JPH10324804A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent antibacterial properties and antifungal properties and retains these properties for a long time especially when used in a watery environment by including a polyarylene sulfide and a metal-ion-containing borosilicate glass in specified amounts. SOLUTION: This composition comprises 100 pts.wt. polyarylene sulfide and 0.1-15.0 pts.wt., desirably 0.5-3.0 pts.wt., more desirably 1.0-2.0 pts.wt. metal- ion-containing borosilicate glass being at least one member selected among silver-ion-containing-, copper-ion-containing and zinc-ion-containing borosilicate glasses. The metal-ion-containing borosilicate glass is a water-soluble one prepared by uniformly dispersing metal ions in a glass composition containing a network-forming oxide of SiO2 or B2 O3 and a network-modifying oxide of Na2 O, gels by the action of water or moisture and slowly dissolves in water while the metal ions are being contained in the gel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin composition, and more particularly to a PA having antibacterial and antifungal properties.
It relates to an S resin composition.

[0002]

2. Description of the Related Art Since PAS has a high melting point, its use has been remarkably widened in recent years as a heat-resistant plastic and has been used in various products. With the expansion of the range of use, it has come to be used in an environment where mold is relatively likely to occur, such as under high temperature and high humidity. Therefore, like other plastic materials, PAS has been a problem of damage from bacteria and fungi.

Hitherto, it has been practiced to add an antibacterial agent and a fungicide to various plastics by imparting antibacterial and fungicidal properties. As antibacterial agent and fungicide, N
-(Fluorodichloromethylthio) -phthalimide, 2
-(4-thiazolyl) -benzimidazole, 2,3
5,6-cytochloro-4- (methylsulfonyl) -pyridine, 10,10'-oxybisphenoxyarsine,
Trimethoxysilyl-propyloctadecyl ammonium chloride, 2-n-octyl-4-isothiazolin-3-one, bis (2-pyridylthio-1-oxide)
Organic antibacterial agents such as zinc and fungicides are generally commercially available.

However, in a resin such as PAS, which is formed at a relatively high temperature, an organic antibacterial agent and a fungicide are decomposed and deteriorated during the molding process, and the effect cannot be sufficiently exhibited. Had disadvantages.

In order to eliminate such disadvantages, Japanese Patent Laid-Open Publication No.
390 and JP-A-7-173392,
Silver, an antimicrobial substance containing a metal ion selected from copper and zinc, preferably silica, diatomaceous earth, alumina,
A PAS resin composition containing a substance adsorbed and supported on inorganic fine particles such as titania, zirconia, acid clay, zeolite, and calcium carbonate is disclosed.

It has been confirmed that the inorganic antibacterial agent has excellent antibacterial properties immediately after molding. But,
Antibacterial properties are particularly required, when used around water in kitchens and bathrooms with relatively high humidity, the metal ions themselves or metal ions are adsorbed during use, and the inorganic fine particles carrying are eluted in water, There is a problem that the effect is reduced in a short time.

[0007] JP-A-6-166823 discloses a bactericidal / mold-resistant resin product in which at least one selected from the group consisting of zinc sulfate and zinc borate is interposed. However, this product still has a problem that when used around water, the antibacterial and fungicidal properties cannot be maintained for a long period of time.

[0008]

SUMMARY OF THE INVENTION The present invention is to provide a polyarylene sulfide resin composition having excellent antibacterial and antifungal properties and maintaining such properties for a long period of time.

[0009]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems. As a result, they have found that the above-mentioned problems can be effectively solved by adding the following predetermined antibacterial agent to the PAS in a predetermined amount, and have completed the present invention.

That is, the present invention is a resin composition comprising (1) 100 parts by weight of (A) polyarylene sulfide and (B) 0.1 to 15.0 parts by weight of a borosilicate glass containing metal ions.

