JPH093292A - Flame retardant antibacterial resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a flame-retardant antibacterial resin composition which is excellent in flame retardancy, antibacterial properties and impact properties and can be used in a wide range of applications. [Constitution] (1) (A) Rubber-reinforced styrene resin 60-
95 wt% (B) Halogen-based flame retardant 5-30 wt%
(C) Resin composition (A) containing 0 to 10% by weight of antimony oxide compound (A) (A + B + C = 100% by weight) 1
A flame-retardant antibacterial resin composition containing 0.1 to 10 parts by weight of (D) a silver-based antibacterial agent and 0.1 to 5 parts by weight of (E) a metal salt of montanic acid with respect to 00 parts by weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant antibacterial resin composition excellent in flame retardancy, antibacterial properties and impact properties.

[0002]

2. Description of the Related Art Styrenic resins such as ABS resins are used in a wide range of fields such as electric / electronic fields, OA equipment fields, and vehicle fields because of their excellent surface appearance, molding processability, and mechanical properties. Has been done. In recent years, it has been feared that bacteria may be generated in these products to affect the human body, and it is desired to impart antibacterial properties to some products. In addition, there is an increasing demand for materials having antibacterial properties and flame retardancy in view of safety against fire. A technique for imparting flame retardancy to styrene resins is a general technique by using a halogen flame retardant. Further, as a method of imparting antibacterial property, there is a method of kneading a commercially available antibacterial agent, but when the antibacterial agent is kneaded and mixed with a styrene resin, there is a drawback that the antibacterial property is difficult to be expressed and the antibacterial property is expressed. Since it is necessary to knead a large amount of antibacterial agent, there is a drawback that impact strength is lowered. Furthermore, in order to impart flame retardancy, when a flame retardant is also kneaded together, impact resistance is greatly reduced and it is difficult to make a material that can be used practically. In order to develop antibacterial properties, JP-A-1-287172 discloses that metal stearate such as aluminum stearate or zinc stearate is blended,
Japanese Patent Application Laid-Open No. 7-33906 discloses addition of wax such as polyethylene wax and metal soap such as magnesium stearate. However, it is difficult to improve both the antibacterial property and the impact strength by the conventional technique, and the impact strength of the antibacterial resin imparted with the flame retardancy is greatly lowered, so that the use thereof is limited. The present invention has been made against the background of the problems of the prior art, flame retardant,
An object is to provide an antibacterial resin composition which has excellent antibacterial properties and impact properties and can be used in a wide range of applications.

[0003]

In view of the above situation, the present inventors have studied the development of a material having a high antibacterial property while maintaining a high impact resistance with a flame retardant antibacterial resin, and as a result, montanic acid has been obtained. It was found that the above problems can be solved by using a specific amount of a metal salt and a specific fatty acid ester,
The present invention has been completed.

[0004]

The present invention provides (1) (A)
Rubber-reinforced styrene resin 50 to 95% by weight (B) Halogen flame retardant 2 to 35% by weight (C) Antimony oxide compound 0 to 15% by weight Resin composition (a)
(A + B + C = 100% by weight) Flame retardant antibacterial resin composition in which (D) 0.1 to 12 parts by weight of silver-based antibacterial agent (E) 0.1 to 7 parts by weight of metal salt of montanic acid is mixed with 100 parts by weight. . And (2) 100 parts by weight of the resin composition (a) according to claim 1, (D), and (D) according to claim 1.
0.1 to 12 parts by weight (E) (E) 0.
1 to 7 parts by weight (F) A flame retardant antibacterial resin composition containing 0.1 to 7 parts by weight of a fatty acid ester obtained from a fatty acid and an aliphatic alcohol and having a melting point of 20 to 80 ° C is provided. It is a thing.

