JPH10204242A - Vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flexible vinyl chloride-based resin composition, having a long-term antimicrobial performance and excellent in heat and light discoloring resistance. SOLUTION: This vinyl chloride-based resin composition comprises a vinyl chloride-based resin, a plasticizer in an amount of 20-200 pts.wt. based on 100 pts.wt. resin, a metallic phosphate holding silver ions in an amount of 0.01-10 pts.wt. based on 100 pts.wt. resin, a heat stabilizer in an amount of 1-10 pts.wt. based on 100 pts.wt. resin and at least one selected from carbonates, silicates and hydroxides of calcium, magnesium and aluminum in an amount of 5-200 pts.wt. based on 100 pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a soft vinyl chloride resin composition having a long-term antibacterial performance.

[0002]

2. Description of the Related Art Vinyl chloride resins are used in vehicles such as automobiles, building materials, home appliances, electric wire coverings, miscellaneous goods, etc. because of their inherent properties, that is, advantages such as colorability, ease of molding, weather resistance, and economy. Widely used. Further, in recent years, various resin compositions such as a vinyl chloride resin composition in which antibacterial properties have been imparted to molded articles touched by the human body due to market demands on cleanliness have been used. In these resin compositions, an organic antibacterial agent, silver-
Zeolite-based antibacterial agents are used by kneading, but vinyl chloride resin compositions are prone to thermal degradation and discoloration during composition production or molding, and organic antibacterial agents have long-term durability, odor and safety. However, silver-zeolite antibacterial agents have been pointed out to undergo discoloration by light.

In particular, since the range of use of the soft vinyl chloride resin composition is wide, the soft vinyl chloride resin composition has a long-lasting antibacterial property, has no odor, and is excellent in safety and heat stability. Appearance was strongly desired. Incidentally, the invention of a vinyl chloride resin composition having antibacterial properties is disclosed in, for example, JP-A-3-66738, JP-A-7-207090, JP-A-8-27306, etc. No mention is made of a soft vinyl chloride-based resin composition having excellent heat resistance and light discoloration resistance and having a long-lasting antibacterial performance.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks and demands, the present inventors have conducted intensive studies to provide a vinyl chloride resin composition having excellent antibacterial properties and exhibiting an antibacterial effect over a long period of time. , A metal phosphate containing silver ions,
The inventors have found that the above objects can be achieved by kneading a heat stabilizer and a carbonate, silicate or hydroxide of a specific metal into a vinyl chloride resin, and have completed the present invention. That is, an object of the present invention is to provide a soft vinyl chloride resin composition having long-term antibacterial performance and excellent heat resistance and light discoloration resistance.

[0005]

Means for Solving the Problems The gist of the present invention is that a vinyl chloride resin, per 100 parts by weight of the resin,
20 to 200 parts by weight of a plasticizer, 0.01 to 10 parts by weight of a metal phosphate holding silver ions, 1 to 10 parts by weight of a heat stabilizer and calcium, magnesium or aluminum carbonate, silicate or hydroxide At least one selected from 5 to 200 parts by weight of the vinyl chloride resin composition.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The vinyl chloride resin which is a constituent component of the vinyl chloride resin composition of the present invention is a suspension polymerization method, a bulk polymerization method, or a mixture of vinyl chloride or a mixture of vinyl chloride and a copolymerizable monomer.
All those produced by ordinary methods such as a fine suspension polymerization method or an emulsion polymerization method are used. Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; and dibutyl. Maleates such as maleate and diethyl maleate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; cyanides such as acrylonitrile and methacrylonitrile Α of vinyl chloride, ethylene, propylene, styrene, etc.
-Olefins, vinylidene chloride, vinylidene halides other than vinyl chloride such as vinyl bromide or vinyl halides, diallyl phthalate, polyfunctional monomers such as ethylene glycol dimethacrylate, etc. However, the present invention is not limited to this. The comonomer is contained in the component of the vinyl chloride resin in an amount of 30% by weight or less, preferably 20% by weight or less.

[0007] The average degree of polymerization of the vinyl chloride resin is not particularly limited.
The average degree of polymerization based on K6721 is 700 to 8000
, Preferably in the range of 700 to 4000.

