JP2977652B2 - Antibacterial polyester resin composition for toothbrush - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial polyester resin composition for toothbrushes having excellent long-term durability, deodorization and antibacterial properties.

[0002]

2. Description of the Related Art Thermoplastic resins have been generally considered as materials having excellent resistance to microorganisms such as fungi and bacteria, but recently, microbial damage to thermoplastic resins has been reported. I have. In order to impart antibacterial properties, it is common to mix an antibacterial agent, but as the antibacterial agents conventionally used, benzimidazole type, phenol ether type, N-haloalkylthio type, etc. There are organic ones. However, the organic antibacterial agent is inferior in heat resistance and durability, and has a problem in safety. In addition, when spinning is performed using a resin containing an organic antibacterial agent as a raw material, foaming, thread breakage, and the like frequently occur during spinning and drawing, resulting in adverse effects such as poor production operability.

[0003] Further, regarding the bristle material, in the case of a toothbrush in which a bristle made of nylon resin is implanted,
Large settling against repeated bending deformation during use,
There was a problem that durability was insufficient. On the other hand, in the case of a toothbrush in which a bristle made of polybutylene terephthalate resin is implanted, the set is small and the durability is improved.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies on the above-mentioned problems of the existing toothbrush bristle, and have completed the present invention. Another object of the present invention is to provide an antibacterial polyester resin composition for toothbrushes having excellent long-term durability, deodorization and antibacterial properties.

[0005]

An object of the present invention is to provide an antibacterial property for a toothbrush, characterized in that a copolymerized polyester resin comprising a dicarboxylic acid component and a diol component contains zeolite carrying an antibacterial metal. a polyester resin composition,

[0006] The copolymerized polyester resin is 90-9
9.7 mol% of terephthalic acid or an ester-forming derivative thereof and 0.3 to 10 mol% of a dimer acid having 36 carbon atoms or an ester-forming derivative thereof are used as a dicarboxylic acid component, and 1,4-butanediol or an ester-forming derivative thereof is used. This is achieved by an antibacterial polyester resin composition for toothbrushes, which is a copolymerized polyester resin containing a derivative as a diol component.

In the present invention, the resin applied to the bristle material is a copolymerized polyester resin, especially 90 to 99.% of a dicarboxylic acid component constituting the copolymerized polyester.
7 mol%, particularly preferably 93-99 mol%, is terephthalic acid or its ester-forming derivative, and 0.3
10 to 10 mol%, particularly preferably 1 to 7 mol% has 3 carbon atoms.
Preferred is a copolymerized polyester resin containing 6 as a dimer acid or an ester-forming derivative thereof as an acid component and 1,4-butanediol or an ester-forming derivative thereof as a diol component. Dimer acid is a dicarboxylic acid having 36 carbon atoms produced by heating and polymerizing an unsaturated fatty acid in the presence of a clay catalyst.

Embedded image The one containing 90% by weight or more of the bifunctional saturated fatty acid represented by the formula (1) is used. Specifically, for example, Prepol 1009 (a hydrogenated type containing 99% by weight of Chemical Formula 1) manufactured by Unichema Chemical Co., Ltd., Prepol 3008 (Prepol 1009
Dimethyl ester).

The polycondensation reaction may be carried out by a method usually used for producing a polybutylene terephthalate resin or a polyethylene terephthalate resin. For example, when performing the transesterification method, a predetermined amount of dimethyl terephthalate,
Dimethyl dimerate and 1,4-butanediol
After heating and melting at 0 ° C. under a stream of N ₂ gas, tetrabutoxytitanate is added as a catalyst. Then, until 210 ° C,
The transesterification reaction is performed while gradually raising the temperature. The transesterification reaction was confirmed to be complete based on the amount of methanol distilled off.
Preliminary depressurization is performed while gradually raising the temperature to ℃. 250 ° C
To carry out a polycondensation reaction under reduced pressure of 1 Torr or less to obtain a copolymerized polybutylene terephthalate resin as a bristle raw material according to the present invention.

In the present invention, a zeolite holding a metal ion having a bactericidal action is used as the metal zeolite (B). Zeolites are generally aluminosilicates having a three-dimensional framework structure, and aluminosilicates are usually represented by the following formula.

Embedded image [Wherein, M represents an ion-exchangeable metal ion and is a normal monovalent or divalent metal. n is the valence of the metal. x and y are coefficients of metal oxide and silica, respectively.
The ratio is based on 1 mol of aluminum oxide. Z is the number of waters of crystallization, and represents the ratio to 1 mol of aluminum oxide. ]

[0010] Many transformations of zeolite are known due to differences in the composition specific pore diameter, specific surface area, etc. of the monovalent or divalent metal substituted in the metal oxide and its oxide. The zeolite used in the present invention has a specific surface area of 15 based on the weight of the anhydrous zeolite excluding water of crystallization.
A zeolite having a molar ratio of silicon oxide to aluminum oxide of at least 0 m ² / g and an SiO ₂ / Al ₂ O ₃ of 14 or less is preferred.

In the present invention, a natural zeolite or a synthetic zeolite may be used as the zeolite.
For example, natural zeolites used in the present invention include:
Arsine, chabaside, clinobutyrolide, erionite, faujasite, mordenite, philipsite and the like.