In a preferred embodiment, (2) a resin composition containing 0.5 to 3.0 parts by weight of the metal ion-containing borosilicate glass (B), and (3) a metal ion-containing borosilicate glass (B) containing silver ion (4) The resin composition according to (1) or (2), which is one or more substances selected from the group consisting of borosilicate glass containing copper, borosilicate glass containing copper ion, and borosilicate glass containing zinc ion. Furthermore, the resin composition according to any one of the above (1) to (3), which contains (C) an inorganic filler in an amount of 0 to 400 parts by weight, can be mentioned.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (B) metal ion-containing borosilicate glass of the present invention generally refers to a glass composition containing a network forming oxide of SiO ₂ , B ₂ O ₃ and a network modifying oxide of Na ₂ O. A water-soluble borosilicate glass containing metal ions uniformly dispersed therein, and the above-mentioned metal ion-containing borosilicate glass gels by the action of water or atmospheric moisture,
The metal ions are gradually eluted into water while being held in the gel.

In the resin molded article containing the metal ion-containing borosilicate glass, metal ions are eluted together with the glass constituents by the action of moisture or moisture in contact with the surface of the molded article, thereby inhibiting the growth of mold and bacteria. . Then, as the metal ions elute from the surface of the resin molded body, metal ions existing inside the resin molded body newly appear on the surface of the molded body,
This phenomenon is repeated continuously.

In the present invention, one or more substances selected from the group consisting of borosilicate glass containing silver ions, borosilicate glass containing copper ions, and borosilicate glass containing zinc ions are preferably used. Such a borosilicate glass is manufactured as follows. Silver ions, copper ions or zinc ions are added to a mixture of SiO ₂ , B ₂ O ₃ , and Na ₂ O as oxides, mixed uniformly, preferably melted at 1300 to 1400 ° C., and then cooled. Solidifies to obtain a glassy substance. The glassy substance is produced by pulverizing to a micron order and then classifying. As the component (B), for example, Amolculin (trademark, manufactured by Nippon Sheet Glass Co., Ltd.) as a borosilicate glass containing silver ions and the like can be mentioned.

The metal ion-containing borosilicate glass (B)
The upper limit thereof is 15.0 parts by weight, preferably 3.0 parts by weight, particularly preferably 2.0 parts by weight, and the lower limit is 0.1 part by weight, based on 100 parts by weight of PAS (A). ,
Preferably it is 0.5 part by weight, particularly preferably 1.0 part by weight. If it is less than the above lower limit, sufficient antibacterial properties and fungicidal properties cannot be imparted to PAS. Even if the amount exceeds the above upper limit, a remarkable increase in the effect cannot be obtained for the increase in the blending amount,
Not only is the cost increased, but also the physical properties of the obtained PAS resin composition, for example, the Izod impact strength, are lowered, which is not preferable.

The component (A) PAS is a known polymer having an arylene sulfide repeating unit, and is particularly preferably polyphenylene sulfide (hereinafter sometimes abbreviated as PPS). The method for producing PAS is not particularly limited, and can be usually produced by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent. For example, a method described in Japanese Patent Publication No. 45-3368, a method using an alkali metal carboxylate described in Japanese Patent Publication No. 52-12240, US Pat.
3, a method using a polymerization aid such as lithium halide, a method using a cross-linking agent such as a polyhalo aromatic compound described in JP-B-54-8719, and a method disclosed in JP-B-63-33775. Under the different water abundances described in
In a method using a multi-step reaction, a method for producing PAS by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent described in JP-A-5-222196, By cooling the gas phase portion of the reaction vessel, a part of the gas phase in the reaction vessel is condensed, and this can be produced by a method of refluxing the liquid phase into a liquid phase.

The organic amide solvents used for the production of PAS are known for PAS polymerization, for example N-methylpyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide, N- Methylcaprolactam and the like, and mixtures thereof can be used.
Is preferred.

Alkali metal sulfides are also known, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. These hydrates and aqueous solutions may be used. Hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

Dihaloaromatic compounds are described in, for example,
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using one or more kinds of para-, meta- or ortho-dihalides of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenylsulfone, m, p'-dichlorodiphenylsulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
Dichlorobiphenyl.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
Polyhalo compounds such as trichlorobenzene can also be used, preferably in a concentration of 5 mol% or less, based on the total amount of the para and metadihalo aromatic compounds.

