JP3440606B2 - Antibacterial ABS resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific resin having antibacterial properties.
Phosphate compound, metal oxide, surfactant, lubricant and A
The present invention relates to a resin composition comprising a BS resin. Composition of the present invention
The product may deteriorate or change over time during processing, storage and use.
Antibacterial A with very little color and excellent antibacterial effect
A BS resin molded product can be easily obtained, and the molded product
Is a variety of fields that require antifungal, antialgal and antibacterial properties, such as
Electric appliances such as electric refrigerators, televisions, washing machines, etc.
It is useful for household items such as bowls, dishes, tables and the like. [0002] Conventionally, silver and copper have been used as inorganic antibacterial agents.
Activated carbon, apatite, zeolite, etc.
And those supported on a device such as These are organic
It is safer than antibacterial agents, and is volatile and decomposed.
Long lasting antibacterial effect and heat resistance
It has the characteristic that it is. Therefore, these antibacterial agents and each
Antibacterial resin composition by mixing with seed polymer compound
And use it as a fiber, film or pellet
It is processed into various shapes and used for various purposes. However, antibacterial agents using activated carbon as a carrier are
Since the fungicide itself is black, it can be obtained by mixing with various polymers.
Antibacterial resin composition is colored
Problematic and antimicrobial components are easy to contact when in contact with liquids
Will elute into the skin and maintain its antibacterial effect for a long time
There is a problem that can not be. Also, apatite and zeo
The antibacterial agent using light as a carrier is an antibacterial agent using activated carbon as a carrier.
Antimicrobial when contacted with neutral liquids
Elution of soluble components is relatively low, and antibacterial effect lasts for a long time
These antibacterial agents are
The shift is also low in acid resistance, in a dilute acidic aqueous solution of about PH4
The skeletal structure is easily destroyed and elutes antibacterial metals.
It is difficult to maintain the antibacterial effect for a long time
There are also safety issues, and mixing with various polymers
Discoloration during storage or use,
There is a problem that causes. In an antibacterial agent using zeolite as a carrier,
Is silver and the antibacterial component to prevent discoloration.
Ammonia or amine as an inhibitory component is ion-exchanged.
An antibacterial agent supported on the substrate has been developed (Japanese Patent Laid-Open No. 64-64).
24860), discoloration is not completely prevented, and
Let's heat-process the resin composition consisting of this antibacterial agent and resin
Then, the resin foams because ammonia is released
However, there is a problem that the processability of the resin composition is reduced,
The fundamental problem has not been solved. [0005] To solve these problems, specific phosphorus is used.
An acid salt compound has been proposed (JP-A-3-8390).
5), the specific phosphate system described in the above-mentioned patent publication
Obtained by mixing antimicrobial agents consisting of compounds with various polymers
Molding resin composition has antibacterial effect for a long time
Resin moldings that can be continued and have excellent gloss
Can be easily obtained. Moreover, this resin composition is
Discoloration and deterioration may occur during processing, storage and use.
Not. However, in the case of ABS resin, the above public
Specific phosphate compounds described in the patent publication
By simply mixing and molding antibacterial agents
Can exhibit sufficient antibacterial properties inherently possessed by
There are no problems, and improvement is desired. Fear
The cause of insufficient antibacterial properties of ABS resin moldings
When molding the resin, the antibacterial agent
Because it is easy to have, the antibacterial agent does not cue on the surface of the molded body
This phenomenon is due to the unique properties of ABS resin.
The inventors believe that it depends. On the other hand, the antibacterial properties of polyolefin resin moldings
Antimicrobial agent to polyolefin resin as a way to improve
In addition to compounding, contains antistatic agent and surface modifier
To give the polyolefin resin molded article anti-scale adhesion properties
Is known (Japanese Patent Application Laid-Open No. H5-25547).
Information). [0007] The present invention relates to an antibacterial agent.
Demonstrate the original excellent antibacterial properties and excellent weather resistance
ABS resin moldings that can be easily obtained
The object of the present invention is to provide an antibacterial ABS resin composition
Is what you do. Means for Solving the Problems The present inventors have made the above-mentioned section.
As a result of intensive studies to solve the problem,
From the specific phosphate compounds described in JP-A-905
In addition to the antimicrobial agent, a specific metal oxide is blended,
Mix surfactant and lubricant in ABS resin and mold
By doing so, obtain a resin molded product with extremely excellent antibacterial properties
And found that the present invention was completed.
