JPS6153380B2 - - Google Patents

Description

[Detailed description of the invention]

In general, when a stearic acid metal salt is used in combination, yoking occurs. Especially when it comes to dark-colored objects such as gray, blue-gray, blue, and brown, or even light-colored objects, the phenomenon in which the surface of a PVC molded product turns white after being exposed to sunlight for several months is called yoking. In the case of colored products, the commercial value is significantly lowered, and when they are used as structural materials, their aesthetic appearance is severely impaired. Particularly in molded products using non-lead formulations, a wide variety of metal soaps are used as stabilizers and processing agents, which causes significant yoking, and to prevent this, expensive tin compounds are often used in combination. It was considered. It is also known that epoxy compounds and zinc compounds are generally effective in preventing color deterioration due to rusting, so-called weather resistance. The present inventors have intensively investigated methods for suppressing chocking in hard molded products. As a result, they have found that at least one polyhydric alcohol selected from pentaerythritol and dehydration condensation polyols of pentaerythritol, monocarboxylic acid, polycarboxylic acid, or those A polyol partial ester compound having a hydroxyl group content of 10 to 40% obtained by reacting with at least one selected from the group consisting of esters, acid halides, and acid anhydrides, a zinc compound, and a polyol obtained by mixing an epoxy compound. The present inventors have discovered that molded products made using a vinyl chloride compound have significantly improved chockability, leading to the completion of the present invention. Examples of the chlorine-containing resin in the present invention include the following. Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer Coalescence, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-
Maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-
Butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride- Chlorine-containing synthetic resins such as maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their mutual or other chlorine-containing resins. Examples include blends with synthetic resins, block copolymers, and graft copolymers. The polyol partial ester compound in the present invention is composed of at least one polyhydric alcohol selected from the group consisting of pentaerythritol and dehydration condensation polyols of pentaerythritol, monocarboxylic acid and polycarboxylic acid, or esters thereof, acid halides and These include polyol partial ester compounds having a hydroxyl group content of 10 to 40%, which are obtained by reacting with at least one selected from the group consisting of acid anhydrides. The dehydration condensation polyols of pentaerythritol used here refer to polypentaerythritol itself or a mixture thereof, such as dipentaerythritol and tripentaerythritol, which are by-products during the production of pentaerythritol.
It also refers to polyols or polyol mixtures obtained by heat dehydration condensation of pentaerythritol in the presence of an appropriate catalyst and/or solvent. For example, pentaerythritol itself has a melting point of 250-260°C and a hydroxyl group content of 50%, but it can be mixed with mineral acids such as phosphoric acid and sulfuric acid, or organic acids such as alkylbenzenesulfonic acid,
Alternatively, a polyol mixture obtained by dehydration condensation at a reaction temperature of 200 to 270°C in the presence of an acid catalyst such as a Lewis acid such as tin chloride or magnesium chloride,
The melting point and hydroxyl group content change depending on the amount of dehydration. The polyol mixture thus obtained contains unreacted pentaerythritol and polypentaerythritol such as dipentaerythritol, tripentaerythritol, and tetrapentaerythritol, as well as complex pentaerythritol condensates. Specific examples of carboxylic acids, esters, acid halides, and acid anhydrides used in esterification are shown below. Monocarboxylic acids include acetic acid, lactic acid, 4-hydroxybutyric acid, fructic acid, oxybivalic acid,
Ricinoleic acid, stearic acid, octylic acid, thioglycolic acid, etc. Polycarboxylic acids include malonic acid, succinic acid, maleic acid, adipic acid, glutaric acid, itaconic acid, malic acid, tartaric acid, citric acid, phthalic acid, isophthalic acid , terephthalic acid, trimellitic acid, pyromellitic acid, etc. Table 1 shows the polyol partial ester compounds used in the examples to explain the present invention.