The rubber-reinforced styrenic resin (A) of the present invention comprises (a) a vinyl monomer in the presence of a rubbery polymer, preferably (b) an aromatic vinyl monomer (c) a vinyl cyanide monomer. A graft polymer resin obtained by graft-polymerizing a monomer component consisting of a monomer and another monomer copolymerizable with these monomers can be mentioned, and is also obtained by polymerizing the above-mentioned monomer component. It may be obtained by blending a thermoplastic resin and the graft polymer resin. From the viewpoint of impact resistance, the content of the rubbery polymer is preferably 5 to 50% by weight. Examples of the rubbery polymer (a) used in the present invention include polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber. , Silicone rubber, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene copolymer and the like. These (a) rubbery polymers are used alone or in combination of two or more.

The content of the (a) rubbery polymer in the component (A) is preferably 5 to 50% by weight, more preferably 5 to 4%.
It is 0% by weight, particularly preferably 5 to 30% by weight.
When the amount of the component (a) is 5% by weight or more, the impact resistance is excellent,
On the other hand, if it exceeds 50% by weight, the rigidity becomes poor. Examples of the aromatic vinyl monomer as the component (b) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene and divinylbenzene, and styrene and α-methylstyrene are particularly preferable. These aromatic vinyl monomers may be used alone or in combination of two or more. The content of the component (b) in the component (A) is preferably 45 to 90% by weight, more preferably 45 to 80% by weight, and particularly preferably 45 to 70% by weight. Examples of the vinyl cyanide monomer as the component (c) include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. These vinyl cyanide monomers may be used alone or in combination of two or more. The content of the component (c) in the component (A) is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight. Other copolymerizable monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; unsaturated compounds such as maleic anhydride. Examples thereof include acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; and imide compounds of unsaturated dicarboxylic acids such as maleimide, N-phenylmaleimide and N-methylmaleimide.

The component (A) used in the present invention is 50 to 9
5% by weight, preferably 55-95% by weight,
It is particularly preferably 60 to 95% by weight. If the amount of the component (A) is less than 50% by weight, the impact strength will be poor, and if it exceeds 95% by weight, the flame retardancy will be poor. Examples of the halogen-based flame retardant (B) used in the present invention include tetrabromobisphenol A and its derivatives, tetrabromophthalic anhydride, brominated diphenyl ether, brominated polycarbonate oligomer and its terminal modified product, brominated epoxy resin and its terminal modified product. , Brominated phenoxy resin, tris dibromophenyl phosphate, brominated polystyrene, chlorinated polyethylene and the like are used. These halogen-based flame retardants are used alone or in combination of two or more. Examples of the (C) antimony oxide compound used in the present invention include antimony trioxide and antimony pentoxide. The component (B) is 2 to 35% by weight, preferably 3 to 30% by weight, and more preferably 5 to 25% by weight. If it is less than 2% by weight, the flame retarding effect is insufficient, and if it exceeds 35% by weight, the impact resistance is lowered. The component (C) used in the present invention is 0 to 15% by weight, preferably 0.5 to 10% by weight, and particularly preferably 1 to 8% by weight. 15% by weight
If it exceeds, the impact resistance will be reduced.

The silver antibacterial agent (D) used in the present invention is an organic or inorganic silver compound, or a substance having a porous structure (porous structure) carrying a silver compound and / or a silver complex salt. Examples thereof include those obtained by carrying out silver ion-exchange on a porous structure, and the like. Examples of silver compounds include silver halides such as silver fluoride, silver chloride and silver bromide, silver nitrate, silver sulfate, silver lactate, silver chlorate, silver picrate, porotane silver, colloidal silver, silver salts of carboxylic acids, and phosphorus. Examples thereof include acid or phosphorous acid alkyl ester, phenyl ester, or alkylphenyl ester silver salt. Further, as the porous structure, silica gel,
Examples include activated carbon, zeolite, zirconium phosphate, calcium phosphate, hydrotalcite, calcium-based ceramics, and the like. The component (D) used in the present invention is 0.1 to 12 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 8 parts by weight. If the amount used is less than 0.1 parts by weight, antibacterial properties will be reduced, and
If it exceeds the weight part, the impact resistance is lowered.

