a deodorizing and antimicrobial agent in the form of a powder itself, and also deodorizing and antimicrobial compositions useful for imparting deodorizing power and antimicrobial properties to various substrates such as paints, synthetic fibers, synthetic resins, and paper, The present invention relates to a deodorizing and antibacterial resin composition using a deodorizing and antimicrobial composition, and a deodorizing and antimicrobial resin molding obtained by molding or molding the resin composition.

Conventionally, many deodorizing and antibacterial agents in various fields have been used. In particular, various products such as films, wallpaper, decorative boards, building materials, fibers, nonwoven fabrics, and medical treatments are required to prevent odors, bacteria, and molds. When odors, bacteria, molds, etc. occur, it is often required to remove these odors, bacteria, molds, etc.

In recent years, voices calling for the comfort of living space have been increasing. In the clean environment, eliminating the discomfort of sight and smell and sanitary discomfort such as microbial pollution, from the viewpoint of living environment in dense houses and building structures constructed with concrete and aluminum sash windows, due to urbanization There is no condition.

Specifically, in recent years, health problems caused by formaldehyde have become a problem. The living environment in enclosed housing structures, especially the smell of formaldehyde in new construction, has already become a social problem as "sick house syndrome." This problem is caused by formaldehyde generated from new construction materials. Therefore, various products such as wallpaper, decorative board, building materials, fibers, nonwoven fabrics, medical products, sundries, and films are required to remove the generated formaldehyde odor. In addition, from the viewpoint of hygiene such as prevention of microbial contamination, functions of antibacterial and mold prevention are also required at the same time.

Accordingly, it is an object of the present invention to provide a deodorizing and antimicrobial composition which can impart excellent deodorizing power and antimicrobial properties to various materials.

The said object is achieved by the following this invention. That is, the present invention is deodorizing and antimicrobial composition comprising an oxide or hydroxide of alkaline earth metal, hydrous silicic acid and cationic surfactant; Provided are a deodorizing and antibacterial resin composition using the deodorizing and antimicrobial composition, and a deodorizing and antimicrobial resin molding obtained by molding or molding the composition.

Deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the present invention are useful for deodorizing acetaldehyde, formaldehyde, acetic acid and the like in various unpleasant odors. In addition, the deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the invention are also excellent in antimicrobial properties.

In addition, the deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the present invention can impart excellent deodorizing power and antimicrobial properties to various articles.

Next, the present invention will be described in more detail with reference to preferred examples.

Deodorizing and antimicrobial compositions according to the present invention are made by combining an oxide or hydroxide of an alkaline earth metal, a hydrous silicic acid and a cationic surfactant. Examples of the oxides or hydroxides of alkaline earth metals include oxides and hydroxides such as barium, calcium, magnesium, and the like, and magnesium hydroxide is particularly effective.

When the amount of the alkali earth metal oxide or hydroxide is 100 parts by weight of the whole deodorizing and antimicrobial composition, it is preferable to use it in a proportion of 80 to 40 parts by weight. If the amount of the oxide or hydroxide of the alkali earth metal is less than the above range, the performance is not satisfactory in that the change of aldehydes, especially formaldehyde, formose is delayed. On the other hand, if the amount of the oxide or hydroxide of the alkaline earth metal exceeds the above range, the proportion of the substance in the composition of the substance which removes formaldehyde by addition reaction with formaldehyde, that is, the cationic surfactant is reduced, and the deodorization of the aldehydes is reduced. The performance is not satisfactory in that the reaction rate is slow and the fastness is inferior.

The hydrous silicic acid used in the present invention is represented by the empirical formula SiO ₂ · nH ₂ O, and particles having a large number of silanol groups on the surface of the silicic acid fine particles agglomerate to become secondary particles. It is an aggregate of ultra-fine hydrous silicic acid obtained by reaction with, and has a large number of voids between particles. These voids work effectively to remove various malodorous components such as formaldehyde.

Such hydrous silicic acid is, for example, trade name "P-801", "P-802", "P-526", "P-527", "P-603", "P-" from Mizusawa Kagaku Co., Ltd., Japan. 604 ", P-554A", "P-73", "P-78A", "P-78D", "P-78F", "P-707", "P-740", "P-752", "P-50", "P-766", "C-1", "S-0", "NP-8", "P-802Y", "P-832", "P-87", "P -363 "," C-002 "," P-402 ", and" P-484 "can be obtained and used in the present invention.

