JP2002037643A - Antimicrobial glass and its resin components - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a consistent ZnO-B2O3-SiO2 base antimicrobial glass and a resin components containing the glass which can avoid such bad influences on the resin as losing brightness and getting cloudy and rough and changing color when mixed with the resin and whose antibacterial action is improved. SOLUTION: A characteristic of the glass is the content in % by weight of ZnO 40-70%, Ag2O 0.01-3.0%, B2O3+SiO2+P2O5 20-55%, R2O (R:Na, Li, K) 0-5%, R'O (R': Mg, Ca, Sr, Ba) 0-30%, Al2O3 0-20%. The other characteristic is the content in % by weight of the antimicrobial glass contained in the resin components which comprises ZnO 40-70%, Ag2O 0.01-3.0%, B2O3+SiO2+P2O5 20-55%, R2O (R: Na, Li, K) 0-5%, R'O(R': Mg, Ca, Sr, Ba) 0-30%, Al2O3 0-20%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antibacterial glass,
The present invention relates to a resin composition containing the same.

[0002]

2. Description of the Related Art Toothbrushes, soap containers, tubs, sinks,
Since resin products such as bathtubs are used under high-humidity conditions for a long time, bacteria and fungi tend to multiply. BACKGROUND ART In order to suppress the growth of bacteria and fungi, an antibacterial agent has been conventionally mixed with a resin. As antibacterial agents, those utilizing silver ions having strong antibacterial properties are often used. For example, zeolite powders carrying silver ions and water-soluble glass powders containing Ag ₂ O as a glass composition are known. I have. However, Ag
₂ O-based material is high in price, also, Ag ₂ O-containing glass powder tends to discolor by the action of long Using ultraviolet light or heat or the like is not preferable. This tendency tends to be noticeable especially when the resin product is white.

[0003] Therefore, glass containing ZnO as a main component has been proposed as an antibacterial agent. This type of glass is inexpensive and does not discolor due to the action of ultraviolet rays or heat. For example, _{JP-A-7-257938, ZnO-B 2 O 3} -Na
Antimicrobial glass powder having a composition of ₂ O system is disclosed.

However, when the above-mentioned known ZnO-containing glass powder is mixed with a resin and used, the gloss of the resin is lost with the lapse of time and the resin becomes cloudy or a rough feeling is generated. Appearance problems occur.

In order to solve the above problem, the present invention
The authors reported that ZnO-B_TwoO_Three-SiO _TwoSystem smell
And Na_TwoAntibacterial with O content limited to 6% by weight or less
Glass powder is proposed in JP-A-11-60268.
You.

[0006]

By the way, the above-mentioned ZnO
Although the system glass is at a level that can be sufficiently used in the market as an antibacterial agent, expectations for the antibacterial agent in the market are greedy, and further improvement in antibacterial performance is required. However, in order to improve the antibacterial performance of the above glass, Zn
It is conceivable that a large amount of the O component is contained.
If a large amount of components is contained, the glass becomes unstable and causes problems such as devitrification during glass forming.

[0007] An object of the present invention is to prevent the resin from losing its luster and becoming cloudy even when used in combination with the resin, to give a rough feeling, to have no adverse effect such as discoloration, etc. An object of the present invention is to provide a ZnO-based stable antibacterial glass having improved performance and a resin composition containing the same.

[0008]

As a result of various experiments, the present inventors have found that a glass composition obtained by coexisting a small amount of Ag ₂ O with a ZnO-based glass is proposed as the present invention. is there.

That is, the antimicrobial glass of the present invention has a ZnO content of 40 to 70% and an Ag ₂ O content of 0.01 to 3.
_{0%, B 2 O 3 +} SiO 2 + P 2 O 5 20~55%, R 2 O
(R: Na, Li, K) 0 to 5%, R'O (R ': M
g, Ca, Sr, Ba) 0~30%, Al 2 O 3 0~2
0%.

