JPS6327546A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved heat-stability in molding and discoloration resistance and chalking property of molded article and suitable as canvas, tarpaulin, etc., by compounding specific amounts of zinc oxide, zinc dithiocarbamate, etc., to a base resin. CONSTITUTION:100pts.(wt.) of a vinyl chloride resin is compounded with (B) 0.1-10pts., preferably 0.5-7pts. of zinc oxide, (B) 0.05-5pts., preferably 0.25-3pts. of a zinc dithiocarbamate of formula (R1 and R2 are 1-18C alkyl, phenyl, etc.) (e.g. zinc dimethyldithiocarbamate), (C) 0.3-5pts., preferably 0.5-3pts. of a polyhydric alcohol (e.g. trimethylolpropane) or a partial ester of polyhydric alcohol and (D) 0.1-7pts., preferably 0.5-5pts. of one or more components selected from hydrotalcite, magnesium oxide, magnesium hydroxide and barium soap.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a vinyl chloride resin composition with improved heat resistance and weather resistance. The present invention relates to a vinyl chloride resin composition with improved heat resistance stability and discoloration, deterioration, and chalking properties (chalking) of molded articles.

(Prior art and its problems) Polyvinyl chloride resin used for canvases, tarpaulins, vehicle parts, cocoon weights, decking materials, wall materials, window frames, etc. will change color, deteriorate, etc. when exposed to ultraviolet rays or sunlight. Since it is easy to cause a chalking phenomenon, M
Organic UV absorbers have been used. However, these M-type ultraviolet absorbers have the drawback of being expensive and having little improvement effect.

On the other hand, it has been proposed that the combination of the ultraviolet absorbing effect of zinc oxide and zinc dithiocarbamate has a mutually beneficial effect in improving weather resistance. The combination of zinc oxide and zinc dithiocarbamate significantly improves weather resistance, but when a large amount of zinc compound is blended with vinyl chloride resin, zinc accelerates the blackening of polyvinyl chloride resin (zinc burning). This phenomenon has the disadvantage of causing heat discoloration during molding. Although zinc oxide and zinc dithiocarbamate combination systems have excellent weather resistance, no method has yet been found to sufficiently suppress the zinc perning phenomenon. / Limited to polyvinyl chloride resin applications.

(Means for Solving the Problems) The present inventors have conducted research on polyvinyl chloride resin compositions containing zinc oxide and zinc dithiocarbamate, which have excellent heat resistance (non-tempering) and weather resistance. As a result, the present invention was completed.

That is, the present invention provides (a) zinc oxide, (b) an alkyl group having a dithiocarpamine number of 1 to 18, a phenyl group, or a cyclohexyl group represented by the structural formula [''I]) (C) for vinyl chloride resin. Provided is a vinyl chloride resin composition comprising a polyhydric alcohol or a partial ester of a polyhydric alcohol, and (d) one or more compounds selected from barium soap, magnesium oxide, magnesium hydroxide, and hydrotalcites. It's about doing.

(Structure of the present invention) As the vinyl chloride resin used in the present invention, there are, in addition to monoa polymers of vinyl chloride, copolymers with monomers that can be copolymerized with vinyl chloride. Copolymers for vinyl chloride include ethylene, propylene, vinyl acetate, styrene, vinyltoluene, acrylic acid, alkyl acrylates (such as methyl acrylate, ethyl acrylate,
butyl acrylate, 2-ethylhexyl acrylate, etc.) % methacrylic acid, alkyl methacrylate (e.g. methyl methacrylate, ethyl methacrylate,
butyl methacrylate, 2-ethylhexyl methacrylate, etc.).

In addition, the vinyl chloride resin is blended with acrylonitrile-butadiene-styrene copolymer, alkyl methacrylate-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate vinyl chloride copolymer, urethane resin, etc. be able to.

The zinc oxide (a) used in the invention may be produced by any of the French fP (indirect method), American method (direct method), and wet method, but if the particles are fine < (0
,01μ~1. Oa preferably O,l p ~0.4μ
), preferably one made by the French method, which has high purity.1. /
0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, and less than 0.1 parts by weight based on 100 parts by weight of polyvinyl chloride resin, there is no effect of improving weather resistance;
If the amount is more than 10i, thermal properties will be significantly lowered by 1liit, which is not preferable.

Zinc dithiocarbamate (b) of structural formula [1) used in the present invention includes zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc dibutyldithiocarbamate,
Zinc dioctyl dithiocarbamate, zinc distearyldithiocarbamate, zinc phenyl ethyl dithiocarbamate, zinc phenyl butyl dithiocarbamate,
Zinc phenyl octernotiorupamate, zinc phenylstearyldithiocarbamate, zinc nophenyldithiorupamate, zinc dicyclohexyldithiocarbamate, etc., and the amount used is from 0.05 parts by weight to 5 parts by weight.
It is preferably 0.25 parts by weight to 3.0 parts by weight. If it is less than 0.05 parts by weight, the effect of improving weather resistance will be small, and if it is more than 5 parts by weight, heat resistance will be reduced and the odor caused by the dithiocarbamic acid group will be strong, impairing the working environment and the quality of molded products.