When the said hydrous silicic acid is 100 weight part of deodorization and antimicrobial composition, it is preferable to use it in the ratio which occupies 50-10 weight part. If the amount of the hydrous silicic acid is less than the above range, the deodorization reaction rate of the aldehydes is low, and the performance is not satisfactory in that it is inferior in fastness. On the other hand, when the usage-amount of hydrous silicic acid exceeds the said range, when the deodorizing and antimicrobial composition of this invention is knead | mixed with resin, performance is also unsatisfactory in the point that the fluidity | liquidity of resin becomes poor.

The cationic surfactant used in the present invention, R is preferably represented by C ₁₂ ~C ₁₄ alkylene group of the empirical formula _{HO-R- NHCH 2 CH 2 OH} . A cationic surfactant makes an aldehyde compound an odorless compound by reacting with aldehyde groups, such as formaldehyde. Such cationic surfactants are, for example, trade names "Miyo-Col 368E", "Miyo-Col QX-33N", "Duspa 125B", "Duspa 125BN", "Duspa 125BS", " It is available as Dospa 1400B "and can be used in the present invention.

The said cationic surfactant can be used individually or in mixture of two or more. However, these include compounds that are insufficient in dispersibility, stability, thermal stability, light resistance, processability and / or the like when prepared by mixing deodorizing and antimicrobial compositions. When the deodorizing and antimicrobial compositions of the present invention are applied to various applications, heat resistance is also important with respect to processability. In this respect, "Duspa 125B" and "Duspa 125BN" are particularly preferable.

When the amount of the cationic surfactant is 100 parts by weight of the deodorizing and antimicrobial composition, it is preferable to use the cationic surfactant in a proportion of 0.1 to 30 parts by weight. If the amount of the cationic surfactant used is less than the above range, the deodorization reaction rate of the aldehydes is slow, and the performance is unsatisfactory in that the antibacterial property is insufficient. On the other hand, when the usage-amount of cationic surfactant exceeds the said range, the composition itself obtained will lose powderiness, and the handleability will deteriorate.

The deodorizing and antimicrobial composition of the present invention comprising the above components can be obtained by simply mixing each of the above components, and can be used for the same various uses as the conventional deodorizing and antibacterial agents.

When deodorizing power and antimicrobial properties are to be imparted to various resin moldings using the deodorizing and antimicrobial composition of the present invention, it can be mixed with the deodorizing and antimicrobial resin composition to obtain a deodorizing and antimicrobial composition.

The resin used in the present invention is a polyolefin resin, such as polyethylene and polypropylene, which has been used for various moldings or moldings for many years for molding or molding various moldings, such as plastic films, plastic sheets, plastic containers, and fibers. Synthetic or modified thermoplastic resins such as vinyl chloride, vinylon, polystyrene, polyamide, polyester, and cellulose acetate. All of these thermoplastic resins can be easily obtained and used in the market for use in the present invention, and these thermoplastic resins may be in a liquid form such as a solid form or a paste form.

The deodorizing and antimicrobial resin composition of the present invention comprises, as an essential component, two components, the resin and the deodorizing and antimicrobial composition. The mixing ratio may be 99.9 to 50 parts by weight of the resin and 0.1 to 50 parts by weight of the deodorizing and antimicrobial composition, preferably 99.9 to 80 parts by weight and 1.0 to 20 parts by weight of the deodorizing and antimicrobial composition. In the resin composition of the present invention, various conventionally known additives for resins such as colorants, fillers, extender pigments, plasticizers, stabilizers, ultraviolet absorbers, and the like can be arbitrarily blended as necessary.

The deodorizing and antimicrobial resin composition according to the present invention can be obtained by simply mixing the above components, or may be one obtained by melt-kneading the mixture to form particles by pellets or the like. It may also be in the state of a masterbatch containing a high concentration of deodorizing and antimicrobial components for later dilution with a natural (ie, no additive) thermoplastic resin.

As described above, deodorizing and antimicrobial resin compositions are useful for the production of deodorizing and antibacterial resin moldings. Examples of the deodorizing and antimicrobial resin moldings of the present invention include containers of a desired shape obtained by molding or molding the deodorizing and antimicrobial resin compositions in various shapes such as plastic films or sheets and deodorizing and antimicrobial resin compositions in various ways. It may include those obtained by molding or molding.

The molding or molding of such a film, sheet, container, or the like can use various conventionally known conditions as it is by a conventionally known inflation extruder, press, calendar, extruder, spinning machine, blow molding machine, injection molding machine, vacuum molding machine, etc. Deodorizing and antimicrobial resin molding according to the present invention can be easily obtained.