The plasticizer contained in the vinyl chloride resin composition of the present invention can soften the composition to facilitate kneading and processing. The plasticizer is not particularly limited as long as it is commonly used for vinyl chloride resins. For example, dibutyl phthalate (DBP), dihexyl phthalate, di-2-ethylhexyl phthalate (D
OP), phthalate plasticizers such as di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate, butylbenzyl phthalate, or phthalate esters of higher alcohols or mixed alcohols having about 11 to 13 carbon atoms; Di-2-ethylhexyl adipate, di-n-octyl adipate, di-n
-Decyl adipate, diisodecyl adipate, di-2
Aliphatic dibasic acid ester-based plasticizers such as -ethylhexyl azelate, dibutyl sebacate and di-2-ethylhexyl sebacate;

Tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellitate, etc. Trimellitic ester plasticizers, tributyl phosphate, tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tribubutoxyethyl phosphate, trichloroethyl phosphate, Tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate Feto, bis (2, 3
Phosphate plasticizers such as -dibromopropyl) -2,3-dichloropropyl phosphate and bis (chloropropyl) monooctyl phosphate;

2,3,3 ', 4'-biphenyltetracarboxylic acid tetraheptyl ester and other biphenyltetracarboxylic acid tetraalkyl ester plasticizers; polyester polymer plasticizers; epoxidized soybean oil, epoxidized linseed oil Epoxidized cottonseed oil, epoxy plasticizers such as liquid epoxy resin, etc .; chlorinated paraffins; chlorinated fatty acid esters such as alkyl pentachloride stearic acid ester; and the like, or a mixture of two or more thereof. I do.

Although the content of the plasticizer varies depending on the type of the vinyl chloride resin, the type and the amount of the other additives, etc., the content of the plasticizer is 20 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin. Parts, preferably in the range of 30 to 150 parts by weight, particularly in the range of 30 to 120 parts by weight. When the content of the plasticizer is less than 20 parts by weight, a sufficient plasticizing effect cannot be obtained, and the composition does not become a soft composition.
If the amount is more than the weight part, problems such as bleeding of the plasticizer occur.

In the vinyl chloride resin composition of the present invention, the presence of a phosphoric acid metal salt holding silver ions is essential.
Examples of the metal of the metal phosphate include aluminum, zirconium, calcium, titanium, and the like, and the metal phosphate also includes a phosphate of calcium containing a hydroxyl group, that is, a phosphate such as hydroxyapatite. It is. In addition, silver ions are usually ion-exchanged in a metal phosphate,
It is held in an adsorbed or intercalated state.

When a metal phosphate containing silver ions is contained in a vinyl chloride resin composition, discoloration due to heat or light is caused by the combined use with a heat stabilizer and a carbonate of a specific metal described later. The effect is small, and the antibacterial performance is excellent for a long time. The content of the metal phosphate holding silver ions is 0.00.0 parts by weight based on 100 parts by weight of the vinyl chloride resin.
It is in the range of 1 to 10 parts by weight. If the content is less than 0.01 part by weight, the antibacterial effect is hardly exhibited, and if added in excess of 10 parts by weight, no remarkable increase in the antibacterial effect is observed, which is economically disadvantageous.

In the present invention, it is essential that the vinyl chloride resin composition contains a heat stabilizer. In particular, a heat stabilizer containing 10% by weight or more of a fatty acid zinc is desirable. That is, the heat stabilizer may be used alone or as a composite stabilizer containing zinc. Fatty acids that bind to zinc are, for example, stearic acid, palmitic acid, lauric acid, octanoic acid, ricinoleic acid, 2-ethylhexoic acid, naphthenic acid, and the like, and the fatty acids are not limited to those described above. Further, as a heat stabilizer, a barium-zinc composite stabilizer, a calcium-zinc composite stabilizer, an aluminum-magnesium-zinc composite stabilizer and the like can be used, and the zinc fatty acid constituting these composite stabilizers is , Stearic acid, lauric acid, ricinoleic acid, 2-ethylhexoic acid, naphthenic acid and the like.

