JPS625188B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyvinyl chloride resin composition, and its purpose is to provide a polyvinyl chloride resin composition that has excellent heat resistance, initial coloring resistance, water resistance, processability, and other various properties. It is in. Polyvinyl chloride resin has various problems such as significant discoloration and decomposition due to heat during processing, and deterioration with long-term use, so various stabilizers are added to polyvinyl chloride resin. It has become customary to do so. Traditionally used lead-based stabilizers such as tribasic lead sulfate, tribasic lead maleate, and lead stearate, as well as stabilizers such as cadmium stearate, have excellent performance, but their toxicity is a problem. In recent years, various non-toxic or low-toxic stabilizers have been proposed to replace these, and have come into widespread use in practice. Various compounds such as barium, calcium, magnesium, and zinc, organic tin compounds, organic phosphorous compounds, and epoxy compounds are used as such stabilizers, and many combinations of these have been proposed, but they are not practical. It is not completely satisfactory. In particular, recently, in addition to improving general stabilizer performance such as heat resistance, initial coloring resistance, weather resistance, etc., improvements have been made in terms of dispersibility and compatibility with resins, water resistance, etc.
There is a demand for various performance improvements such as workability, strength and appearance of the product. In order to meet the above-mentioned severe demands, the inventors of the present invention have finally completed the present invention after extensive research into the selection and combination of specific compounds from a wide variety of stabilizer compounds and additive components. It came to this. The present invention provides (a) for 100 parts of polyvinyl chloride resin.
0.1 to 2.5 parts of basic magnesium carbonate, (b) 1 selected from alkaline earth metal salts and zinc salts of organic acids
A polyvinyl chloride resin composition containing 0.1 to 5 parts of a species or two or more compounds, (c) 0.1 to 5 parts of dipentaerythritol, and (d) 0.1 to 10 parts of a lubricant,
By such a formulation, a composition with excellent heat resistance, initial coloring resistance, water resistance, and processability can be obtained for the first time, and the stabilizer component also has good dispersibility and compatibility with the resin. This made it possible to obtain products with great strength and beautiful appearance. Good results cannot be expected when an alkaline earth metal hydroxide such as normal magnesium carbonate, magnesium hydroxide, or calcium hydroxide is used in place of the basic magnesium carbonate in the above-mentioned components. In the former case, heat resistance deteriorates, and in the latter case, initial coloring resistance decreases. Basic magnesium carbonate is usually 3-
It is expressed as 5MgCO ₃ .Mg(OH) ₂ .3 - 7H ₂ O, and can be obtained by methods such as the carbon ammonium method, the soda ash method, and the water mug (gas method). The preferred amount is in the range of 0.1 to 2.5 parts per 100 parts of the resin, and if it is in excess, there is a risk of coloring. Furthermore, if other polyhydric alcohol components are used instead of dipentaerythritol, the compatibility with the resin will be insufficient, the miscibility with plasticizers and lubricants will also be unsatisfactory, and temporary overheating may occur during processing. There is also a tendency for other stabilizers to precipitate at the bottom. Additionally, polyhydric alcohols may precipitate on the surface of the molded product, leading to a decline in the quality of the final product.
It also has the disadvantage of poor workability. For example, pentaerythritol has extremely high water solubility and strong sublimation properties, and during molding, the sublimate solidifies and accumulates on the sizing die, making it difficult to continue production. The preferred amount of dipentaerythritol is 0.1 to 5 parts per 100 parts of polyvinyl chloride resin; if it is less than this range, the heat resistance and initial coloring resistance will not be sufficient, and if it is too much, it will be difficult to process. There is a risk of harming your sexuality. As the alkaline earth metal salt of an organic acid, the metal component is calcium, magnesium, barium, or strontium, and the organic acid component is benzoic acid, salicylic acid, pt-butylbenzoic acid, lauric acid, myristic acid, Preferred are palmitic acid, stearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, neodecanoic acid, 2-ethylhexoic acid, naphthenic acid, carbolic acid, octylcarboxylic acid, nonylcarboxylic acid, and the like. Zinc salts include zinc benzoate, zinc salicylate, zinc pt-butylbenzoate, zinc laurate, zinc myristate, zinc valmitate, zinc stearate, zinc isostearate, zinc behenate, zinc ricinoleate, and linoleic acid. Examples include zinc acid, zinc linoleate, zinc oleate, zinc neodecanoate, zinc 2-ethylhexoate, zinc behenate, and zinc naphthenate. Any of these may be used in combination of two or more. In addition, the preferred amount of these organic acid metal salts is 0.1 to 5 parts; if it is less than this range, the heat resistance and initial coloring resistance will not be sufficient, and if it is too much, it will cause bubbling on the surface of the molded product. There is a possibility that it will come. Suitable lubricant components include hydrocarbons such as liquid paraffin, micro wax, polyethylene wax, etc. fatty acids such as higher fatty acids such as stearic acid and oxyfatty acids, and fatty acid amides or esters. Stearic acid amide, palmitic acid amide, methylene bis stearamide, ethylene bis stearamide, oleic acid amide, lower alcohol ester, polyhydric alcohol ester, fatty acid polyglycol ester, butyl stearate, hydrogenated castor oil, ethylene glycol monostearate Examples of alcohols include cetyl alcohol and stearyl alcohol. The preferred amount of these lubricants is 0.1 to 10 parts; if the amount is less than this range, the lubricity and processability will be poor and the appearance of the molded product will be adversely affected, and if the amount is too much, the strength of the product will be reduced. In addition to the above-mentioned components, the composition of the present invention may contain various other stabilizers and stabilizing aid components, such as organic phosphite esters, acid phosphite esters, etc. for the main purpose of improving heat resistance. ,
Epoxidized soybean oil, epoxy resin, sulfur-containing compounds such as dilauryl thiodipropionate, bisphenol A, 2,6-di-t-butyl-4-methylphenol, 2-phenylindole, 1,4
Compositions incorporating antioxidants comprising organic compounds such as -butanediol-bis-β-aminocrotonate and nitrilotriacetic acid are preferred embodiments of the present invention. In addition to these, fillers, plasticizers, foaming agents,
It goes without saying that it may contain various commonly used additives such as antistatic agents, flame retardants, surfactants, colorants, mold release agents, viscosity modifiers, antifungal agents, and ultraviolet absorbers. The formulation should be determined appropriately depending on the intended properties and use. Below, performance test results for various formulations of the composition of the present invention are shown together with reference examples. Example 1 Calcium stearate 0.4 parts, zinc stearate 1.0 parts for 100 parts by weight of polyvinyl chloride resin
1.0 parts, dipentaerythritol 1.0 parts, butyl stearate 1.0 parts, titanium oxide 0.3 parts, and the specified amounts of the inorganic compounds shown in Table 1 were added, and the roll temperature was increased.
The mixture was kneaded at 170°C for 5 minutes to form a sheet with a thickness of 0.2 mm. This sheet was then pressed at 170°C for 5 minutes to evaluate its initial colorability. Further, the heat resistance was evaluated by measuring the time until blackening of the sheet in a gear oven at 180°C. To measure the chlorine capture ability, cut the sheet into small pieces, put 2g of this into a test tube, and fix Congo Red test paper at the tube opening.
The test tube was immersed in an oil bath maintained at 180°C, and the time required for the test paper to turn blue due to hydrogen chloride generation due to thermal decomposition was measured and evaluated.