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely. In the text, "part" or "" is based on weight.

Example 1

In 97 parts of low density polyethylene, a mixture consisting of magnesium hydroxide having a weight ratio of 6: 3: 1, a functional silicate (trade name "P-766") and a cationic surfactant ("Duspa 125B") (deodorization according to the present invention and Antimicrobial composition) 3 parts. 40mm extruder (L / D

= 28, C.R.:3.1, Dulme screw, cylinder temperature 130 ° C., screw speed 70 rpm), thereby obtaining a deodorizing and antimicrobial resin composition of the present invention in the form of a pallet.

Subsequently, the deodorizing and antimicrobial resin composition was introduced into an inflation extruder (30 mm extruder, an inflation die with a diameter of 50 mm, cylinder temperature: 140 ° C., screw speed: 60 rpm), and blow film extrusion was performed. As a result, a polyethylene film having a thickness of 50 µm was obtained.

Example 2

The plastic film of the present invention was obtained in the same manner as in Example 1 except that the deodorizing and antimicrobial resin composition and the deodorizing and antimicrobial resin composition of the present invention were prepared using the following components.

95 parts of low density polyethylene

A mixture of magnesium hydroxide / functional silicate (trade name “P-707”) / cationic surfactant (trade name “Duspa 125B”) weight ratio 5: 3: 2

Example 3

The plastic film of the present invention was obtained in the same manner as in Example 1 except that the deodorizing and antimicrobial composition and the deodorizing and antimicrobial resin composition of the present invention were prepared using the following components.

97 parts of polypropylene

Calcium hydroxide / silicate silicate (trade name "P-740") / cationic surfactant ("Duspa

125B ") weight ratio 5: 4: 1

Example 4

The plastic film of the present invention was obtained in the same manner as in Example 1 except that the deodorizing and antimicrobial composition and the deodorizing and antimicrobial resin composition of the present invention were prepared using the following components.

Polystyrene 97 parts

A mixture of calcium hydroxide / functional silicate (trade name “P-752”) / cationic surfactant (trade name “Duspa 125B”) weight ratio 4: 4: 2

Example 5

70 parts of polypropylene and 30 parts of deodorizing and antimicrobial composition "(Magnesium hydroxide, hydrous silicic acid (trade name" P-766 ") and cationic surfactant (trade name" Duspa 125B ") weight ratio 6: 3: 1) The mixture was mixed for 2 minutes at a rotational speed of 1,500 rpm with a Henschel mixer, followed by kneading in a 40 mm extruder (L / D: 28, CR: 3.1, dulge screw, cylinder temperature: 200-215 ° C., screw speed 90 rpm). Palletized deodorant and antimicrobial resin composition was obtained by diluting it 10 times with natural resin (polypropylene) The composition diluted with the spinning machine was stretched after spinning at 200 to 215 ° C. to obtain 15 denier fibers. And the thread was not broken at the time of stretching.

Example 6

70 parts of polyester and 30 parts of deodorizing and antimicrobial composition "(Magnesium oxide, hydrous silicic acid (brand name" P-766 ") and cationic surfactant (brand name" Duspa 125B ") weight ratio 5: 4; 1) 2 minutes at a rotational speed of 1,500 rpm with a Henschel mixer, followed by kneading with a 40 mm extruder (L / D: 28, CR: 3.1, dulge screw, cylinder temperature: 270-280 ° C., screw speed 90 rpm) The resin composition was diluted 10-fold with a natural resin (polyester) The composition diluted with the spinning machine was stretched after spinning at 280-290 degreeC, and it was set as 15 denier fibers. Thread breaking did not occur during spinning and stretching.

<Evaluation>

The deodorization and antimicrobial effects of various molded products obtained in Examples 1 to 6 were examined by the following test methods. The result of the late Tables 1-5 was obtained.

「Deodorization performance test method」

Acetic acid deodorization test

Into a 300 ml Erlenmeyer flask, dilute acetic acid solution (2.5 µl) was added to the sample. The flask was stored at 25 ° C., and after a predetermined time, acetic acid residual concentration in the flask was measured using a guitar gas detector. The results are shown in Table 1.

(Formaldehyde deodorization test)

Into a 300 ml Erlenmeyer flask, a 3.5 formaldehyde aqueous solution (1 µl) was added to the sample. The flask was stored at 25 ° C., and after a predetermined period of time, the remaining concentration of formaldehyde in the flask was measured using a guitar gas detector. The results are shown in Table 2.