Further, as a small amount of additives, a monohalide as a terminal terminator and a modifier may be used in combination.

The PAS obtained can be separated from by-products by post-treatment methods known to those skilled in the art.

The PAS resin composition of the present invention can contain (C) an inorganic filler as an optional component.
(C) The inorganic filler is not particularly limited, and for example, a powdery / flaky filler, a fibrous filler, and the like can be used. Examples of the powdery / flaky filler include alumina, talc, mica, kaolin, clay, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, Hydrotalcite,
Zirconium oxide, glass beads, carbon black and the like can be mentioned. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition, a filler such as a ZnO tetrapot, a metal salt (eg, zinc chloride, lead sulfate, etc.), an oxide (eg, iron oxide, molybdenum dioxide, etc.), and a metal (eg, aluminum, stainless steel, etc.) may be used. it can. These can be used alone or in combination of two or more. Further, these fillers may be treated with a silane coupling agent or a titanate coupling agent as necessary.

The amount of the component (C) inorganic filler is preferably up to 40 parts by weight per 100 parts by weight of the component (A) PAS.
0 parts by weight, particularly preferably 200 parts by weight. If the component (C) exceeds the above upper limit, the moldability deteriorates, which is not preferable. In order to increase the mechanical strength, it is preferable to add 0.01 parts by weight or more.

Further, if necessary, in addition to the above components,
Known additives and fillers such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, colorants, and the like can be added.

The method for producing the resin composition of the present invention is not particularly limited. For example, each component is mechanically mixed with a mixer such as a Henschel mixer that is generally widely used, and then melt-kneaded with a conventional device such as an extruder.
It can be extruded and pelletized. It can also be mixed / molded as a masterbatch. Alternatively, each component of the composition may be separately charged into an extruder and melt-kneaded. The resin composition thus produced is molded into a desired shape by, for example, injection molding or compression molding.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0028]

EXAMPLES The components used in the examples and comparative examples are as follows. (A) PPS:-T-1 (trademark, manufactured by Topren Co., Ltd.)-T-4 (trademark, manufactured by Topren Co., Ltd.) (B) Antibacterial agent:-Borosilicate glass containing silver ions (Amorculin P-1)
0, trademark, manufactured by Nippon Sheet Glass Co., Ltd.) (C) Inorganic filler:-Glass fiber (CS 3J-961S, trademark, manufactured by Nitto Boseki Co., Ltd.)-Calcium carbonate (SL-1000, trademark, manufactured by Takehara Chemical Industry Co., Ltd.) (D) Other additives-Titanium white (EPD193Y-1, trademark, manufactured by Tokyo Ink Co., Ltd.) Comparative antibacterial agent:-Silver ion-containing zeolite (zeomix, trademark, manufactured by Sinanen Co., Ltd.)

[0029]

Examples 1 to 5 and Comparative Examples 1 to 3 Each substance (excluding glass fibers) in the amounts (parts by weight) shown in Tables 1 and 2 was mixed with a Henschel mixer for 4 minutes, and then the glass fibers were added. Mix for an additional 3 minutes. After mixing, a barrel setting temperature of 320 mm
The pellets were prepared by melting and kneading at 400 ° C. and a rotation speed of 400 rpm.

Next, the pellets are supplied to an injection molding machine,
Cylinder temperature 320 ° C, mold temperature 130 ° C, 60mm
After forming a dumbbell piece of × 60 mm × 2 mm, the dumbbell piece was cut to prepare a test piece of 10 mm × 10 mm × 2 mm.