The heat stabilizer is not limited to the above-mentioned stabilizers, but preferably contains at least one kind of the above-mentioned stabilizers. It is appropriately used in the range of 1 to 10 parts by weight with respect to parts by weight. If the content is less than 1 part by weight, the heat stability during processing and molding remains uneasy, and the discoloration after long-term use is also poor. Moreover, even if it exceeds 10 parts by weight, it is economically disadvantageous. Some heat stabilizers contain metals such as cadmium, lead, and tin, and have the same effect.However, those containing cadmium, lead, etc. are harmful, and tin-based stabilizers have odors. However, it is desirable to avoid these uses.

The vinyl chloride resin composition of the present invention requires the presence of at least one of calcium, magnesium or aluminum carbonate, silicate or hydroxide together with the heat stabilizer. These compounds include:
For example, calcium carbonate, magnesium carbonate, aluminum carbonate, calcium silicate, magnesium silicate, aluminum silicate, calcium hydroxide, magnesium hydroxide,
Examples thereof include aluminum hydroxide or a compound composed of a carbonate, silicate or hydroxide containing two or more kinds of the above metals, for example, basic magnesium aluminum hydroxy carbonate (hydrotalcite). Hydrotalcite is also used as a heat stabilizer, and when it is used for the purpose of the heat stabilizer, it is used in the above-mentioned range of the amount of the heat stabilizer used.

These compounds are usually used as fillers for synthetic resins.
(1) enhance the dispersibility of the metal phosphate holding silver ions and exhibit its antibacterial effect for a long period of time; (2) make the light discoloration resistance due to the provision of opacity less noticeable; (3) extrudability; Effects such as improvement of injection moldability and (4) improvement of economic efficiency are exhibited. Thus, the addition amount of these compounds is preferably in the range of 5 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin. When the amount is less than 5 parts by weight, the above-mentioned effects cannot be sufficiently exhibited, and when the amount exceeds 200 parts by weight, there occurs a problem that the mechanical properties of a molded article obtained by molding the composition are deteriorated, It is easy to impair product value.

The vinyl chloride resin composition of the present invention may contain, if necessary, an electric insulation improver such as clay, a filler other than those described above, a moldability improver such as an acrylic resin, a lubricant,
Various additives, such as an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a foaming agent, a colorant, and an impact modifier, are used in a range which is usually used for a vinyl chloride resin. You may mix | blend in the range which does not impair physical properties. Also,
A thermoplastic resin other than the vinyl chloride resin, a synthetic rubber, or the like may be added.

The vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a plasticizer, a metal phosphate containing silver ions, a heat stabilizer, and a carbonate, silicate or hydroxide of calcium, magnesium or aluminum. Is charged into a predetermined mixer or kneader, if necessary, in a temperature range where the vinyl chloride resin does not deteriorate, for example, 100 to 230 ° C., preferably 13
It is easily prepared by uniformly mixing or kneading while heating to a temperature of 0 to 230 ° C.

The mixer or kneader used for mixing or kneading for mixing the above-mentioned components is not particularly limited as long as it can substantially uniformly mix and knead the compound. Examples thereof include a Henschel mixer, a ribbon blender, and a planetary mixer. Examples of the kneading machine include a single-screw extruder, a twin-screw extruder, a roll mill, a Banbury mixer, a kneader, and an intensive mixer while heating. The following can be kneaded. The vinyl chloride resin composition of the present invention may be in the form of a powder or a pellet.

The vinyl chloride resin composition of the present invention can be prepared by using various molding methods such as extrusion molding, injection molding, inflation molding, rotational molding, press molding, calendering, etc. It is formed into molded products as interior / exterior material parts for construction, household electric appliance parts, etc. Also,
It is also effectively used as a material for covering electric wires. Further, the vinyl chloride resin composition of the present invention is a co-extrusion method of laminating another resin or metal in a die or in the vicinity of the outside of the die,
The above-described parts may be manufactured using a molding method such as an insert injection molding method or a simultaneous injection molding method.

[0022]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless departing from the gist thereof. In addition, the antibacterial property test and the light resistance test with respect to the vinyl chloride resin composition were performed as follows, and the results are shown in Table 1.

