JPS5938981B2 - Chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plasticized chlorine-containing resin composition having excellent heat resistance and weather resistance.

Plasticized chlorine-containing resin is a plastic material used in a wide range of applications, but it has low stability against heat and light, and when molded products made of this material are used outdoors, their mechanical strength decreases and cracks occur. It has drawbacks such as coloring, sticky surface, etc.

In order to eliminate these drawbacks, molding is performed by adding tin-based stabilizers, antioxidants, ultraviolet absorbers, etc. to chlorine-containing resins, but there are no products that have improved all of the above drawbacks. I haven't gotten it yet.

In view of the above-mentioned drawbacks, the present invention was developed as a result of intensive studies to obtain a plasticized chlorine-containing resin that has excellent weather resistance and heat resistance stability, and is non-toxic. This invention was made based on the discovery that when a specific substance is further added to a plasticized chlorine-containing resin composition containing a derivative, the stability against heat and light is significantly improved. That is, the gist of the present invention is to add a chlorine-containing resin, a plasticizer, calcium soap, zinc soap,
It exists in a chlorine-containing resin composition to which a polyhydric alcohol or a partial ester derivative of a polyhydric alcohol, a zinc chelate complex compound, and zinc oxide are added.

The chlorine-containing resin used in the present invention is a resin containing chlorine in its molecules, such as polyvinyl chloride,
Polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride or a copolymer mainly composed of vinylidene chloride with ethylene, vinyl acetate, acrylic acid ester, acrylontrile, etc., chlorinated polyvinyl chloride, chlorinated polyethylene etc. can be mentioned.

As the plasticizer used in the present invention, any plasticizer that is normally used for plasticizing chlorine-containing resins can be used, and specific examples thereof include dioctyl adipate, dioctyl balmitate, dioctyl sebacate,
Examples include butyl ricinoleate, dioctyl phthalate, diisodecyl phthalate, synchhexyl phthalate, dihexyl phthalate, ethylene glycol dibenzoate, triethylene glycol benzoate, etc.
These may be used alone or in combination of two or more.

The amount added is not particularly limited, but depending on the purpose, it may be 20 to 20 parts by weight per 100 parts by weight of the chlorine-containing resin.
Generally, 100 parts by weight is added. Further, the calcium soap or zinc soap used in the present invention is a higher fatty acid salt of calcium or zinc, such as calcium stearate, calcium laurate, calcium ricinoleate, zinc stearate, zinc laurate,
Examples include zinc ricinoleate, zinc 2-ethylhexoinate, etc. The amount added is not particularly limited, but calcium soap is 0.00 parts by weight per 100 parts by weight of chlorine-containing resin.
It is preferable to add 0.05 to 10 parts by weight, and 0.1 to 5.0 parts by weight of zinc soap.

The polyhydric alcohol used in the present invention is a compound having multiple hydroxyl groups in its molecule, such as pentaerythritol, dipentaerythritol, mantol, solpeel, glycerin, etc., and partial esters of polyhydric alcohols. The derivative refers to a partial ester in which the polyhydric alcohol is partially esterified with an organic acid, and one or more hydroxyl groups remain.

Polyhydric alcohols and partial ester derivatives of polyhydric alcohols may be used alone or in combination of two or more, but a mixture of polyhydric alcohols and partial ester derivatives of polyhydric alcohols is preferred. More preferably, the mixture is a melt-mixed mixture. Further, the amount of polyhydric alcohol or polyhydric alcohol partial ester derivative added is not particularly limited, but chlorine-containing resin 10
It is preferable to add 0.1 to 7.5 parts by weight per 0 parts by weight. The organic acid mentioned above is not limited in any way as long as it can react with the hydroxyl group of a polyhydric alcohol to produce an ester compound, but the stabilizing effect decreases as the number of carbon atoms in the organic acid increases. Therefore, those with 10 or less are preferable, such as acetic acid, propionic acid, butyric acid,
Saturated monocarboxylic acids such as valeric acid, caproic acid, natonic acid, hydrofuric acid, pelargonic acid, and hydropurinic acid; unsaturated monocarboxylic acids such as acrylic acid, crotonic acid, angelic acid, and allyl acetic acid; oxalic acid and malonic acid. , saturated dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, and unsaturated dicarboxylic acids such as maleic acid. In the present invention, a zinc chelate complex compound formed by bonding a ligand to zinc is used, but the compound is preferably a compound in which two or more sulfur ligands are bonded to zinc; for example, a compound having the general formula (In the above formula, Rl, R2
, R3, and present are each a hydrocarbon group having 1 to 18 carbon atoms.

Zinc dithiocarbamates represented by the general formula (in the above formula, R5 and R6 are each a hydrocarbon group having 1 to 18 carbon atoms).

) Zinc dixanthates represented by the general formula (wherein R7 and R8 are each hydrogen or a substituent such as an optionally plural alkyl group) 2
- Zinc salts of mercaptobenzimidazole and the like are preferred.