The resin composition of the present invention is a resin composition containing an antibacterial glass, wherein the composition of the antibacterial glass is 40 to 70% by weight of ZnO, Ag _{2
O0.01~3.0%, B 2 O 3 +} SiO 2 + P 2 O 5 2
_{0~55%, R 2 O (R} : Na, Li, K) 0~5%,
R'O (R ': Mg, Ca, Sr, Ba) 0 to 30%,
Al ₂ O ₃ is characterized by being comprised of 0 to 20%.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial glass of the present invention is ZnO
The antibacterial property is further improved by adding a small amount of Ag ₂ O to a ZnO-based glass having a large content. Conventional A
The g ₂ O antibacterial glass, it is necessary to increase the addition amount of Ag ₂ O to Motas sufficient antibacterial performance. For this reason, problems such as an increase in raw material cost and discoloration due to heating or irradiation with ultraviolet light were liable to occur. However, such a problem does not occur when a small amount of Ag ₂ O is added.

Next, the reason why the composition range is limited to the above range will be described below.

[0013] ZnO is a major factor conferring antibacterial properties,
Provides antibacterial properties as Zn ²⁺ ions. The content of ZnO is 40 to 70% by weight, preferably 41 to 67% by weight. ZnO is less than 40 wt%, the reduced glass of the antimicrobial performance, it is difficult to improve the antimicrobial activity unless large amounts put Ag ₂ O. On the other hand, if it exceeds 70% by weight, vitrification becomes difficult.

Ag ₂ O is used for the purpose of improving the antibacterial performance of glass. The content of Ag ₂ O is 0.01 to 3.0.
% By weight, preferably 0.05 to 3.0% by weight. A
When the content of g ₂ O is less than 0.01% by weight, the effect of improving the antibacterial activity of the glass is insufficient. On the other hand, Ag ₂ O is 3.
If the content exceeds 0% by weight, discoloration of the resin is likely to occur, and the raw material cost increases.

B ₂ O ₃ + SiO ₂ + P ₂ O ₅ is a glass forming component, and the content of B ₂ O ₃ + SiO ₂ + P ₂ O ₅ is 20 to
It is 55% by weight, preferably 20 to 50% by weight. B ₂ O
_{When 3} + SiO ₂ + P ₂ O ₅ is less than 20% by weight, vitrification becomes difficult. On the other hand, if the content of B ₂ O ₃ + SiO ₂ + P ₂ O ₅ exceeds 55% by weight, the water resistance of the glass becomes too large, and Zn ²⁺ and Ag ⁺ ions are hardly eluted, leading to a decrease in antibacterial performance.

R ₂ O (R: Na, Li, K) may be added up to 5% by weight for the purpose of improving the melting property of the glass.
However, as described above, the appearance of the resin such as discoloration is affected, so that the content is preferably 2% by weight or less if possible.

R'O (R ': Mg, Ca, Sr, Ba)
Has the effect of lowering the viscosity of the glass and acts like a flux that helps the glass melt. Up to 30% by weight, preferably up to 20% by weight, can be added.

Al ₂ O ₃ also promotes vitrification and can be added up to 20% by weight, preferably up to 15% by weight.

By the way, ZnO-based glass, specifically, can be roughly divided ZnO-B ₂ O ₃ based glass, ZnO-SiO ₂ based glass, into three ZnO-P ₂ O ₅ based glass.

ZnO-B_TwoO_ThreeSystem glass is indicated as weight%
With ZnO 40-70%, Ag_TwoO0.01-3.0
%, B_TwoO_Three+ SiO_Two+ P_TwoO_Five 20-55%,
B_TwoO _Three 1-40%, SiO_Two 0-35%, P_TwoO_Five 
0-40%, R_TwoO (R: Na, Li, K) 0
5%, R'O (R ': Mg, Ca, Sr, Ba) 0 to 3
0%, Al_TwoO_Three Consists of 0-20%.

ZnO—SiO ₂ -based glass is, when expressed in terms of weight%, 40 to 70% ZnO and 0.01 to 3.0 Ag ₂ O.
_{%, B 2 O 3 + SiO} 2 + P 2 O 5 20~55%, noted,
_{SiO 2 1~35%, B 2 O} 3 0~40%, P 2 O 5
0 to 40%, and R ₂ O (R: Na, Li, K) 0
5%, R'O (R ': Mg, Ca, Sr, Ba) 0 to 3
0% composed of Al ₂ O ₃ 0~20%.

