JPH03271208A - Master batch of metal salt compound particle capable of eluting aqua ion of silver and/or copper and antimicrobial resin composition - Google Patents

Abstract

PURPOSE:To provide a readily employed and safe master batch having good dispersibility in resins by coating metal salt compound particles capable of eluting the aqua ions of silver or copper with a wax or a combination of the wax and a discoloration-preventing agent for resins. CONSTITUTION:The master batch of metal salt compound particles comprises at least one kind of the particles of a metal salt compound (e.g. silver nitrate, silver sulfate, silver stearate, copper sulfate or copper chloride) capable of eluting the aqua ions of the silver or copper and a wax (e.g. vegetable wax, beeswax or montan wax) coated on the particles. Or the master batch of the metal salt compound particles comprises a composite material comprising the above-mentioned particles and a resin discoloration-preventing agent (e.g. UV light absorbent, UV light stabilizer, antioxidant) and a wax coated on the composite material. The master batch is safe even when touched with hand, and is suitably kneaded with a resin to provide an excellent stable antimicrobial resin composition.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a masterbatch of metal salt compound particles capable of eluting silver and/or copper aqua ions and an antibacterial resin composition. It can provide household goods, building materials, paints, fibers, fishing nets, etc. that have antibacterial properties.

(Prior art) Antibacterial resin compositions containing silver compounds, copper compounds, etc. are known (Japanese Patent Application Laid-Open Nos. 64-46464, 1998-11).
No. 3051, etc.), these involve kneading silver compounds, copper compounds, etc. into resin as they are.

However, when the silver salt compound or copper salt compound particles were kneaded into the resin as they were, the dispersion was extremely poor and a uniform antibacterial resin composition could not be obtained. Therefore, small lumps of these compounds may be exposed on the surface of the resin composition.
Touching the area may irritate the skin, especially if the silver compound is present. In addition, many silver compounds, copper compounds, etc. strongly attack the skin, and kneading them into resin as they are poses a major problem in terms of work safety.

Because of this, it is easy to use and safe to touch,
A masterbatch that can be kneaded into resin and has good dispersibility has been desired.

(Problems to be Solved by the Invention) The present invention was made with the aim of overcoming the drawbacks of conventional antibacterial resin compositions using silver compounds, copper compounds, etc.

(Means for Solving the Problem) The present inventors have developed at least one kind of metal salt compound particles capable of eluating silver and/or copper aqua ions, and at least one kind of wax coated on the metal salt compound particles. It was discovered that the masterbatch, which mainly consists of metal salt compound particles, is safe to the touch, and that an antibacterial resin composition into which an appropriate amount of this masterbatch is kneaded has stable and excellent antibacterial and antifungal properties. Based on these findings, we have accomplished the present invention.

The present invention will be explained below.

The metal salt compound that can elute silver and copper aqua ions used in the present invention is prepared by adding 100 g of pure water at room temperature.
The silver salt compound can be selected from inorganic or organic silver salt compounds and copper salt compounds that have a solubility of 0.1 mg or more in the resin and do not decompose below the resin processing temperature.
Examples include silver nitrate, silver sulfate, silver chloride, silver stearate, silver behenate, etc. Examples of copper salt compounds include, but are not limited to, copper VX acid, copper nitrate, copper chloride, etc. Moreover, it is desirable that the particle size of the metal salt compound is 0.5 III or less.

The waxes used in the present invention include plant-based natural waxes (carnauba wax, candelilla wax, rice wax, water vein, jojoba oil, etc.), animal-based natural waxes (honey vein wax, lanolin wax, whale vein wax, etc.), and mineral-based natural waxes. Waxes (Montanwa Nox, Osikelite, Ceresin, etc.), Petroleum Fuchs (Paraffin wax, Microcrystalline wax, Petrolactam, etc.), Synthetic hydrocarbon waxes (Polyethylene wax, Polypropylene wax, Fischer-Tropsch wax, etc.), Modified waxes (Montanwa Sox, etc.) derivatives, paraffin wax derivatives, microcrystalline wax derivatives, etc.), higher fatty acids (stearic acid, lauric acid, etc.), metal soaps derived from fatty acids having 12 to 30 carbon atoms (calcium stearate, zinc stearate, etc.), antistatic agents. (Glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, etc.)
, hydrogenated castor oil, hydrogenated castor oil derivatives, chlorinated hydrocarbons, and blended waxes containing the above waxes as main components.

The masterbatch of metal salt compound particles coated with wax according to the present invention comprises at least one of the metal salt compound particles.
It is obtained by adding and mixing the seeds and at least one kind of wax, and coating the partially or completely melted wax by the heat generated by the mixing or heating. Mixing is usually carried out in air at atmospheric pressure, but mixing may also be carried out under different pressures or in an inert gas. The shape of the masterbatch can be granulated, powdered, grained, crushed, etc., and can be selected depending on the purpose. Further, there is no particular restriction on the ratio of the metal salt compound particles to the total weight of the master batch.