Was. That is, the present invention provides an ABS resin represented by the following formula [1]:
Phosphate antibacterial agents, zinc oxide and titanium dioxide
At least one metal oxide selected, a surfactant, and
Antimicrobial ABS resin group characterized by containing lubricant
It is an adult. Ag _a A _b M _Two (PO _Four ) _Three ・ NH _Two O [1] (A is an alkali metal ion, an alkaline earth metal ion,
Small amount selected from ammonium ion or hydrogen ion
At least one type of ion, M is a tetravalent metal, and n is
It is a number satisfying 0 ≦ n ≦ 6, and both a and b are a +
It is a positive number satisfying mb = 1. Where m is the valence of A
You. Hereinafter, the present invention will be described in detail. ○ ABS resin The ABS resin in the present invention is made of rubber as a continuous phase of the resin.
Is a thermoplastic resin having a dispersed structure. ABS
The abbreviation is acrylonitrile (Acryl) which is a raw material component.
onitile), butadiene (Butadien)
e) and Styrene
These three components are the constituent components of the ABS resin.
The ABS system of the present invention
Resins are not necessarily limited to these three components.
Not. Preferred specific examples include diene rubbers.
Styrene and styrene in the presence of
Vinyl monomer containing acrylonitrile as the main component.
Graft polymers obtained by dical graft polymerization include
Can be Elastomer composition as a component of ABS resin
In terms of components, polybutadiene and styrene-butadiene
Polymer, acrylonitrile-butadiene copolymer, poly
In addition to diene rubbers such as isoprene and polychloroprene,
Ethylene-polypropylene copolymer, ethylene-polypropylene
Copolymer, ethylene-propylene-diene monomer-ternary
Copolymer, chlorinated polyethylene, polyisobutylene, etc.
Mainly composed of olefin rubber and alkyl (meth) acrylate
Acrylic rubber and the like, and diene rubber
More preferred. Using the above various elastomer components
The graft copolymer produced depends on the type of elastomer.
ABS resin, AES [acrylonitrile- (ethlene-pro
pylene-dien rubber) -styrene] resin, ACS [acrylonit
rile-chlorinated polyethylene-styrene] resin, AAS
Abbreviated as [acrylate-acrylonitrile-styrene] resin, etc.
However, in the present invention, these are collectively referred to as ABS trees.
It is called fat. [0010] The graft graft polymerized on the elastomer
Nyl monomer is mainly composed of styrene and acrylonitrile.
Minutes, but if necessary, a vinyl monomer such as α-
Methyl styrene, aromatic substituted styrenes, (meth)
Lylic acid ester, (meth) acrylonitrile, (meth)
Replaces acrylic acid, maleic anhydride, and phenylmaleimide
The N-substituted maleimides represented may be used in combination. All vinyl
The preferred ratio of styrene in the monomer is 50 to 90 weight
%, More preferably 60 to 85% by weight. Acri
The preferred proportion of lonitrile is 40 to 10% by weight,
35 to 15% by weight is more preferred. As a method of polymerization
Are emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization
Etc., and a polymerization method combining these can also be adopted.
You. Preferred Polymerization of Elastomer Component in ABS Resin
The proportion is 5 to 40% by weight, more preferably 10 to 40% by weight.
30% by weight. ABS resin is compatible with other resins.
Heat resistance and impact resistance of ABS resin
As long as the inherent properties of the resin are not impaired, various resins or
It can also be blended with rubber, for example vinyl chloride,
Polycarbonate, polyurethane, nylon, etc. and brane
You can also do it. Preferred of these resins or rubber
A good mix ratio is usually per 100 parts by weight of ABS resin
Up to 100 parts by weight. Further, the ABS resin composition
Various other additives as needed to improve physical properties
Can also be blended. Specific examples include pigments, dyes,
Antioxidants, light stabilizers, flame retardants, antistatic agents, foaming
Agents, impact modifiers, glass fibers, moisture barriers and extenders
is there. In addition to inorganic antibacterial agents, organic antibacterial agents and fungicides
Add immediate effect to increase the immediate effect and increase the efficacy
You can also do it. Preferred blending ratio of these additives
Is 100 parts by weight of ABS resin (hereinafter simply referred to as "part").
You. ) Up to 10 parts. ABS resin is powdered
May be difficult to mold and may not have sufficient antibacterial effect
Use pellet-shaped compacts during molding
Is preferred. There is no particular limitation on the shape of the pellet,
For example, there are a spherical shape, a prismatic shape, a cylindrical shape, and a disk shape. Inorganic antibacterial agent The phosphate antibacterial agent in the present invention is represented by the following formula [1].