[0023]

[Table 1] Antibacterial test; 1 ml of a test bacterial solution was dropped on a sample (molded resin plate), and the relative humidity was 99% and the temperature was 25.
℃, immediately after dropping, after storage for 6 hours and 24 hours.
Measure the number of viable bacteria on the specimen at or after storage. For the measurement, the specimen was washed out with 100 ml of a phosphate buffer solution containing 0.85% salt, and the viable cell count of this solution was measured by a mixed dilution plate culture method using a normal agar medium, and the viable cell count per specimen was determined. Was converted to The test bacterial solution used was E. coli.
(Escherichia coil IFO 3301) and Staphylococcus aureus (Sta
phylococcus aureus IFO 12732)
Diluted with 0.85% saline buffer solution, about 10 ⁵
It was adjusted to 10 ⁶ cells / ml.

[0024]

[Table 2] Light discoloration resistance: Irradiation was performed for 200 hours under the condition of a black panel temperature of 83 ° C using a light resistance tester manufactured by Suga Test Instruments Co., Ltd. (Fal-5H type). The degree of discoloration of the test piece before and after irradiation was visually determined. ◎: Almost no discoloration and no problem in practical use ：: Slight discoloration but not enough to cause a problem in practical use ×: Discolored and difficult to be put to practical use

Examples 1 to 8, Comparative Examples 1 to 3 100 parts by weight of vinyl chloride resin (PVC, manufactured by Mitsubishi Chemical Corporation) having an average degree of polymerization of 800, 40 parts by weight of di-2-ethylhexyl phthalate (DOP), epoxidized soybean oil 3 parts by weight, 2 parts by weight of a barium-zinc composite stabilizer (stabilizer) containing 15% by weight of zinc stearate and 1 part by weight of an ultraviolet absorber, and antibacterial agents of the type and amount (parts by weight) described in Table 1; Calcium carbonate (CaCO ₃ ), aluminum silicate (Al ₂
After uniformly mixing SiO ₅ ) and magnesium hydroxide (Mg (OH) ₂ ) in a beaker, 9
The sheet was transferred to an inch mill roll and kneaded for 5 minutes to prepare a sheet. The sheet was further subjected to hot pressing at 180 ° C. for 5 minutes to prepare a sheet having a thickness of 1 mm, which was subjected to an antibacterial test and a light resistance test. The results are shown in Table 1.

The following antibacterial agents were used. <Metal phosphate metal salt holding silver ion> Antibacterial agent A: silver-aluminum polyphosphate (Rasap AN60
Antibacterial agent B: silver-zirconium phosphate (NOVALON AGT330,
Toagosei Co., Ltd.) Antibacterial agent C: Silver-hydroxyapatite (Antibacterial Cera P-02,
(Shinto V CELLAX) <Silver compounds other than metal phosphate> Antibacterial agent D: Silver-zeolite (Zeomic AJ10D, Sinanen Zeomic)

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

The vinyl chloride resin composition of the present invention can be obtained by using a metal phosphate, a heat stabilizer and a carbonate, silicate or hydroxide of a specific metal together with silver ions.
Demonstrates antibacterial performance over a long period of time, has excellent properties such as heat resistance and light discoloration resistance, and has no odor, and is highly safe.
Vehicle interior and exterior parts, construction interior and exterior parts, home appliance parts,
It is suitably used as a material for resin-coated electric wires and the like, particularly for resin molded articles that come into contact with the human body.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/10 C08K 5/10 5/51 5/51

Claims (2)

[Claims] 1. A vinyl chloride resin, 20 to 200 parts by weight of a plasticizer per 100 parts by weight of the resin, 0.01 to 10 parts by weight of a metal phosphate holding silver ions, 1 to 10 parts of a heat stabilizer.
A vinyl chloride resin composition comprising 5 parts by weight and 5 to 200 parts by weight of at least one selected from carbonate, silicate and hydroxide of calcium, magnesium or aluminum. 2. The vinyl chloride resin composition according to claim 1, which is a heat stabilizer containing at least 10% by weight of a fatty acid zinc.