The polyhydric alcohol (C) used in the present invention is one having three or more hydroxyl groups in the molecule, such as trimethylolpropane, glycerin, diglycerin, -entaerythritol, dipentaerythritol, mannitol, Sorbitol, tetrahydroxyethyl isocyanurate, etc. In addition, the partial ester of polyhydric alcohol refers to a compound in which the polyhydric alcohol is partially esterified with an organic acid, and has two or more remaining hydroxyl groups, and as an organic acid, it reacts with the hydroxyl group of the polyhydric alcohol. There are no limitations as long as an ester can be produced. Examples of organic acids include monocargenic acids such as acetic acid, propionic acid, and octylic acid; unsaturated monocargenic acids such as acrylic acid and crotonic acid; malonic acid;
Saturated dicardic acids such as phosphoric acid and adipic acid, maleic acid,
Examples include unsaturated nocardanoic acids such as fumaric acid, and aminocarzanoic acids such as methionine. The amount used is 0,
3 parts by weight to 5 parts by weight, preferably 0.5 parts by weight to 3.0 parts by weight
If it is less than 0.3 parts by weight, the effect of improving heat resistance will be small, and if it is more than 5.0 parts by weight, it will inhibit compatibility with polyvinyl chloride and cause plume or plate-out phenomena, which is not preferable.

The hydrotalcite as component (a) used in the present invention is a double salt compound consisting of magnesium and aluminum represented by the following general formula [■].

Mg, -xAtx(OH)2CO3x7n-mH2
0CII ] In the above formula, Q It is more preferable. Also, as barium soap (d),
Higher fatty acid salts of Noronium, such as barium octylate, barium laurate, barium stearate,
These include barium oleate, barium benzoate, and barium salts of these derivatives.

Addition of one or more types of barium soap is an essential component that suppresses zinc and graining without impairing weather resistance, but preferably hydrotalcites are not necessarily included in component (d). It is desirable that the proportion of hydrotalcites in component (d) is at least 20
Preferably, it contains 0 parts by weight or more. In addition, C. ``When combining magnesium oxide, magnesium hydroxide, and barium soap without using dorotalcites, it is desirable to use two or more types in combination. 6 Regarding polyvinyl chloride resin (
The amount of component d) used is from 01 parts by weight to 7 parts by weight, preferably from 0.5 parts by weight to 5 parts by weight; if it is less than 0.1 parts by weight, the effect of improving heat resistance will be small, and if it is more than 7 parts by weight, This is not preferable because it inhibits compatibility with polyvinyl chloride resin and causes plate-out phenomenon and poor dispersion.

In order to obtain the vinyl chloride resin composition of the present invention, the above (a)
) zinc oxide, (b) zinc dithiocarbamate represented by formula [1], (c) polyhydric alcohol or partial ester of polyhydric alcohol, and (d) /hydrotalcites,
One or more types of magnesium oxide, magnesium hydroxide, and barium soap are added together and mixed in a conventional manner.
The composition may be prepared by mixing wires, etc. In this case, commonly used plasticizers, colorants, fillers, lubricants, zinc soaps, calcium soaps, organic tin compounds, antistatic agents, ultraviolet absorbers, flame retardants, etc. may be added as necessary.

(Effects of the present invention) The composition of the present invention has excellent heat resistance during processing and weather resistance of molded products, so it can be used in applications where it is exposed to ultraviolet rays or sunlight, such as canvas, tarpaulin, and sheets for building materials. , iron wire and steel pipe plugging materials, vehicle parts, rain gutters, decking materials, wall materials,
M is used for window frames, signboards, etc.

The following examples show the effects of the vinyl chloride resin composition according to the present invention, but the present invention is not limited to these examples. The term "bu" below refers to the "jujobu" section.

Examples 1 to 9 and Comparative Examples 1 to 5 After uniformly mixing 100 parts of polymerized LFF-800 vinyl chloride resin with the formulation shown in Table 1, it was mixed with a kneading roll at 180°C for 5
Knead for a minute and remove the sheet. This sheet was used for one day, and its thermal stability in an open environment at 190°C was examined. On the other hand, the sheet taken out from the mixed wire roll was pressed and a 1 mm thick press sheet was exploded. The obtained press sheet was subjected to a Sunshine Wederometer and an outdoor Bacro test to examine its colorability. The results are shown in Table 1.

Examples 10 to 16 and shell ratio examples 6 to 8 100 parts of vinyl chloride resin with a degree of polymerization of 1100, DOP 3
Test pieces were exploded using 0 parts of calcium carbonate, 15 parts of calcium carbonate, and the ingredients shown in Table 2 in the same manner as in Examples 1 to 9, and the same tests were conducted. As shown in Table 2, the results showed that the products of the present invention exhibited excellent heat resistance and weather resistance.

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Claims (1)

[Claims] 1. Vinyl chloride resin containing (a) zinc oxide, (b) structural formula [
Zinc dithiocarbamate represented by [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ R_1, R_2; Alkyl group with 1 to 18 carbon atoms, phenyl group, cyclohexyl group (c) Polyhydric alcohol or polyhydric alcohol (d) one or more compounds selected from hydrotalcites, magnesium oxide, magnesium hydroxide, and barium soap. 2. The amount added to 100 parts by weight of vinyl chloride resin is (
a) 0.1 to 10 parts by weight of zinc oxide, (b) 0.05 parts by weight of zinc dithiocarbamate represented by the structural formula [I]
(c) 0.3 to 5 parts by weight of a polyhydric alcohol or a partial ester of a polyhydric alcohol;
(d) 0.1 to 7 parts by weight of one or more compounds selected from hydrotalcites, magnesium oxide, magnesium hydroxide, and barium soap. Compositions as described.