ZnO-P_TwoO_FiveSystem glass is indicated by weight%
With ZnO 40-70%, Ag_TwoO0.01-3.0
%, B_TwoO_Three+ SiO_Two+ P_TwoO_Five 20-55%,
P_TwoO _Five 1 to 40%, B_TwoO_Three 0-40%, SiO_Two 
0-35%, R_TwoO (R: Na, Li, K) 0
5%, R'O (R ': Mg, Ca, Sr, Ba) 0 to 3
0%, Al_TwoO_Three Consists of 0-20%.

The antibacterial glass of the present invention may be, for example, a powder,
It can be provided in various forms such as fibrous form and flake form. Above all, when provided in the form of glass powder, the specific surface area is increased, so that high antibacterial performance is obtained. In the case of glass powder, the average particle size is 0.5 to 20 μm, preferably 1.0 to 20 μm.
〜１０10 μm. That is, the average particle size of the glass powder is 0.1.
If it is smaller than 5 μm, it becomes difficult to knead it with a resin or the like due to the aggregation effect, and if it is larger than 20 μm, Zn per unit weight is
^{The amount of 2+} ions and Ag ⁺ ions eluted is undesirably small.

The antibacterial glass of the present invention can be used as an antibacterial agent for filling a thermoplastic resin or a thermosetting resin. For example, polyolefin resin, polycarbonate resin,
ABS resin, AS resin, polyamide resin, polyurethane resin, polyvinyl alcohol resin, polyester resin, polyethylene terephthalate resin, polyethylene oxide resin, polyphenylsulfide resin, acrylic resin, melamine resin, phenol resin, epoxy resin, Urea resin, polyimide resin, aliphatic nylon resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl acetate resin, fluorine resin or silicone resin, major engineering plastics, and composites thereof, and Glass fibers, boron fibers, and carbon fiber reinforced materials can also be used.

The antibacterial glass of the present invention is not limited to resin filling, but can be used for various antibacterial applications such as antibacterial glaze of glass and ceramic, antibacterial paint of metal and the like.

The resin composition of the present invention contains the above-mentioned antibacterial glass, and its content is 0.01 to 7
It is desirably 0% by weight, particularly 0.05 to 30% by weight. The reason for limiting the content in this way is that if the content is less than 0.01% by weight, it becomes difficult to impart sufficient antibacterial properties to the resin. On the other hand, if the glass content exceeds 70% by weight, dispersion in the resin becomes difficult, which is the limit of masterbatch molding. In addition, the effect of the antibacterial performance hardly changes, so that the cost is not very effective.

In the resin composition of the present invention, various additives usually contained in a resin can be contained in addition to the antibacterial glass.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

[0029]

[Table 1]

Table 1 shows examples of the present invention (samples No. 1 to No. 1).
9) and Comparative Examples (Sample Nos. 10 and 11) are shown.

Each sample was prepared as follows.

First, the above-mentioned raw materials were sufficiently mixed so as to have a predetermined mixing amount, then put into a platinum-rhodium alloy crucible and melted at 1200 to 1550 ° C. for 4 hours. After melting,
It was formed into a film-like cullet having a thickness of about 1 mm. This was pulverized by a ball mill, passed through a sieve having an opening of 50 microns, and adjusted so that the average particle size of the glass powder was about 5 μm using an air-permeable specific surface area measuring device <manufactured by Shimadzu Corporation>. Obtained.

The antibacterial property is determined according to the test method defined by the Antibacterial Technology Products Association, "Testing method for evaluating antibacterial activity of antibacterial agents, minimum growth inhibitory concentration measurement method I (revised 1998), MIC measurement method by liquid medium dilution method". The antimicrobial properties were evaluated as MIC values. (Test bacteria: Escherichia coli) As is clear from Table 1,
In all the examples, the MIC value was 400 (μg / ml) or less. Since the standard value of 800 (μg / ml) or less as an antibacterial agent shown by the Antibacterial Technology Products Association has been sufficiently cleared, it can be seen that good antibacterial properties are exhibited. No. ₂ containing no Ag ₂ O of the comparative example. 10 samples were 500 (μg
/ Ml), the Zn. 11 is 800
(Μg / ml), each of which satisfies the reference value as an antibacterial agent, but the antibacterial performance was inferior to each of the examples.

[0034]

[Table 2]

Next, in order to further show the effect of the addition of Ag ₂ O, No. 2 was used. 1 and No. 1 10 antibacterial glass and polypropylene resin, antibacterial glass content is 0.1 ~
It mixed so that it might become 0.5%, shape | molded into about 50 * 50 * 2mm plate shape, and evaluated the antibacterial property and the external appearance of resin. Table 2 shows the results.