[Table] Specific examples of zinc compounds used in the present invention are shown below. Namely, zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate, zinc (meta)borate, zinc (meta)silicate, zinc (nitrous)phosphate, zinc aluminate, zinc titanate, zinc stannate, and rhodan. Metal soaps with inorganic compounds such as zinc oxide and monocarboxylic or polycarboxylic acids are used. Examples of monocarboxylic acids include acetic acid, lactic acid, octylic acid, lauric acid, oleic acid, stearic acid, isostearic acid, ricinoleic acid, benzoic acid, para-tert-butylbenzoic acid, chlorobenzoic acid, salicylic acid, acrylic acid, Examples of polycarboxylic acids include malonic acid, succinic acid, maleic acid, adipic acid, glutaric acid, itaconic acid, malic acid, tartaric acid, citric acid, phthalic acid, isophthalic acid, terephthalic acid, and trimeric acid. acids, pyromellitic acid, etc. The epoxy compound in the present invention is a compound having an oxirane oxygen in the molecule in some structure. For example, glycidyl ethers that are ether-condensed with phenolic or alcoholic hydroxyl groups and epichlorohydrin, alicyclic epoxies obtained by oxidizing compounds with cyclohexene rings or dicyclopentadiene rings, and fatty acid compounds with double bonds. These include epoxidized fatty acid esters obtained by oxidizing esters. Compounds used in Examples to explain the present invention are shown in Table 2.