(Hereinafter abbreviated as antibacterial agent [1]). Ag _a A _b M _Two (PO _Four ) _Three ・ NH _Two O [1] (A is an alkali metal ion, an alkaline earth metal ion,
Small amount selected from ammonium ion or hydrogen ion
At least one kind of ion, M is a tetravalent metal ion
N is a number satisfying 0 ≦ n ≦ 6, and a and b are not
These are also positive numbers satisfying a + mb = 1. Where m is A
Valence. The antibacterial agent [1] belongs to the space group R3c.
It is a crystalline compound and each constituent ion has a three-dimensional network structure
Is formed. In the above formula [1], A is an alkali metal
On, alkaline earth metal ions, ammonium ions
Or at least one ion selected from hydrogen ions
Yes, preferred embodiments include lithium, sodium and
Alkali metal ions such as potassium, magnesium or potassium
Alkaline earth metal ions such as Lucium or hydrogen ions
Among these, the stability of the compound and the low cost
Lithium, sodium, ammonium
Ions and hydrogen ions are the preferred ions. M in the above formula [1] is a tetravalent metal ion
Preferred examples include zirconium ions and titanium.
There are tan ion or tin ion, considering the safety of the compound
Then, zirconium ions and titanium ions are more favorable.
More preferably, a particularly preferred tetravalent metal ion is zirconium ion.
Is on. Preferred specific examples of the antibacterial agent [1] are as follows:
There are things below. Ag _0.005 Li _0.995 Zr _Two (PO _Four ) _Three Ag _0.01 (NH _Four ) _0.99 Zr _Two (PO _Four ) _Three Ag _0.05 Na _0.95 Zr _Two (PO _Four ) _Three Ag _0.2 K _0.8 Ti _Two (PO _Four ) _Three Ag _0.1 H _0.9 Zr _Two (PO _Four ) _Three Ag _0.5 Na _0.25 H _0.25 Zr _Two (PO _Four ) _Three Ag _0.9 Na _0.1 Zr _Two (PO _Four ) _Three Ag _0.7 Na _0.3 Sn _Two (PO _Four ) _Three A method for synthesizing the antibacterial agent [1] used in the present invention
Examples of the method include a firing method, a wet method, and a hydrothermal method.
It can be easily obtained as below. By firing method
When synthesizing, lithium carbonate (Li _Two CO _Three ) Or sodium carbonate
Um (Na _Two CO _Three ) And other compounds containing alkali metals, acids
Zirconium (ZrO) _Two ), Etc. containing zirconium
Compound and ammonium dihydrogen phosphate (NH _Four H _Two PO _Four )
The compound containing an acid group is added in a molar ratio of about 1: 4: 6.
And bake it at 1100-1400 ° C
Thus, a compound represented by the following formula [2] is obtained. A ' _x Zr _Two (PO _Four ) _Three [2] (A ′ is an alkali metal ion, an alkaline earth metal ion
Or at least one of ammonium ions
X is 1 when A ′ is monovalent
And when A is divalent, it is ２) at room temperature to 100 ° C. at an appropriate concentration.
By immersing in an aqueous solution containing
[1] is obtained. Note that the A ion in the above formula [1] is water
The compound which is an element ion is a compound represented by the above formula [2]
At room temperature to 100 ° C, such as nitric acid, sulfuric acid and hydrochloric acid.
By immersing in an aqueous acid solution, the general formula H _(1-z) A '
_z M _Two (PO _Four ) _Three (Z is 0 or a number less than 1)
To obtain a compound [3],
By immersing in an aqueous solution containing
[1] is obtained. When synthesizing by the wet method,
Stir aqueous solution of zirconium nitrate and sodium nitrate
While adding oxalic acid and further adding phosphoric acid.
I can. Adjust the pH of the reaction solution to 3.5 with aqueous sodium hydroxide solution.
After heating and refluxing for 78 hours, the precipitate was filtered, washed with water, and dried.
Dry, pulverized, and mesh zirconium phosphate [NaZr
_Two (PO _Four ) _Three ] Is obtained. Antibacterial gold at appropriate concentration
Immersed in an aqueous solution containing a genus
[1] is obtained. The value of a in the above equation [1] is
In an aqueous solution in which the compound represented by [2] or [3] is immersed
Concentration of antibacterial metal ions in aqueous solution
Time or temperature at which the compound represented by [2] or [3] is immersed
By adjusting the degree, etc., the required characteristics and usage conditions
It can be adjusted as appropriate according to the situation. The composition of the present invention and the composition obtained by molding the composition
Mold, antibacterial and anti-algal
In order to exhibit the property, the value of a in the above equation [1] is large.