(Acetaldehyde Deodorization Test)

Into a 300 ml Erlenmeyer flask, 2.5 acetic aqueous solution (1 µl) was added, and a sample was added thereto. The flask was stored at 25 ° C, and after a predetermined time, acetaldehyde residual concentration in the flask was measured using a guitar gas detector. The results are shown in Table 3.

TABLE 1

Table 1: Acetic acid deodorization test results

Acetic Acid Concentration (ppm) Test sample 5 minutes later 30 minutes later 120 minutes later Blank 45 45 45 1 film (50 mm x 200 mm) Example 1 2 Undetected Undetected 1 film (50 mm x 200 mm) Example 2 3 Undetected Undetected 1 film (50 mm x 200 mm) Example 3 One trace Undetected 1 film (50 mm x 200 mm) Example 4 2 Undetected Undetected 1 film (50 mm x 200 mm) Example 5 Undetected Undetected Undetected 0.2g filament Example 6 Undetected Undetected Undetected 0.2g filament Comparative example 6 3 trace 0.2g filament

Blank is a case where a polyethylene film prepared in a manner similar to Example 1 was used as a test sample except that the deodorizing and antimicrobial composition of the present invention was not used.

Comparative Example is a deodorizing and antimicrobial composition, in which a filament prepared in a similar manner to Example 5 was used as a test sample of Comparative Example, except that no cationic surfactant was added.

These footnotes are the same in Tables 2 and 3.

TABLE 2

Table 2: Formaldehyde Deodorization Test Results

Formaldehyde concentration (ppm) Test sample 5 minutes later 30 minutes later 120 minutes later Blank 105 105 105 1 film (50 mm x 200 mm) Example 1 10 6 2 1 film (50 mm x 200 mm) Example 2 10 7 2 1 film (50 mm x 200 mm) Example 3 12 8 3 1 film (50 mm x 200 mm) Example 4 10 5 One 1 film (50 mm x 200 mm) Example 5 Undetected Undetected Undetected 0.2g filament Example 6 Undetected Undetected Undetected 0.2g filament Comparative example 15 10 5 0.2g filament

TABLE 3

Table 3: Acetaldehyde Deodorization Test Results

Acetaldehyde concentration (ppm) Test sample 5 minutes later 30 minutes later 120 minutes later Blank 35 35 35 1 film (50 mm x 200 mm) Example 1 10 6 One 1 film (50 mm x 200 mm) Example 2 10 7 2 1 film (50 mm x 200 mm) Example 3 9 4 One 1 film (50 mm x 200 mm) Example 4 5 3 trace 1 film (50 mm x 200 mm) Example 5 3 trace Undetected 0.2g filament Example 6 One Undetected Undetected 0.2g filament Comparative example 15 10 10 0.2g filament

`` Antibacterial test ''

Tested strains ;

Gram negative bacteria: Escherichia coli: Escherichia coli IFO 3972

Gram-positive bacteria: Staphylococcus aureus IFO 12732

Test method ;

Pre-culture: 37 ° C. in NUTRIENT broth medium, shaking culture (E. coli: 16 hours, Staphylococcus aureus: 12 hours)

Antibacterial test: The sterilized sample (about 50 x 50 mm, 0.05 g in the case of fibers) was dried and placed in a sterile saale. On the other hand, the preculture was diluted to prepare the inoculum shown in Table 4 and Table 5, respectively. In the case of the preculture of E. coli, the preculture was diluted with a solution so as to adjust the number of viable cells per ml to 3.1 × 10 ⁵ to prepare the inoculation solution. The solution is prepared by diluting the NUTRIENT broth medium with phosphate buffer (pH 7.2) so that its nutrient concentration is lowered to 1/500. On the other hand, in the case of the preculture of the yellow cloth, the incubation was prepared by diluting the preculture with a solution to adjust the viable cell count per ml to 8.5 × 10 ⁴ . This solution is prepared by diluting the NUTRIENT broth medium with phosphate buffer (pH 7.2) so that its nutrient concentration is lowered to 1/50. About each cell line, the inoculation solution in which the viable cell number was adjusted as described above was inoculated with 0.1 ml on the surface of each test sample, 4 places on a diagonal, and 0.5 ml of a total of one place on the center. After 24 hours of incubation at 30 ± 1 ° C. and relative humidity of 90 or more, the cells were washed with 4.5 ml of phosphate buffer. The number of viable cells in this test solution was measured by the mixed stone plate method using agar medium. In addition, as a control, only a tester for Shaale bacteria was tested.