[Table] In addition to the above-mentioned compounds, various compounds generally known as stabilizers may be used in combination with the present invention without impairing the characteristics of the present invention. Particularly effective compounds that can be used here include the following. Examples of metal salt compounds include magnesium, calcium, and barium compounds, and specific examples include inorganic compounds and monomers such as their oxides, hydroxides, carbonates, basic carbonates, and basic phosphates. Metal soaps with carboxylic acids or polycarboxylic acids are used. Examples of monocarboxylic acids include acetic acid, lactic acid, octylic acid, lauric acid, oleic acid, stearic acid, isostearic acid, ricinoleic acid, benzoic acid, para-tertiary butylbenzoic acid,
Examples of polycarboxylic acids include malonic acid, succinic acid, maleic acid, adipic acid, glutaric acid, itaconic acid, malic acid, tartaric acid, and citric acid. , phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. The phenolic antioxidant is a compound selected from the group of compounds having 1 to 4 phenol groups in the same molecule, in which the hydroxyl group is hindered by at least one tertiary or secondary alkyl group. Examples include styrenated para-cresol, 2,6-di-tert-butyl, 4-methylphenol, butylated anisole, 4,4'-methylenebis(6-tert-butyl, 3-methylphenol), 2- 2'-methylenebis(6-tert-butyl, 4-methylphenol), 1,3,5-trimethyl, 2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene ,
Tetrakis[3-(4-hydroxy-3,5-ditertiary-butylphenyl)propionyloxymethyl]methane and the like. In the present invention, plasticizers, lubricants, processing aids, weather resistance improvers, antistatic agents, antifogging agents, reinforcing agents, fillers, pigments, etc. may be used in combination depending on the application, processing method, molding method, etc. . The pigment used in the present invention is manufactured by Sumika Color Co., Ltd.
"Brown DX" manufactured by Co., Ltd., but the present invention is not limited thereto. EXAMPLES The superior effects of the present invention will be explained using Examples, but the present invention is not limited to these Examples. Example 1 Polyol partial ester compounds listed in Table 1
The following composition containing No. 2 and epoxy compounds No. 1 and No. 3 listed in Table 2 was rolled and then press-bonded to form a plate. Vinyl chloride resin (=750) 100 parts Polyol partial ester No. 2 1.0〃 Epoxy compound No. 1 or 3 1.0〃 Zinc stearate 1.0〃 Pigment 1.0〃 On the other hand, in the above composition, pentaerythritol was used in place of the polyol partial ester. A composition containing the following lead-based stabilizer was used as Comparative Example 1, and a composition containing the following lead-based stabilizer was used as Comparative Example 2, and pleats were molded in the same manner. Vinyl chloride resin (=750) 100 parts Tribasic lead sulfate 2.5〃 Lead stearate 0.5〃 Calcium stearate 0.5〃 Pigment 1.0〃 Example 1 and Comparative Examples 1 and 2 were exposed to sunlight on an exposure table facing south at 45 degrees. Sampling was carried out every month of exposure and a comparative evaluation of chockability was performed. The results are as follows: Example 1-1: The product containing epoxy compound No. 1 did not show any yoking after 12 months of outdoor exposure. Example 1-2: In the case of the product containing epoxy compound No. 3, no yoking was observed after 12 months of outdoor exposure. Comparative Example 1: Challenging occurred after 8 months Comparative Example 2: Challenging occurred after 4 months Example 2 The following composition was blended with polyol partial ester No. 3 listed in Table 1 and epoxy compound No. 5 listed in Table 2. The material was molded into a plate using a single-screw extruder at 170-190°C. Vinyl chloride resin (=1000) 100 parts Polyol partial ester No.3 1.0〃 Epoxy compound No.5 1.0〃 Zinc stearate 1.0〃 Barium stearate 0.5〃 LX-40A-2 (*) 0.5〃 Calcium carbonate 10.0〃 Pigment 1.0〃 (*) Lubricant manufactured by Kyodo Yakuhin Co., Ltd. On the other hand, Comparative Example 3 is a lubricant manufactured by Kyodo Yakuhin Co., Ltd., in which the same amount of dipentaerythritol was added instead of the polyol partial ester and DOP (dioctyl phthalate) was added instead of the epoxy compound in the above composition. Furthermore, a composition containing the following lead-based stabilizer was designated as Comparative Example 4,
Each plate was molded in the same manner. Vinyl chloride resin (=1000) 100 parts Tribasic lead sulfate 2.5〃 Lead stearate 0.5〃 Dibasic lead stearate 0.7〃 Calcium stearate 0.3〃 Calcium carbonate 10.0〃 Pigment 1.0〃 Example 2 and Comparative Example 3, 4 was exposed to sunlight on an exposure table facing south at 45 degrees, and sampling was performed every month to conduct a comparative evaluation of the yoking properties. The results are as follows: Example 2: Chiyoking occurred after 9 months of outdoor exposure Comparative Example 3: Chiyoking occurred after 6 months of outdoor exposure Comparative Example 4: Chiyoking occurred after 2 months of outdoor exposure Example 3 Polyol partial esters listed in Table 1 The following composition containing No. 3 and epoxy compound No. 4 listed in Table 2 was molded into a plate using a single screw extruder at 170 to 190°C. Vinyl chloride resin (=1000) 100 parts Polyol partial ester No. 3 1.0〃 Epoxy compound No. 4 1.0〃 Zinc carbonate 0.3〃 Barium stearate 0.5〃 LX-40A-2 0.5〃 Pigment 1.0〃 On the other hand, among the above compositions, polyol A similar plate was molded as Comparative Example 5, in which the same amount of dipentaerythritol was mixed in place of the partial ester and DOP in place of the epoxy compound, and Comparative Example 6, in which the following lead-based stabilizer