It is better if the value of a is 0.001 or more.
Can exhibit antifungal, antibacterial and antialgal properties
You. However, if the value of a is less than 0.01, it will prevent mold,
It is difficult to demonstrate antibacterial and antialgal properties for a long time
There is a possibility that the value of a should be 0.01 or more
Is preferred. Also, in consideration of economy, the value of a is 0.7.
The following are appropriate: The chemical and antibacterial agents [1] used in the present invention
Improves physical stability and increases discoloration after exposure to heat and light
In order to obtain an antibacterial agent that has been frequently prevented, phosphate compounds
After carrying silver ions on
preferable. By passing through this baking step, an antibacterial agent
The chemical and physical stability of [1] is significantly improved,
It is possible to obtain an antibacterial agent that is colorless and has excellent weather resistance.
Wear. Also, almost no moisture attached before firing was present.
Processability of resin containing antibacterial agent [1]
Up. In this step, phosphorus ions carrying silver ions
Baking the acid salt compound at 500 to 1300 ° C.
Is more preferable, more preferably 600 to 1000C, particularly
Preferably, firing is performed at 700 to 900 ° C.
When calcined at a temperature below 500 ° C, the antibacterial agent [1]
Effect to improve mechanical and physical stability is not sufficient
Bake at temperatures higher than 1300 ° C
And the antibacterial activity is reduced, or fine particles of phosphate
Since the compounds are fused together, an antibacterial agent in the form of fine particles is obtained.
May be difficult to perform. There are no particular restrictions on the firing time
Adjustment without considering the firing furnace capacity, productivity, etc.
be able to. Regarding the heating rate and the cooling rate,
There is no limitation, and convenience is adjusted in consideration of firing furnace capacity, productivity, etc.
Can be adjusted. The antimicrobial and weather resistance are extremely excellent.
In order to obtain the fungicide [1], the phosphate antibacterial according to the present invention is used.
Preferably, the agent carries hydrogen ions. Re
If the phosphate antimicrobial agent has an ammonium ion,
By performing the calcination process described above, ammonium ion
Thermal decomposition of phosphates and hydrogen ions remain, resulting in phosphate-based antibacterial
If the baking process is applied to the agent, hydrogen ions can be supported
it can. Preferred firing conditions at this time are as follows:
C. to 1100 C. for a time of about 0.5 to 2 hours.
You. On the other hand, the antibacterial agent [1] has ammonium
If there is no or very small amount, use as antibacterial agent [1]
It is preferable to add a step for supporting hydrogen ions.
As a typical method, phosphate compounds are acidified.
There is a method of immersion in a solution, etc.
The above-mentioned method of calcining a phosphate compound having
It is a highly productive method compared to the method. In addition, acidic
Phosphate compounds immersed in solution carry silver ions
Whatever was done or not
No. For supporting hydrogen ions on phosphate compounds
Preferred specific examples of the acidic solution to be immersed are hydrochloric acid, sulfuric acid
And an aqueous solution such as nitric acid. Acid concentration of acid solution, temperature,
The immersion time is not particularly limited, but generally, the higher the acid concentration, the higher the immersion time.
The higher the temperature and the higher the temperature, the more
Therefore, a preferable acid concentration is 0.1 N or more.
The preferred processing temperature is 40 ° C. or higher, more preferably 6 ° C.
0 ° C or more and 100 ° C or less, preferred immersion
The time is at least 10 minutes, more preferably at least 60 minutes. The antibacterial agent [1] used in the present invention is a hot or light
Stable to exposure, 500 ° C, in some cases
Structure and set even after heating at 800 ° C to 1100 ° C
The composition does not change at all, and does not change color even when irradiated with ultraviolet light
Not shown. The antibacterial agent [1] used in the present invention is a liquid
In contact with water in a state,
No change is seen. Therefore, the processing required to obtain various molding processes
Processing and storage, and even when used like traditional antibacterial agents
Be limited by the heating temperature or shading conditions.
And not. In the present invention, an antibacterial agent is used as the antibacterial agent.
An antimicrobial composition comprising [1] in combination with a specific metal oxide
Used. ○ Metal oxide The metal oxide used in the present invention is zinc oxide and diacid.