Each evaluation test was performed as follows. <Antibacterial test> Escherichia coli IFO 3972 used in the test Pseudomonas aeruginosa IFO 13275 Staphylococcus aureus IFO 12732 Test method 1) Shake flask method Evaluation Test Manual II
2. It was carried out in accordance with the edition of the Textile Sanitary Processing Council.
The bacterial solution containing the test piece was placed in a shake flask at 25 ° C.
After shaking for 24 hours, the number of viable bacteria in the bacterial solution was measured.
In Tables 1 and 2, 0 hour indicates the number of viable bacteria in the bacterial solution at the start of shaking, and 24 hours later, the number of viable bacteria in the bacterial solution at the end of shaking. 2) Film adhesion method It was carried out in accordance with the voluntary standard and antibacterial test method for silver and other inorganic antibacterial agents, the antibacterial test method I for antibacterial processed products (1995 edition), edited by the Silver and Other Inorganic Antibacterial Agents Study Group. After dripping the bacterial solution onto the test piece, cover it with a polyethylene film,
The solution was stored under conditions of 90 ° C. and a relative humidity of 90% or more, and the number of viable bacteria on the test piece after 24 hours was measured. In Tables 1 and 2,
0 hour indicates the viable cell count on the test piece immediately after dropping, and 24 hours after the test indicates the viable cell count on the test piece at the end of the test. <Mold prevention test> Preparation of fungus Aspergillus niger IFO 6341 Penicillium citrinum IFO 6352 Chaetomium globosum ATCC 6205 Cladosporium cladosporioides IFO 6348 Rhizopus oryzae IFO 31005 Mixed spore suspension used for the test After culturing at 25 ° C. for 10 days, the formed spores were each treated with 0.005% sodium dioctyl sulfosuccinate.
After being suspended in sterilized water to which the weight% was added to form a single spore suspension, each single spore suspension was mixed by an equal amount to prepare a mixed spore suspension.

Test method The test was carried out in accordance with JIS Z 2911. After spraying 0.83 ml of the mixed spore suspension on the test piece, the mixture was cultured for 28 days at 28 ° C. and a relative humidity of 97%, and the growth state of the mold on the test piece surface was visually observed. The numbers in Tables 1 and 2 indicate the following.

3: No hyphal growth was observed.

2: The area of the hyphal growth part is 1 / the total area
Not more than 3.

1: The area of the hyphal growth part is 1 / the total area
More than 3.

The above results are shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2] In Examples 1 to 3, the blending amount of (B) the antibacterial agent with respect to (A) PPS was changed within the range of the present invention. All exhibited remarkably good antibacterial and antifungal properties. It was recognized that the antibacterial property and the antifungal property tended to be improved when the amount of (B) was increased. Example 4 is obtained by adding titanium white as a coloring agent to the composition of Example 2.
Good antibacterial and antifungal properties were not affected. Example 5
Is (A) the kind of PPS is changed, and (C) only glass fiber is blended as an inorganic filler. Similarly, it showed remarkably good antibacterial and antifungal properties.

On the other hand, in Comparative Example 1, the amount of the antibacterial agent (B) was less than the range of the present invention. Compared with Examples 1 to 3, the antibacterial property and the antifungal property were remarkably poor. Comparative Example 2 was the same as Example 5 except that the amount of (B) was less than the range of the present invention. Again, the antibacterial property and the antifungal property were remarkably bad. Comparative Example 3 is a test result of a sample corresponding to the antibacterial and fungicidal PAS resin described in Japanese Patent Application No. 7-173392. Antibacterial properties and mold prevention were extremely poor. Thus, it was found that even when silver adsorbed and supported on an inorganic substance such as zeolite was kneaded with PPS, good antibacterial properties and mildewproof properties as in the present invention could not be obtained.

[0040]

According to the present invention, there is provided a polyarylene sulfide resin composition having excellent antibacterial and antifungal properties and maintaining the properties for a long period of time.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Takashi Kawamura 1-139 Hiroo, Shibuya-ku, Tokyo Ebisu Prime Square Tower Tonen Chemical Co., Ltd. In-house

Claims (3)

[Claims] (A) Polyarylene sulfide 100
Parts by weight, and (B) borosilicate glass containing metal ions
Resin composition containing 0.1 to 15.0 parts by weight 2. Borosilicate glass containing metal ions (B)
A resin composition containing 0.5 to 3.0 parts by weight. 3. Borosilicate glass containing metal ions (B)
The resin composition according to claim 1 or 2, wherein is one or more substances selected from the group consisting of silver ion-containing borosilicate glass, copper ion-containing borosilicate glass, and zinc ion-containing borosilicate glass.