Examples of the synthetic zeolite include A-type zeolite, X-type zeolite, Y-type zeolite, mordenite and the like. In the present invention, these may be used alone or in combination. Of these, particularly preferred are A-type zeolites, X-type zeolites, Y-type zeolites, and synthetic or natural mordenite among the synthetic zeolites.

The shape of the zeolite used in the present invention is preferably in the form of powder particles, and the particle size is preferably 50 μm or less, more preferably 0.5 μm or more and 20 μm or less. In the zeolite used in the present invention, one or more metal ions are retained in the above-mentioned natural or synthetic zeolite. Specifically, the metal ion of the metal oxide in the zeolite is replaced by the metal ion.

In the present invention, preferred examples of the metal ion include copper, silver, zinc, nickel and the like as the metal used. These may be used alone or in combination. The amount of metal ions contained in the zeolite is based on the total weight of the anhydrous zeolite excluding water of crystallization.
Preferably 30% by weight or less for silver ions, and preferably 35% by weight for copper or zinc ions, respectively.
It is as follows.

These metal ions may be used alone or in combination. When used in combination, the proportion of metal ions is preferably 35% by weight or less based on the total weight of the zeolite in terms of anhydrous zeolite excluding water of crystallization.
It does not matter if other metal ions are also included in the substituted metal ions.

The amount of the metal zeolite to be mixed with the above-mentioned copolymerized polyester resin is as follows.
Preferably, the metal zeolite is used in an amount of 0.1 part by weight.
05 parts by weight to 10.0 parts by weight, more preferably 0.15 parts by weight
Parts by weight to 5.0 parts by weight. The method for producing the bristle using such a material is not particularly limited, and may be performed by a commonly used melt spinning method. The diameter of the bristle is usually 0.1 to 0.4 mm.

[0017]

As described above, the metal ion in the zeolite holding the metal ion having the ion exchange function in the material diffuses and moves in the copolymerized polyester resin, and as a result, the metal ion is continuously produced. Are eluted, and the antibacterial property is maintained over a long period of time. Hereinafter, the present invention will be described specifically with reference to examples.

[0018]

EXAMPLES Unichema dimethyl terephthalate, which contains 99% by weight of dimethyl ester of dimer acid shown in Chemical formula 1
The prepolymer 3008 and 1,4-butanediol manufactured by Chemical Co., Ltd. are converted to poly (99% by mole) of dimethyl terephthalate, 1% by mole of dimethyl dimerate, and 100% by mole of 1,4-butanediol by a transesterification method commonly used. Polycondensation was performed according to the polymerization method of butylene terephthalate resin to obtain a copolymerized polyester resin. The above polyester resin and metal zeolite (Kanebo Co., Ltd., Bacte killer average particle size 2 μm) were mixed in predetermined amounts shown in Table 1, and mixed by stirring with a high speed mixer (manufactured by Ishikawa Seisakusho). A screw twin-screw extruder manufactured by Toshiba Machine Co., Ltd. (screw diameter 65 m / m, L / D
= 28) and kneaded by heating to obtain a strand having a diameter of 3 m / m. After cooling the strand, strand cut
The mixture was cut to about 4 to 5 m / m with a pelletizer to produce kneaded pellets. Using the kneaded pellets thus obtained, a single screw extruder (screw diameter 60 m / c) adjusted to a cylinder temperature of 270 ° C. and a die / nozzle temperature of 260 ° C.
m, L / D = 28), quenched to 40 ° C., and subsequently stretched 10-fold at a temperature of 100 ° C.
Winding was performed at 0 m / min to obtain a 0.2 mm bristle. The antibacterial property of the bristle manufactured under the above conditions was evaluated by a shake flask method. The results are shown in Table 1 together with the spinning operability.

[0019]

[Table 1] * 1. Zeolite solid particles in which metal ions of zeolite are replaced with copper ions in an amount of 5 parts by weight with respect to 100 parts by weight of A-type zeolite. The preparation method is described in JP-A-59-1332.
According to the method described in JP-A-35-35. * 2. Zeolite solid particles obtained by substituting silver ions in zeolite metal oxide in an amount of 5 parts by weight with respect to 100 parts by weight of A-type zeolite. The preparation method is described in JP-A-59-1332.
According to the method described in JP-A-35-35. * 3. The antibacterial property was evaluated by the shake flask method using Streptococcus mutans bacteria. * 4. The operability during the production of bristle was evaluated according to the following criteria. A: good B: good C: bad

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) A46D 1/00 C08K 3/34 C08L 67/02

Claims (1)

(57) [Claims] 1. A toothbrush for antibacterial polyester resin composition characterized in that the antibacterial metal to copolymer polyester resin comprising a dicarboxylic acid component and a diol component for the additional inclusion of supported zeolite, said co 90 to 99.7 mol% of terephthalic acid or its ester-forming derivative and 0.3 to 10 m
ol% of a dimer acid having 36 carbon atoms or an ester-forming derivative thereof as a dicarboxylic acid component and 1,4-butanediol or an ester-forming derivative thereof as a diol component, which is an antibacterial polyester for toothbrushes. Resin composition.