At least one compound selected from titanium oxide
You. Zinc oxide is represented by the chemical formula of ZnO,
It is called a natural product or a synthetic product. Diacid
Titanium chloride may be either natural or synthetic, amorphous
It may be either crystalline or crystalline. Titanium dioxide is
Depending on crystal system, anatase, rutile and brookite
Although classified, in the present invention, any crystal type
Since it may be used and can be easily obtained industrially,
Anatase and rutile are preferred. Metal oxidation
Although there is no particular limitation on the particle size and shape of the product,
Considering the dispersibility in fat, the average particle size is 10 μm or less
Are preferable, and the shape of the particles is preferably spherical rather than acicular.
No. Generally used as white pigment can be used
Noh. Preferred composition ratio of metal oxide in the present invention
If the antibacterial agent [1] and the above-mentioned metal oxides are 100
Parts to 5 to 90 parts of metal oxide based on parts. metal
When the compounding ratio of the oxide is less than 5 parts, the metal oxide and the
Improvement of antibacterial activity and discoloration of resin due to coexistence of fungicide [1],
It may be difficult to achieve the effect of preventing deterioration.
If the metal oxide content exceeds 90 parts, the antibacterial agent [1]
It may be difficult to exert an antibacterial effect.
In order to exhibit sufficient antibacterial effect, antibacterial agent
The silver ion concentration in the product should be 0.5% by weight or more.
And more preferably 2% by weight or more.
No. The preferred compounding ratio of the antibacterial agent composition is AB
It is 0.01 to 10 parts based on 100 parts of the S-based resin.
If the amount is less than 0.01 part, the antibacterial property of the ABS resin composition may be reduced.
May not be able to get enough, while more than 10 parts
Even if it is mixed well, there is almost no improvement in antibacterial activity, but rather ABS
There is a risk of deteriorating physical properties. Surfactants Surfactants include nonionic, anionic and cationic surfactants.
And amphoteric ones. Preferred non-ionic specific examples
As fatty acid glycerin esters, polyoxyethylene
Glycol fatty acid esters, sorbitan fatty acid esthetics
And polyoxysorbitan fatty acid monostearate, etc.
Polyoxysorbitan fatty acid esters and other polyvalent alcohols
Fatty acid ester; fatty acid alkylolamide, g
(2-Hydroxyethyl) alkylamine, polyoxye
Tylenealkylamine, polyoxyethylenealkylamine
Mid; polyoxyethylene alkyl phenyl ether,
And polyoxyethylene alkyl ether. Anio
Preferred specific examples of the sulfonate include alkyl sulfonates,
Alkyl benzene sulfonate, alkyl sulfate
Acid, alkyl ethoxy sulfate, alkyl phosphoric acid
Ester acids and the like. Further, preferred specific examples of the cationic type
For example, alkyl trimethyl ammonium salt (trim
Tyl type), acyloylamidopropyltrimethylammonium
Ium methosulfate, alkylbenzyldimethyla
Ammonium salts, acyl choline chloride and the like. Bisexual good
A better example is betaine. Among these
Has a large effect of enhancing antibacterial properties and the resin of the present invention
Coloring the composition or the resin molding obtained therefrom
Is a kind of nonionic surfactant
Polyhydric alcohol fatty acid ester surfactants are preferred
No. The surfactant may be used alone or in combination.
it can. O Lubricants Lubricants can be classified by chemical structure into hydrocarbons, metal soaps, and fats.
Fatty acids and fatty acid amides, fatty acid esters
You. Preferred examples of hydrocarbons include liquid paraffin.
, Polyethylene waxes, chlorinated hydrocarbons, etc.
You. As a preferred specific example of the metal soap, stearic acid
Lead, cadmium stearate, barium stearate,
Examples include calcium stearate and zinc stearate.
As preferred specific examples of fatty acids and fatty acid amides,
Stearic acid, stearic acid amide, balmitic acid ami
, Methylene bis stearoamide, ethylene bis
There are aromaides and the like. Among these, it enhances antibacterial properties
The resin composition or the resin molding
Metal soaps are preferred because of less coloration. What
The lubricant can be used alone or in combination. As will be described later, the composition of the present invention is
Contains antibacterial agent composition, surfactant and lubricant in high concentration in advance
And a molded body using this and an ABS resin
Can be prepared, and a polyhydric alcohol
Fatty acid ester surfactants, metal soaps as lubricants
When used, even if they are contained at a high concentration
There is no coloring. The surfactant of the resin composition of the present invention
The preferred compounding ratio is 0.2 parts per 100 parts of the ABS resin.