There is no particular restriction on the ratio of the wax to the total weight of the masterbatch. Note that the masterbatch may contain useful additives such as fillers, inorganic ultraviolet absorbers (titanium oxide, zinc oxide, carbon black, etc.), pigments, and the like.

The anti-discoloration agents for resins used in the present invention include ultraviolet absorbers (benzotriazole-based, benzophenone-based, aryl ester-based, oxanilide-based, cyanoacrylate-based, formamidine-based, nickel-based compounds, etc.), ultraviolet stabilizers (hindered amine-based compounds, etc.), antioxidants (phenol-based, hindered phenol-based, and sulfur-based compounds, etc.), processing stabilizers (phosphorus-based compounds, etc.)
and metal deactivators (hydrazine compounds, etc.).

In the masterbatch of metal salt compound particles multi-coated with a discoloration inhibitor for resin and wax according to the present invention, there is no particular restriction on the ratio of the metal salt compound particles to the total weight of the masterbatch.

There is no particular restriction on the proportion of the discoloration inhibitor for resins and the waxes relative to the total weight of the masterbatch. As a discoloration inhibitor for resins, it is more effective to use not only a UV absorber (or UV stabilizer) but also an antioxidant and a processing stabilizer. It may also contain additives such as fillers, inorganic ultraviolet absorbers (titanium oxide, zinc oxide, carbon black, etc.) and pigments.

In addition, the antibacterial resin is kneaded with an appropriate amount of master hatch of metal salt compound particles having a multi-coated structure, in which metal salt compound particles are coated with a discoloration inhibitor for resins in advance and then coated with wax. The composition has excellent heat resistance and light resistance, and the reason is considered to be as follows. When the masterbatch is kneaded into the resin, the waxes on the surface layer of the Fuster Patch act as a lubricant to protect the discoloration inhibitor for the resin underneath and prevent it from being scraped off from the surface of the metal salt compound particles. it is conceivable that.

The wax to be coated later is selected from waxes having a melting point lower than the melting point of the discoloration inhibitor for the resin.
The shape of this masterbatch, which is desirable because better results can be obtained in terms of heat resistance and light resistance, can be in the form of granules, powder, granules, crushed, etc., and can be selected depending on the application.

The masterbatch of metal salt compound particles multiple-coated with a discoloration inhibitor for resins and waxes according to the present invention is obtained by mixing at least one kind of the metal salt compound particles and at least one kind of discoloration inhibitor for resins, Heat generated by mixing or/
After the metal salt compound particles are coated with the discoloration inhibitor for resin which is partially or completely melted by heating, at least one type of wax is added and mixed, and by the heat generated by the mixing and/or the heating, It is obtained by further coating the partially or completely melted waxes.

The resin used in the present invention includes thermoplastic resin, thermosetting resin,
Crosslinked rubbers, synthetic fibers, semi-synthetic fibers, and recycled fibers can be used alone or in combination, including polyethylene, polypropylene, ABS resin, nylon, polyamide, polyester, vinyl chloride, polyvinylidene chloride, polystyrene, polyacetal, and polyvinyl alcohol. , polycarbonate, vinylidene, Eva resin, acrylic resin,
It can be selected from the group consisting of fluororesins, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, urethane resins, polyurethane elastomers, polyester elastomers, rayon, cupro, acetate, natural rubber and synthetic rubber. Additionally, useful additives 1 added to these resins may include fillers, plasticizers, stabilizers, lubricants, antioxidants, ultraviolet absorbers, antistatic agents, metal deactivators, pigments, etc. .

The antibacterial resin composition according to the present invention can be applied to molded products (films, sheets, pipes, molds, etc.), foams, paints, adhesives, resin coatings, fibers, composite materials, etc. when categorized by shape. , its shape and size are not particularly limited.

In the case of fibers, they can be used in fabrics, paper, nonwoven fabrics, etc. in combination with different types of fibers that are not made of antibacterial resin compositions. In addition, if the proportion of the metal salt compound particles to the total weight of the composition is less than 0.001% by weight in terms of metal ions, no antibacterial properties will be observed, and if it exceeds 10% by weight, the properties of the resin will be significantly impaired, so it cannot be used. More preferably, it is in the range of 0.005 to 5% by weight, and the ratio of the discoloration inhibitor for resin to the total weight of the composition is 0.000 to 5% by weight.
If it is less than 1% by weight, there is little improvement in discoloration, and if it is less than 5% by weight,
If it exceeds this, there will be problems such as blooming.

More preferably, the wax is in the range of 0.005 to 1% by weight, and the proportion of the wax to the total weight of the composition is 0.01.
Weight % to 30 weight % is desirable. The smaller the proportion of Wa Nox, the greater the amount of metal ions eluted from the antibacterial resin composition, so it is more preferably in the range of 001 to 2% by weight. The resin composition can be obtained by kneading a masterbatch of metal salt compound particles according to the present invention into a resin using, for example, an extruder.

(Effects of the Invention) The wax-coated metal salt compound particle masterbatch of the present invention does not irritate the skin even when touched by hand, is easy to handle, and does not cause uneven dispersion when kneaded into resin. Therefore, a uniform antibacterial resin composition can be provided.