Examples of the hydrocarbon groups R1 to R6 include alkyl groups, allyl groups, and cycloalkyl groups.
and more specifically, zinc diethyldithiocarbamate, zinc dipropyldicarbamate, zinc dibutyldithiocarbamate, zinc dioctyldithiocarbamate,
Zinc dithiocarbamates such as zinc distearyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc synchro/xyldithiocarbamate, zinc ethylxanthate, zinc butylxanthate, zinc octylxanthate, zinc stearylxanthate,
Zinc dixanthates such as zinc benzylxanthate, zinc cyclohexylxanthate, zinc citalopentylxanthate, zinc salt of 2-mercaptobenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptoethylbenzimidazole Examples include zinc salts of 2-mercaptobenzimidazoles, such as zinc salts and zinc salts of 2-mercaptobutylbenzimidazole.

The zinc chelate complex compound is preferably added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.

Furthermore, although the zinc oxide used in the present invention has properties that improve the weather resistance of the resin, it can also improve the composition by interacting with additives such as the zinc chelate complex compound. It has the ability to provide added weather resistance.

The amount of zinc oxide added is preferably 0.2 to 10 parts by weight per 100 parts by weight of the chlorine-containing resin, and the particle size thereof is preferably smaller. To obtain the chlorine-containing resin composition of the present invention, the chlorine-containing resin, a plasticizer,
Calcium soap, zinc soap, polyhydric alcohol or partial ester derivative of polyhydric alcohol, zinc chelate complex compound, and zinc oxide may be added together and mixed, kneaded, etc. in a conventional manner to form a composition. Antistatic agents, surface treatment agents, ultraviolet absorbers, flame retardants, pigments, anti-blackening agents, etc. may be added as necessary.

Since the chlorine-containing resin composition of the present invention has the above-mentioned structure, the added calcium soap, zinc soap, polyhydric alcohol or partial ester derivative of polyhydric alcohol, zinc chelate complex compound, and zinc oxide can be mixed together. This action imparts excellent heat resistance and weather resistance to the plasticized chlorine-containing resin composition, thereby preventing the occurrence of cracks and discoloration during outdoor use, and also preventing the surface from becoming sticky. This significantly improves the performance of the composition.

Next, examples of the present invention will be described.

In the following, parts simply refer to parts by weight. Example 1 and Comparative Examples 1 to 5 100 parts of vinyl chloride resin with a degree of polymerization of 1100, 50 parts of dioctyl phthalate, 0.3 parts of calcium stearate,
0.6 parts of zinc stearate, 2.0 parts of a molten mixture of dipentaerythryl and its monoacetate ester, 0.5 parts of zinc dibutyldithiocarbamate, 1.0 parts of zinc oxide.
After uniformly dispersing and mixing 0 parts and 0.1 parts of phthalocyan blue, kneading was carried out for 3 minutes with a 150°C kneading roll, and then pressed for 4 minutes with a press at 180°C to create a test piece with a thickness of 1 mm. did.

The resulting test piece was irradiated with a high-pressure mercury lamp, and the time it took for the piece surface to become sticky (stickiness onset time) and the time it took for it to turn black (blackening time) were measured; the former was 3.
000 hours, and the latter 2500 hours.

Further, when the test piece was exposed outdoors, no change was observed after 24 months. In addition, for comparison, we prepared a composition in which each of zinc stearate, dipentaerythritol and its monoacetate ester, zinc dibutyldithiocarbamate, and zinc oxide were omitted from the above composition, and this composition was treated in the same manner as above. I made a test piece and tested it. The results were as shown in Table 1.

Examples 2 to 8 Test pieces were prepared in the same manner as in Example 1, except that a zinc chelate complex compound shown in Table 2 was used in place of zinc dibutyldithiocarbamate in Example 1. I did a test.

Claims (1)

[Scope of Claims] 1. A chlorine-containing resin composition in which a plasticizer, a calcium soap, a zinc soap, a polyhydric alcohol or a partial ester derivative of a polyhydric alcohol, a zinc chelate complex compound, and zinc oxide are added to a chlorine-containing resin. 2. The composition according to item 1, wherein the zinc chelate complex compound is a compound having two or more sulfur ligands. 3. The composition according to item 2, wherein the zinc chelate complex compound is a zinc dithiocarbamate. 4. The composition according to item 2, wherein the zinc chelate complex compound is a zinc dixanthate. 5. The composition according to item 2, wherein the zinc chelate complex compound is a zinc salt of 2-mercaptobenzimidazole. 6 The amount added to 100 parts by weight of chlorine-containing resin is 20 to 100 parts by weight of plasticizer and 0.05 to 10 parts by weight of calcium soap.
parts by weight, zinc soap 0.1-5 parts by weight, polyhydric alcohol or partial ester derivative of polyhydric alcohol 0.1-7.
5 parts by weight, 0.01 to 5 parts by weight of the zinc chelate complex compound, and 0.2 to 10 parts by weight of zinc oxide.