Examples of the (E) metal salt of montanic acid used in the present invention include calcium montanate, magnesium montanate, aluminum montanate and the like, and calcium montanate is preferable. The (E) metal salt of montanic acid used in the present invention is 0.1 to 7 parts by weight, preferably 0.2 to 6 parts by weight, and more preferably 0.2 to 5 parts by weight. If the amount used is less than 0.1 parts by weight, the antibacterial property will be deteriorated, and if it exceeds 7 parts by weight, the impact resistance will be deteriorated.

The (F) fatty acid ester used in the present invention is, for example, a fatty acid ester obtained from a fatty acid and an aliphatic alcohol by a dehydration reaction and having a melting point of 20 to 80 ° C. Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid. Examples of the aliphatic alcohol include propyl alcohol, amyl alcohol, octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, aralkyl alcohol and behenyl alcohol. The component (F) is preferably octadecyl stearate. The component (F) used in the present invention is preferably 0.1 to 7 parts by weight, more preferably 0.2 to 6 parts by weight, and particularly preferably 0.2 to 5 parts by weight. When the amount used is 0.1 parts by weight or more, the impact strength developing property is further excellent, but when it exceeds 7 parts by weight, the heat resistance decreases.

The resin composition of the present invention includes fillers such as glass fiber, carbon fiber, glass beads, talc, mica and kaolin, known coupling agents, antioxidants, plasticizers, colorants, lubricants, electrification agents. Additives such as inhibitors can be added. Further, the resin composition of the present invention, other polymers depending on the required performance, such as polyethylene, polypropylene, polyamide, polyester, polycarbonate, polysulfone, polyvinylidene fluoride,
A polyamide elastomer or the like can be appropriately blended. The flame-retardant antibacterial resin composition of the present invention can be obtained by kneading the components using various extruders, Bavary mixers, kneaders, rolls and the like. When kneading the components, the components may be kneaded at once, or may be kneaded by a multi-stage addition method. The resin composition of the present invention thus obtained can be formed into various molded products by injection molding, sheet extrusion, vacuum molding, foam molding, or the like.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified. Moreover, various evaluations in the examples were measured as follows. Escherichia coli was used as the antibacterial bacterium, and the Escherichia coli solution was sprayed onto the surface of the molded product of 5 × 5 cm ² , and after 24 hours, the viable cell count was examined to measure the antibacterial activity against Escherichia coli. Flammability 5 "x 1/2" x according to the method specified in UL94 standard
A vertical combustion test was performed on a 1/10 "thick test piece. The heat distortion temperature specified in heat resistance ASTM D-648 was measured. Impact resistance Shimadzu high speed impact tester Servo Pulser EHF-2H
The breaking energy of a test piece having a thickness of 50 × 80 × 2.4 mm was measured using -20 L under the following conditions. Test piece cradle diameter 3
0φ, 12.7 R at the tip of the striking rod, 3.1 m / s striking speed

Preparation of Rubbery Polymers (a) -1 and 2 The rubbery polymers are shown in Table 1 as the component (a) used in the (A) rubber-reinforced styrene resin of the present invention.

[0014]

[Table 1]

Monomer components of (b) and (c) of the present invention in the presence of adjusted rubbery polymers (a) -1 and (2 ) of resins (a) ' -1 to (a)'-3. To obtain a resin polymerized with and a resin polymerized only with the components (b) and (c). The resin compositions of these are shown in Table 2.

[0016]

[Table 2]

Preparation of Resins (A) -1 to (A) -3 (A) -1 (a) '-1 50 parts of (a)'-3 was mixed with 20 parts of a rubbery polymer. Adjusted (A) -2 (a) '-2 60 parts of (a)'-3 and 40 parts of rubber polymer to adjust halogen-based flame retardants (B) -1, 2 As (B) -1, Pratherm EP16 manufactured by Dainippon Ink and Chemicals, Inc., which is a brominated epoxy oligomer, was used. Tetrabisphenol A was used as (B) -2. Preparation of Antimony Oxide Compound (C) Antimony trioxide was used as the antimony oxide compound. Zeomic XAW10D manufactured by Sinanen Zeomic Co., Ltd. was used as a preparation (D) -1 for the silver antibacterial agents (D) -1 to 3 . (D) -2 as Novaron A manufactured by Toagosei Chemical Industry Co., Ltd.
G300 was used. As (D) -3, Amteclean Z manufactured by Matsushita Amtech Co., Ltd. was used. Preparation of metal montanate (E) Calcium montanate was used as the metal montanate. Octadecyl stearate (melting point 62 as adjustment (F) -1 of fatty acid ester (F)
C) was used. (F) -2 octadecyl laurate (melting point 37
C) was used. Methyl laurate (melting point: 5 ° C.) was used as (F) -3.