[Table] Example 2 For 100 parts by weight of polyvinyl chloride resin, 0.5 parts of basic magnesium carbonate, 0.4 parts of calcium stearate, 1.0 parts of zinc stearate, 1.0 parts of low molecular weight polyethylene wax, 5.0 parts of calcium carbonate, and Table 2. Heat resistance and initial coloring resistance were tested in the same manner as in Example 1 by adding a predetermined amount of the indicated polyhydric alcohol. In addition, the sheet after roll kneading was placed in water at 100°C to evaluate the water elution property by measuring the elution of organic substances, and on the other hand, the blended composition was extruded at a temperature of 180 to 200°C, and the build-up resistance during processing was evaluated. was tested.

【table】

[Table] Example 3 To 100 parts by weight of polyvinyl chloride resin, add 1.5 parts of basic magnesium carbonate, 0.8 parts of dipentaerythritol, 5.0 parts of talc, and the specified amounts of the organic acid salts and lubricants shown in Table 3, and prepare Brabender. Dynamic heat resistance and lubricity were measured using a Plasticorder manufactured by Co., Ltd. The results are shown in Table 3.

[Table] Example 4 For 100 parts by weight of polyvinyl chloride resin, 50 parts of dioctyl phthalate, 2.0 parts of epoxidized soybean oil,
Heat resistance and initial coloring were determined in the same manner as in Example 1 by adding 0.5 part of triphenyl phosphite, 0.4 part of barium nonylphenolate, 0.8 part of zinc stearate, and the specified amounts of polyhydric alcohols and metal salts shown in Table 4. Tested.

【table】

Claims (1)

[Claims] 1 For 100 parts of polyvinyl chloride resin, (a) 0.1 to 2.5 parts of basic magnesium carbonate, (b) 0.1 to 5 parts of one or more compounds selected from alkaline earth metal salts and zinc salts of organic acids. (c) 0.1 to 5 parts of dipentaerythritol, and (d) 0.1 to 10 parts of a lubricant.