The antibacterial test method was measured using "Test Method for Antibacterial Activity of Antibacterial Products I (1998 Edition) Film Adhesion Method" of the Antibacterial Technology Products Council. (Test bacterium: Escherichia coli) In this test method, an antibacterial property is evaluated if the difference between increase and decrease values is 2.0 or more. For the appearance of the resin,
After boiling for 00 hours, compare the surface of the resin with that before the test,
Those that maintained the initial gloss were rated good, and those that were white and cloudy and lost the gloss were rated poor.

As shown in Table 2, the comparative example (No. 10) using the glass powder containing no Ag ₂ O shows sufficiently excellent antibacterial properties when the content of the antibacterial glass is 0.5% or more.
On the other hand, an example using a glass containing Ag ₂ O (No.
In 1), the amount of antibacterial glass to be filled in the resin is 0.1%
However, it exhibits sufficient antibacterial properties and can improve cost performance. In addition, neither the example nor the comparative example affected the appearance of the resin product. Therefore, it is preferable as an antibacterial glass for resin filling.

[0038]

As described above, the antibacterial glass of the present invention is stable as glass, and can impart sufficient antibacterial properties even when filled in a resin. Moreover, since it does not affect the appearance of the resin product, it is preferable as an antibacterial agent for filling the resin.

Therefore, a toothbrush requiring cleanliness,
It is suitably used for resin products such as soap containers, basins, wash basins, bathtubs and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 3/093 C03C 3/093 3/17 3/17 C08K 3/40 C08K 3/40 C08L 101/00 C08L 101/00 F term (reference) 4G062 AA10 BB01 BB07 BB09 DA01 DA02 DA03 DA04 DA05 DA06 DB01 DB02 DB03 DB04 DC01 DC02 DC03 DC04 DC05 DC06 DD01 DD02 DD03 DD04 DD05 DD06 DE05 DE06 DF01 EA01 EA02 EA03 EA10 EB01 EC03 EB01 EC03 ED03 ED04 EE01 EE02 EE03 EE04 EF01 EF02 EF03 EF04 EG01 EG02 EG03 EG04 FA01 FA10 FB01 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HHH HHH HHH HHH HHH HHH KK05 KK07 KK10 MM15 NN40 4H011 AA02 BA01 BB18 BC18 DA02 DD07 4J002 AA001 BB001 BC061 BD041 BD101 BD121 BE021 BF021 BG001 BN151 CC031 CC1 81 CC211 CD001 CF001 CF061 CG001 CH021 CK021 CL001 CM041 CN011 CP031 DL006 FA086 FD186 GC00 GG01

Claims (8)

[Claims] 1. ZnO 40-70% by weight%, A
g ₂ O 0.01 to 3.0%, B ₂ O ₃ + SiO ₂ + P ₂ O _{5
20~55%, R 2 O (R} : Na, Li, K) 0~5
%, R'O (R ': Mg, Ca, Sr, Ba) 0 to 30
%, Al ₂ O ₃ 0-20%. 2. Antimicrobial glass according to claim 1, provided in the form of glass powder. 3. The antibacterial glass according to claim 2, wherein the average particle size is 0.5 to 20 μm. 4. The antibacterial glass according to claim 1, which is used for filling a resin. 5. A resin composition containing an antibacterial glass, wherein the composition of the antibacterial glass is Zn by weight%.
O 40-70%, Ag ₂ O 0.01-3.0%, B ₂
O ₃ + SiO ₂ + P ₂ O ₅ 20 to 55%, R ₂ O (R: N
a, Li, K) 0 to 5%, R'O (R ': Mg, Ca,
Sr, Ba) 0~30%, the resin composition characterized in that it consists of Al ₂ O ₃ 0~20%. 6. The resin composition according to claim 5, wherein the antibacterial glass is contained in the form of a powder. 7. The antibacterial glass powder has an average particle size of from 0.5 to 0.5.
7. The resin composition according to claim 6, wherein the thickness is 20 μm. 8. The antibacterial glass content is 0.01 to 70.
6. The resin composition according to claim 5, wherein the content is% by weight.