01 to 10 parts, more preferably 0.1 to 5 parts.
If the amount is less than 0.01 part, the antibacterial property of the ABS resin composition is reduced.
It may not be possible to obtain enough, while more than 10 parts
Even if blended, there is almost no improvement in the antibacterial effect, but rather ABS
There is a possibility that the physical properties of the resin may be reduced. In addition, the present invention
A preferred blending ratio of the lubricant in the resin composition is ABS.
0.01 to 5 parts per 100 parts of the base resin, more preferably
0.05 to 2 parts. ABS if less than 0.01 parts
The antibacterial properties of the resin composition cannot be sufficiently obtained,
Inferior properties and may cause poor appearance of the molded product,
On the other hand, even if it is more than 5 parts, the antibacterial effect is hardly improved.
Rather, the kneading of the compounding composition is insufficient,
Failure may occur. O The molded antimicrobial composition, surfactant, lubricant and ABS resin are
Appropriate temperature or pressure according to the characteristics of the ABS resin used
By mixing by force, mixing or kneading,
An antibacterial ABS resin molded article can be easily obtained.
After uniform mixing in this way, any known processing
Can be formed into various forms using technology and machinery
You. Examples of specific molding methods include extrusion molding and injection molding.
Out forming, calendering, vacuum forming and foam forming.
You. In addition, each component of the antibacterial agent composition, surfactant and lubricant
ABS resin containing a high concentration of
H) is prepared in advance, and this and ABS resin are used as raw materials.
It is also possible to form by molding. In addition, the above-mentioned granular material is produced
The order of mixing these components is not limited.
A particulate material (A) comprising an antibacterial agent composition and an ABS resin; and
Granules (B) consisting of surfactant, lubricant and ABS resin
Make multiple types of granular materials with different components, etc.
You may mix and shape at the time of molding. As a processing method for obtaining granules, a known method is known.
Can be adopted, for example, inorganic antibacterial agent, gold
Oxides, surfactants, lubricants and ABS resin powders
After mixing with a Hensyl mixer, use an extruder
Pellet-forming method, inorganic antibacterial agent, metal acid
Chloride, surfactant and lubricant directly with ABS resin pellets
Intimately mix and pelletize the resulting mixture with an extruder.
And the like. Antibacterial ABS system obtained as described above
The resin molded product is stable because the antibacterial agent is chemically and physically excellent
Silver in the acidic solution
And has no hygroscopicity, and is extremely excellent in workability. That
Above, at the time of mixing of inorganic antibacterial agent and resin, and after that antibacterial
Without deterioration during storage or use of the conductive resin composition,
Anti-fungal, antibacterial and anti-algal for a long time even in harsh environments
Has the property. Use: Antibacterial ABS resin obtained by molding the composition of the present invention.
The molded article needs antifungal, antialgal and antibacterial properties, and
It is effective in various fields where BS resin moldings are used.
You. As a specific application, for example, refrigerated in the case of weak electricity
Storage, washing machine, vacuum cleaner, fan, air conditioner, electric pot, V
TR, TV, tape recorder, OA equipment, etc.
In the interior and exterior of the clerk, telephone, and miscellaneous goods, housing parts, various contents
Tableware, sporting goods, daily necessities, building materials, optical equipment and stationery
And kitchen utensils. The resin molded article molded using the composition of the present invention is
It is not clear why it can exhibit excellent antibacterial properties
However, the present inventors presume as follows. That is,
Including a surfactant and a lubricant in the resin composition
By improving the dispersibility of the inorganic antibacterial agent in the resin,
In addition, the surfactant easily migrates to the surface of the resin molding
In addition, due to its migration, the surface of the resin
There is a high probability that the particles of the agent will start
It is considered that it exhibits excellent antibacterial properties. Hereinafter, the present invention will be described in more detail with reference to Examples.
Will be described. EXAMPLES <Reference Example 1> (Preparation of antibacterial agent) Aqueous solution of zirconium sulfate and ammonium dihydrogen phosphate
The aqueous solution of zirconium and phosphorus will be in a ratio of 2: 3
A precipitate is formed by mixing
After adjusting the pH to 2 using an aqueous solution of lithium,
Crystallized by heating at 150 ° C for 24 hours under conditions
Zirconium phosphate was obtained. Phosphate-based compound obtained above
Was added to an aqueous solution of silver nitrate and stirred at room temperature for 4 hours.