was further blended. . Vinyl chloride resin (=1000) 100 parts Tribasic lead sulfate 2.5〃 Lead stearate 0.5〃 Dibasic lead stearate 0.7〃 Calcium stearate 0.3〃 Pigment 1.0〃 The above Example 3 and comparative rows 1 and 2 facing south 45 The specimens were exposed to sunlight on a high-temperature exposure stand, and samples were taken every month to compare and evaluate the chockability. The results are as follows. Example 3: Chiking occurred after 12 months of outdoor exposure Comparative Example 5: Chiyoking occurred after 7 months of outdoor exposure Comparative Example 6: Chiyoking occurred after 4 months of outdoor exposure Example 4 Polyol partial esters No. 1 and 2 listed in Table 1 The following composition containing epoxy compound No. 2 listed in the table was molded into a plate using an in-line screw injection molding machine at 180 to 200°C. Vinyl chloride resin (=700) 100 parts Polyol partial ester No.1 1.0〃 Epoxy compound No.2 1.0〃 Zinc oxide 0.2〃 Barium stearate 1.0〃 LX-40A-2 0.5〃 Kane Ace PA-20 (*) 0.5〃 Carbonic acid Calcium 10.0〃 Pigment 1.0〃 (*) Processing aid manufactured by Kanebuchi Kagaku Kogyo Co., Ltd. On the other hand, Comparative Example 7 was prepared by adding the same amount of dipentaerythritol in place of the polyol partial ester in the above composition and excluding the epoxy compound. Comparative Example 8 was prepared by using a composition containing the following lead-based stabilizer and the following plates were injection molded in the same manner. Vinyl chloride resin (=700) 100 parts Tribasic lead sulfate 3.0 Calcium stearate 0.5 LX-40A-2 0.3 Kane Ace PA-20 0.3 Calcium carbonate 10.0 Pigment 1.0 Above Example 4 and Comparative Example 7, No. 8 was exposed to sunlight on an exposure stand facing south at 45 degrees, and sampling was conducted every month to conduct a comparative evaluation of the yoking properties. The results are as follows. Example 4: Chiking occurs after 8 months of outdoor exposure Comparative Example 7: Chiyoking occurs after 5 months of outdoor exposure Comparative Example 8: Chiyoking occurs after 2 months of outdoor exposure Example 5 Polyol partial ester No. 2 listed in Table 1 The following composition containing epoxy compound No. 1 listed in Table 2 was formed into a sheet by roll rolling. Vinyl chloride resin (=750) 93 Kane Ace FM (*1) 7 Polyol partial ester 0.5 Epoxy compound No.1 0.5 Zinc stearate 1.5 Magnesium chloride 2.0 Biosorb (*2) 0.3 Irganox 1010 (*3) 0.2 Viscol 550P (*4 ) 0.4 Stearyl alcohol 0.5 Pigment 1.0 (*1) Acrylic resin manufactured by Kanebuchi Chemical Co., Ltd. (*2) Ultraviolet absorber manufactured by Kyodo Yakuhin Co., Ltd. (*3) Antioxidant manufactured by Ciba-Geigy Co., Ltd. ( *4) Polyolefin lubricant manufactured by Sanyo Kasei Co., Ltd. Comparative Example 9 was a composition that did not contain epoxy compound No. 1, and Comparative Example 9 was a composition containing the following lead-based stabilizer, and each was molded in the same way. . Vinyl chloride resin (=750) 100 Tribasic lead sulfite 3.0 Lead stearate 0.5 Calcium stearate 0.3 Pigment 1.0 The above Example 5 and Comparative Examples 9 and 10 were exposed to sunlight on an exposure stand facing south at 45 degrees, and exposed to sunlight every month. A sample was taken and a comparative evaluation of the yoke properties was carried out. The results are as follows: Example 5: Comparative example of yoking pressure after 14 months of outdoor exposure 9: Comparative example of yoking pressure after 8 months of outdoor exposure 10: Example of yoking pressure after 2 months of outdoor exposure 6 1st The following composition containing polyol partial ester No. 3 listed in the table and epoxy compound No. 4 listed in Table 2 was rolled and then press-bonded to form a plate. Ethylene-vinyl acetate-vinyl chloride graftomer resin (Toyo Soda Co., Ltd. Lieuron HI-E-2) 100 Polyol partial ester No. 3 0.6 Epoxy compound No. 4 0.5 Zinc stearate 1.5 Magnesium oxide 2.0 Barium stearate 0.3 Viscol 550P 0.3 Stearyl Alcohol 0.3 Pigment 1.0 Comparative Example 11 was a composition that did not contain epoxy compound No. 4, and Comparative Example 12 was a composition containing the following lead-based stabilizer, which were molded in the same manner. Ethylene-vinyl acetate-vinyl chloride graftomer resin (Toyo Soda Co., Ltd. Lieuron HI-E-2) 100 Tribasic lead sulfate 3.0 Lead stearate 0.5 Barium stearate 0.3 Pigment 1.0 Above Example 6 and Comparative Example 11, 12 was exposed to sunlight on an exposure stand facing south at 45 degrees, and sampling was conducted once a month to conduct a comparative evaluation of the yawking properties. The results are as follows. Example 6: Comparative example 11: Chiyoking pressure after 13 months of outdoor exposure Comparative example 12: Chiyoking pressure after 7 months of outdoor exposure Comparative example 12: Chiyoking pressure after 2 months of outdoor exposure

Claims (1)

[Scope of Claims] 1 Consists of at least one polyhydric alcohol selected from pentaerythritol and dehydration condensation polyols of pentaerythritol, and monocarboxylic acids and polycarboxylic acids, or their esters, acid halides, and acid anhydrides. Hydroxyl group content of 10 to 40% obtained by reacting with at least one selected from the group
A chlorine-containing resin composition that suppresses yoking, characterized in that a polyol partial ester compound, a zinc compound, and an epoxy compound are used together. 2. The composition of claim 1, wherein the polyol partial ester of 1 is an acetic acid and saturated dibasic acid ester of dipentaerythritol. 3. The composition according to claim 1, wherein the epoxy compound has an epoxy equivalent of 200 or less. 4. The composition according to claim 2, wherein the epoxy compound is diglycidyl ether of bisphenol A and a condensate thereof.