The master batch of metal salt compound particles coated with the anti-discoloration agent for resins and waxes of the present invention has a structure in which the anti-discoloration agent for resins and the waxes are coated in multiple layers,
It is excellent in preventing discoloration due to heat and ultraviolet rays, and can be used in applications where discoloration of resins is a problem.

The antibacterial resin composition using the mustard bar of metal salt compound particles of the present invention can be used in a wide range of everyday household items (Pp4
For example, antibacterial functions can be imparted to textile products, kitchen utensils, food packaging materials, sanitary products, interior materials for buildings, etc.), which is of great benefit.

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1 <Preparation of a masterbatch coated only with waxes> 20 g of silver nitrate, which had been pickled in a mortar and passed through a sieve (100 mesh), and polyethylene wax (Hoechst Japan, PE520) at 180 o were mixed in a high-speed mixer (manufactured by Mizoso Kagaku). and stir at approximately 5,000 revolutions per minute.
A masterbatch coated only with granular wax of 1φ was obtained.

Example 2 (Preparation of a mustard base coated with anti-discoloration agent for resins and waxes) 80 g of silver nitrate crushed in a mortar and passed through a sieve (100 mesh), hindered phenolic antioxidant (Japan-f-) <iggy, IRGANOX 1425WL
) 2 to 1, phosphorus-based processing stabilizer (Japan Ciba Geigy, IR
GAFO316g) 6g and benzotriazole UV absorber (Japan Chihakaigyi, TINtJVIN 3
26) 20 pieces were placed in a high-speed mixer (manufactured by Mizosou Kagaku) and stirred at about 8,000 revolutions per minute to coat the silver nitrate with the discoloration inhibitor melted by frictional heat. 22.
50 and polyethylene wax (Hoechst Japan, PE
520) Put 177.5g into another high-speed mixer,
The mixture was stirred at about 5,000 revolutions per minute to obtain a masterbatch coated with a granular discoloration inhibitor for resins and waxes having a size of 1 to 5 IIIlφ.

Example 3 (Silver ion elution test of masterbatch) The masterbatches obtained in Examples 1 and 2 were soaked in a mortar, and the 010 was added to 50ml of pure water, stirred with a stirrer for 30 minutes, and filtered. Table 1 shows the results of measuring the silver ion concentration of the R solution using an ion meter (Model 10L-30, manufactured by Denki Kagaku Keiki Co., Ltd.).

This measurement result shows that silver nitrate is well covered with wax.

Example 1 95 Su 03 Example 4 (Masterbatch mixing test) Regarding the masterbatches obtained in Examples 1 and 2, silver nitrate was 01% by weight (
Using an injection molding machine (setting temperature 220"C), knead into polypropylene resin (Mitsui Petrochemical J-700P) so that the amount is 60x49x
Test pieces of 2.5+nm (test piece symbols are IA and 2A, respectively) were obtained. Initial discoloration of this test piece and light fastness test using a fade-o-meter (63°
The results are shown in Table 2.

IA (Example 1) Light gray Light brown 2A<
Example 2> None ’ None Example 5 (
Antibacterial Test) A bag was made by heat-sealing a polyethylene film (Flozen M, manufactured by Tetsusei Kagaku) so that the test piece of 60×d9×2.5 mm obtained in Example 4 would fit therein. When this bag was filled with the previous test piece and a blank polypropylene resin test piece of the same size, E. coli (IFO3301) and Staphylococcus (IFO3) were tested.
An antibacterial property test was carried out using 060) using the pressurized contact method.

After dropping 0.3 m J2 of the bacterial solution into the polyethylene bag containing these test pieces, the bacterial solution was spread over both sides of the test piece, and then the air inside the film was expelled and the bag was sealed. After that, the cells were placed in an incubator under pressure with a weight, and after 24 hours, the bacteria in the bag were washed out with phosphate buffer (10ml!), and 1mJ of this washout was cultured using the pour plate culture method using 5CDLP agar medium. The number of surviving bacteria was measured. From the results (Table 3), remarkable antibacterial effects were observed for all test pieces.

(Initial number of bacteria added) blank A A table centre 5.6X10' 1.8X10' <10 <10 2.7X104 2.8X104 <10 <10

Claims (1)

[Scope of Claims] 1. A metal salt mainly consisting of at least one type of metal salt compound particle capable of eluting silver and/or copper aqua ions, and at least one type of wax coated on the metal salt compound particle. Compound particle masterbatch. 2. (a) at least one kind of metal salt compound particles that can elute silver and/or copper aqua ions; (b) at least one kind of discoloration inhibitor for resin coated on the metal salt compound particles; ) A masterbatch of metal salt compound particles mainly consisting of at least one type of wax further coated on a composite consisting of the metal salt compound particles and the discoloration inhibitor for resin. 3. An antibacterial resin composition comprising the masterbatch according to claim 1. 4. An antibacterial resin composition comprising the masterbatch according to claim 2.