After washing with water, drying and crushing, Ag
Antibacterial having a content of 11% by weight and having the following composition formula:
Agent [A] was obtained. Ag _0.53 Na _0.13 H _0.34 Zr _Two (PO _Four ) _Three The obtained antibacterial agent [A] has an average particle size of 0.47 microns.
It is a white powder. 30% by weight of this antibacterial agent [A] and acid
70% by weight of zinc oxide is put into a small grinder and mixed, and an antibacterial agent
Composition [A] was obtained. Reference Example 2 The zinc oxide in Reference Example 1
Instead, the same as in Reference Example 1 except that titanium dioxide was used.
Thus, an antibacterial agent composition [B] was obtained. Example 1 (Preparation of antibacterial ABS resin molded article)
Manufactured by Daicel Chemical Industries, Ltd.
(Melt index MI = 20, hereinafter abbreviated as ABS resin)
97.5% by weight of the antibacterial agent composition [A]
0.5% by weight, glycerin monostearic surfactant
Rate (hereinafter abbreviated as surfactant [A]) 1.0 weight
%, Calcium stearate as lubricant (hereinafter referred to as lubricant
Abbreviated as [A]. ) 1.0% by weight
Mix evenly and add Toshiba Machine Co., Ltd. IS-55EPN
Injection molding at 220 ° C using 10cm x 10cm x 2
mm antimicrobial plates were prepared. The following example
And the size of the plate manufactured in the comparative example is 10c.
mx 10 cm x 2 mm. Example 2 (Preparation of antibacterial ABS resin molded article)
96.5% by weight of ABS resin and antibacterial agent composition [A]
0.5% by weight, surfactant [A] 2.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 3 (Preparation of antibacterial ABS resin molded article)
97.5% by weight of ABS resin and antibacterial agent composition [A]
Glycerin monolau as a surfactant
Rate (hereinafter abbreviated as surfactant [b])) to 1.0
% Except for the addition of 1.0% by weight of lubricant [A]
An antibacterial plate was prepared in the same manner as in Example 1. Example 4 (Preparation of antibacterial ABS resin molded article)
96.5% by weight of ABS resin and antibacterial agent composition [A]
0.5% by weight, surfactant [b] 2.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 5 (Preparation of antibacterial ABS resin molded article)
97.0% by weight of ABS resin and antibacterial agent composition [A]
1.0% by weight, surfactant [A] 1.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 6 (Preparation of antibacterial ABS resin molded article)
Antibacterial agent composition [A] based on 96.0% by weight of ABS resin
1.0% by weight, surfactant [A] 2.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 7 (Preparation of antibacterial ABS resin molded article)
97.0% by weight of ABS resin and antibacterial agent composition [A]
1.0% by weight, surfactant [b] 1.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 8 (Preparation of antibacterial ABS resin molded article)
Antibacterial agent composition [A] based on 96.0% by weight of ABS resin
1.0% by weight, surfactant [b] 2.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Example 9 (Preparation of antibacterial ABS resin molded article)
97.5% by weight of ABS resin and antibacterial agent composition [B]
0.5% by weight, surfactant [I] 1.0% by weight,
Same as Example 1 except that 1.0% by weight of agent [A] was added.
An antibacterial plate was prepared by the operation described above. Comparative Example 1 The same operation as in Example 1 was performed using only the ABS resin.
Produced. Comparative Example 2 Antibacterial agent composition [A] with respect to 99.5% by weight of ABS resin
The same operation as in Example 1 except that only 0.5% by weight was blended.
Made by the work. Comparative Example 3 Antibacterial agent composition [A] with respect to 99.0% by weight of ABS resin
The same operation as in Example 1 except that only 1.0% by weight was blended.
A plate was produced by the operation. Comparative Example 4 Antibacterial composition [A] with respect to 98.5% by weight of ABS resin
0.5% by weight, and surfactant [A] 1.0% by weight
A plate was prepared in the same manner as in Example 1 except that
did. Comparative Example 5 Antibacterial agent composition [A] with respect to 98.0% by weight of ABS resin
1.0% by weight and 1.0% by weight of surfactant [A]
A plate was prepared in the same manner as in Example 1 except that
did. Comparative Example 6 Antibacterial agent composition [A] with respect to 98.5% by weight of ABS resin
0.5% by weight and surfactant [b] 1.0% by weight
A plate was prepared in the same manner as in Example 1 except that
did. Comparative Example 7 Antibacterial composition [A] with respect to 98.0% by weight of ABS resin
1.0% by weight, surfactant 1.0% by weight
A plate was prepared in the same manner as in Example 1 except that
did. COMPARATIVE EXAMPLE 8 An antibacterial agent [A] was used instead of the antibacterial agent composition [A].