Examples 1 to 10 and Comparative Examples 1 to 6 The ingredients shown in Table 3 were mixed in a mixer for 3 minutes to obtain 50
mm Cylinder temperature 180-210 ℃ with twin screw extruder
Was melt-extruded to obtain pellets. The pellets were injection molded at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. to obtain various test pieces for evaluation. Table 3 also shows the evaluation results of these test pieces. The combustion test was carried out according to the UL94 standard V-0 test.

[0019]

[Table 3]

As is clear from Examples 1 to 9 in Table 3, the resin composition of the present invention is excellent in flame retardancy, antibacterial property and impact strength. Comparative Example 1 is a case where the amounts of the component (D) and the component (E) are out of the range of the present invention, but the antibacterial property is poor. Comparative Example 2 has a large amount of the component (D) outside the range of the present invention, but the impact resistance is poor. In Comparative Example 3, the component (E) is less than the range of the present invention, but the antibacterial property is poor. Comparative Example 4 has a large amount of the component (E) and the component (F) outside the scope of the present invention, but is inferior in impact resistance and heat resistance. In Comparative Example 5, the components (A), (B) and (C) are out of the scope of the present invention, and the components (A) are small and the components (B) and (C) are large. Inferior in heat resistance. In Comparative Example 6, the components (A) and (B) are out of the range of the present invention, and the component (A) is large and the component (B) is small, but the combustion quality is poor.

Examples 11 to 15 and Comparative Examples 7 to 11 Similarly to Examples 1 to 9, test pieces were prepared with the formulations shown in Table 4 and evaluated. Combustion test is UL94 V-
It carried out based on 2 tests.

[0022]

[Table 4]

As is clear from Examples 10 to 13 in Table 4, the resin composition of the present invention is excellent in flame retardancy, antibacterial property and impact strength. Comparative Example 7 is a case where the components (A) and (B) are out of the range of the present invention and the amount of the component (A) is large and the amount of the component (B) is small, but the combustion quality is poor. In Comparative Example 8, the component (D) is out of the range of the present invention and the amount of the component (D) is small, but the antibacterial property is poor. Comparative Example 9 is a case in which the component (E) is replaced with magnesium stearate, but the antibacterial property is poor. In Comparative Example 10, the component (E) was replaced with aluminum stearate, but the antibacterial property was poor. Comparative Example 11 is a case where the component (F) is replaced with methyl laurate, which is outside the scope of the present invention, but the impact resistance is poor.

[0024]

INDUSTRIAL APPLICABILITY The flame-retardant antibacterial resin composition of the present invention is excellent in flame retardancy, antibacterial property and impact resistance and is useful in a wide range of applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C08K 5/10 C08K 5/10 (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. A rubber-reinforced styrenic resin 50-95.
Wt% (B) Halogen-based flame retardant 2 to 35 wt% (C) Antimony oxide compound 0 to 15 wt% Resin composition (a) (A + B + C = 100)
(% By weight) A flame-retardant antibacterial resin composition containing (D) 0.1 to 12 parts by weight of (D) 0.1 to 7 parts by weight of metal salt of montanic acid per 100 parts by weight. 2. The resin composition (a) according to claim 1, (D) 0.1 to 12 parts by weight (E) to 100 parts by weight (E), and (E) according to claim 1. 0.1 to 7 parts by weight (F) A flame-retardant antibacterial resin composition containing 0.1 to 7 parts by weight of a fatty acid ester obtained from a fatty acid and an aliphatic alcohol and having a melting point of 20 to 80 ° C.