TABLE 4

Table 4: Antibacterial test results of E. coli

Sample Viable Count (cells / ml) Suppression rate () Inoculation solution (initial viable count) 3.1 × 10 ⁵ - control 1.9 × 10 ⁵ - Example 1 <10 > 99.9 Example 2 <10 > 99.9 Example 3 <10 > 99.9 Example 4 <10 > 99.9 Example 5 <10 > 99.9 Example 6 <10 > 99.9 Comparative example 7.9 × 10 ⁶ 0

The control is a case where it is left as it is without putting a sample.

In Comparative Example, a film prepared in a similar manner to Example 1 was used as a test sample except that no cationic surfactant was added as the deodorizing and antimicrobial composition.

These footnotes are also the same in Table 5.

TABLE 5

Table 5: Antibacterial test results of Staphylococcus aureus

Sample Viable Count (cells / ml) Suppression rate () Inoculation solution (initial viable count) 8.5 × 10 ⁴ - control 6.7 × 10 ⁴ - Example 1 <10 > 99.9 Example 2 <10 > 99.9 Example 3 <10 > 99.9 Example 4 <10 > 99.9 Example 5 <10 > 99.9 Example 6 <10 > 99.9 Comparative example 6.8 × 10 ⁴ 0

Example 7

The pellet-shaped deodorizing and antimicrobial granules (100 g) obtained in Example 1 were enclosed in a filter portion of a vacuum cleaner (manufactured by Hitachi Co., Ltd., trade name "CV-C45"), and then indoors (temperature: 26 ° C, humidity: 75). The walls and bottom of the were vacuumed. The formaldehyde concentration in the room decreased from 0.279 ppm to 0.003 ppm (formaldehyde removal rate: 80), and in the closet, the formaldehyde concentration decreased from 0.467 ppm to 0.003 ppm (formaldehyde removal rate: 90).

Deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the present invention are useful for deodorizing acetaldehyde, formaldehyde, acetic acid and the like in various unpleasant odors. In addition, the deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the invention are also excellent in antimicrobial properties.

In addition, the deodorizing and antimicrobial compositions, deodorizing and antimicrobial resin compositions and deodorizing and antimicrobial resin moldings according to the present invention can impart excellent deodorizing power and antimicrobial properties to various articles.

Claims (9)

Oxides or hydroxides of alkaline earth metals; Hydrous silicic acid; And Deodorizing and antimicrobial composition comprising a cationic surfactant. The total amount of the alkaline earth metal oxide or hydroxide is 80 to 40 parts by weight, the hydrous silicic acid is 50 to 10 parts by weight, and the cationic surfactant is 0.1 to 30 parts by weight. Deodorizing and antimicrobial composition. The deodorizing and antimicrobial composition according to claim 1, wherein the oxide or hydroxide of the alkaline earth metal is magnesium hydroxide. The deodorizing and antimicrobial composition according to claim 1, wherein the cationic surfactant is represented by empirical formula: HO-R-NHCH ₂ CH ₂ OH, wherein R is an alkylene group having C ₁₂ to C ₁₄ . 99.9 to 50 parts by weight of thermoplastic resin; And A deodorizing and antimicrobial resin composition comprising 0.1 to 50 parts by weight of a deodorizing and antimicrobial composition comprising an oxide or hydroxide of an alkaline earth metal, a hydrous silicic acid and a cationic surfactant. The composition according to claim 5, wherein when the composition is 100 parts by weight in total, 80 to 40 parts by weight of an oxide or hydroxide of an alkaline earth metal, 50 to 10 parts by weight of hydrous silicic acid, and 0.1 to 30 of a cationic surfactant. Deodorizing and antimicrobial resin composition, characterized in that parts by weight. 6. The deodorizing and antimicrobial resin composition according to claim 5, wherein the oxide or hydroxide of the alkaline earth metal is magnesium hydroxide. 6. The deodorizing and antimicrobial resin composition according to claim 5, wherein the cationic surfactant is represented by the empirical formula wherein R is an alkylene group having C ₁₂ to C ₁₄ : HO-R-NHCH ₂ CH ₂ OH. Deodorizing and antimicrobial resin moldings obtained by molding deodorizing and antimicrobial resin compositions, the deodorizing and antimicrobial resin compositions 99.9 to 50 parts by weight of thermoplastic resin; And A deodorizing and antimicrobial resin molding comprising 0.1 to 50 parts by weight of a deodorizing and antimicrobial composition comprising an oxide or hydroxide of an alkaline earth metal, a hydrous silicic acid and a cationic surfactant.