Except for this, a plate was produced in the same manner as in Example 8. Tables 1 and 2 show the composition ratios of Examples and Comparative Examples.
Indicates a match. [Table 1] [Table 2] Test Example 1 (Antibacterial Test) Each plate prepared in Examples 1 to 9 and Comparative Examples 1 to 8
The antibacterial activity was evaluated by the following method. Escherichia coli as test bacteria
Cut the antibacterial plate into 3cm x 3cm squares using
10 bacteria per rate ^Four -10 ^Five To be individual
Was uniformly inoculated on the surface with the bacterial solution, and stored at 27 ° C. Save
0 hours after the start (initial bacterial count) and after 6 hours storage
And a test piece in a culture medium (SCDLP liquid medium)
The above viable cell count was washed out, and this washing solution was used as a test solution. this
For test solution, pour plate culture using culture medium for cell count
The number of viable cells was measured by the
It was converted to the number of viable bacteria per 3 cm × 3 cm. Also, test
The same operation was carried out without using a piece to serve as a control. above
The results of the antibacterial test thus obtained are shown in Tables 3 and 4.
Indicated. The initial number of bacteria was 1.1 × 10 ^Five And contrast
The number of bacteria is 8.8 × 10 ^Four Met. [Table 3] [Table 4] Test Example 2 (Weather Resistance Test) The plates prepared in Examples 1 to 9 and Comparative Examples 1 to 8
And a weather resistance tester (UC- manufactured by Toyo Seiki Seisakusho Co., Ltd.)
The weather resistance was evaluated using 1). Test article of weather resistance tester
One cycle was 8 hours, and the
The following 4 hours process of irradiating ultraviolet rays and humidity of 95 at 40 ° C.
% For 4 hours. Continuous
After 5 cycles of operation, the color difference meter (Nippon Denshoku Industries Co., Ltd.
Using a color difference meter SZ- # 80), five
The color (L, a, b) after the circle is measured, and this color and
By comparing the color with the color immediately after the shape (0 cycle),
The difference ΔE was determined. For each antibacterial plate,
After (0 cycle) and after 5 cycles of weather resistance test
5 and Table 6. The weather resistance of the blank plate
As a result of the test, the color difference was zero after 5 cycles and 5 cycles.
Were 0 and 1.24, respectively. [Table 5] [Table 6] From the results shown in Tables 3 and 4, the ABS tree
The fat is mixed with an antibacterial agent composition or a surfactant and
Injection molding (Comparative Examples 1 to 7) or metal oxide
Injection molding with only antibacterial agent mixed without containing
(Comparative Example 8), the molded article hardly exhibits antibacterial properties
However, in addition to the antibacterial agent composition, the ABS
Antibacterial properties are remarkably improved by injection molding with blending of lubricant and lubricant
It improves (Examples 1-9). In addition, in Tables 5 and 6 above,
From the results, the antibacterial agent composition and the surfactant
Improves the weather resistance of the molded resin by adding a lubricant
You can see that The resin molded article obtained by molding the composition of the present invention.
Exhibits the original excellent antibacterial properties of antibacterial agents, and
Excellent weather resistance. Obtained by molding the composition of the present invention.
Molded articles require anti-mold, anti-algal or antibacterial properties and
It is useful in various fields where BS resin moldings are used.
You.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-66254 (JP, A) JP-A-3-38504 (JP, A) JP-A-5-78498 (JP, A) 136233 (JP, A) JP-A-6-240094 (JP, A) JP-A-6-287403 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 55/02 C08K 3 / 22 C08K 3/32 C08K 5/00

Claims (1)

(57) [Claims] 1. An ABS resin, a phosphate antibacterial agent represented by the following formula [1], at least one metal oxide selected from zinc oxide and titanium dioxide, and an interface. An antimicrobial ABS resin composition comprising an activator and a lubricant. _{Ag a A b M 2 (PO} 4) 3 · nH 2 O (1) (A is an alkali metal ion, alkaline earth metal ions,
At least one ion selected from ammonium ions or hydrogen ions, M is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, and both a and b are a +
It is a positive number satisfying mb = 1. Here, m is the valence of A. )