JP3526111B2 - Hard vinyl chloride resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rigid vinyl chloride resin composition, and more particularly, to a method in which a zinc compound, hydrotalcites, polyvinyl alcohol and polymethyl methacrylate are added in combination. A hard vinyl chloride resin composition characterized by the following: [0002] Vinyl chloride resin compositions are resins having excellent flame retardancy and chemical resistance, and are used for various purposes. However, the vinyl chloride resin has a disadvantage that it is easily decomposed thermally and causes dehydrochlorination, resulting in a decrease in mechanical strength and coloring, thereby impairing commercial properties. In order to solve the above-mentioned drawbacks, various stabilizers have been developed. In particular, it is known that lead compounds and mixtures of cadmium compounds and barium compounds have excellent stabilizing effects. However, in recent years, the use of lead compounds and cadmium compounds has tended to be restricted from the viewpoint of safety,
The stabilization is being changed to a combination of highly safe zinc compounds and inorganic compounds such as organic salts of alkaline earth metals, hydrotalcite, and zeolite. For example, a method for stabilizing a vinyl chloride resin with a zinc compound and hydrotalcites is disclosed in
80445. However, the above-mentioned stabilization using a zinc compound and hydrotalcites does not provide satisfactory stabilizing effects such as thermal stability and coloring properties.
JP 7552 proposes the use of a combination of polyhydric alcohols such as pentaerythritol and trimethylolpropane. Although the polyhydric alcohol has an effect of improving thermal stability, it has poor compatibility with a vinyl chloride resin, blooms to impair the appearance, and does not have a sufficient stabilizing effect. Japanese Patent Application Laid-Open No. 61-174270 describes a polyhydric alcohol which can be used in combination with polyvinyl alcohol, and Japanese Patent Application Laid-Open No. 1-178543 discloses a method for improving bloom by using polyvinyl alcohol. However, the stabilizing effect was not yet satisfactory. [0007] In addition, hard vinyl chloride resins are used with a processability improver such as polymethyl methacrylate, methacrylate / butadiene / styrene copolymer and acrylonitrile / butadiene / styrene copolymer for the purpose of improving processability and impact resistance. It is widely known that it has been added. It is known that the above improver sometimes improves the stability by improving the processability. However, there is no particular finding that the improver and the stabilizer are expected to have a synergistic effect. It was not expected that an excellent stabilizing effect would be obtained with a particular modifier. As described above, the stabilization of the vinyl chloride resin is not yet satisfactory. Particularly, in the case of the hard vinyl chloride resin, a plasticizer is added in an amount of 0 to 100 parts by weight of the vinyl chloride resin.
Since only 5 parts by weight are added, the melt viscosity is high, processing at a high temperature is necessary, and the share required during processing is large.
Therefore, a high degree of stabilization is required, and an excellent stabilization method has been desired. Accordingly, it is an object of the present invention to provide a hard vinyl chloride resin composition having excellent coloring properties and heat stability. Means for Solving the Problems As a result of intensive studies, the present inventors have found that a combination of hydrotalcite, a zinc compound and polyvinyl alcohol is used in combination with a rigid polyvinyl chloride resin modified with polymethyl methacrylate. It has been found that the above object can be achieved by the addition. [0012] The present invention has been made based on the above-mentioned findings.
1 to 5 parts by weight, 0.01 to 10 parts by weight of hydrotalcites, 0.01 to 5 parts by weight of polyvinyl alcohol, and 0.05 to 10 parts by weight of polymethyl methacrylate Is to provide a composition. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the rigid vinyl chloride resin composition of the present invention will be described in detail. Examples of the vinyl chloride resin used in the present invention include polyvinyl chloride, chlorinated polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, and vinyl chloride-vinyl chloride. Examples include butadiene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, and vinyl chloride-styrene-maleic anhydride terpolymer. The zinc compounds used in the present invention include zinc stearate, zinc carboxylate such as zinc laurate and zinc oleate, zinc benzoate, and the like.
Examples include zinc aromatic carboxylate such as zinc p-tert-butylbenzoate, zinc salt of an organic acid such as zinc salt of amino acid and zinc salt of phosphoric acid ester, and inorganic zinc salt such as zinc oxide and zinc carbonate. The amount of the zinc compound to be added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The above addition amount is 0.0
If the amount is less than 1 part by weight, a sufficient stabilizing effect cannot be obtained. If the amount exceeds 5 parts by weight, the thermal stability becomes insufficient due to zinc burning. Further, as the hydrotalcites used in the present invention, compounds represented by the following general formula (I) are preferably used. Zn _X Mg _Y Al ₂ (OH) _{2 (X + Y) +4} CO ₃ .nH ₂ O (I) (where X, Y and n are respectively 0 ≦ X ≦ 2, 4 ≦
The number satisfies X + Y ≦ 6 and 0 ≦ n ≦ 20. The above-mentioned hydrotalcites may be natural products or synthetic products, but synthetic products in which contamination of the resin by impurities is small are preferable. The composition of the hydrotalcites may be one in which part or all of magnesium in the above general formula (I) is substituted with another alkaline earth metal, and part or all of carbonate anion may be perchlorate anion or the like. May be substituted. Further, as the above-mentioned hydrotalcites, those subjected to a surface treatment with a fatty acid or the like can also be used. The addition amount of the above hydrotalcites is
0.01 to 10 parts by weight per 100 parts by weight of vinyl chloride resin
Parts by weight, preferably 0.05 to 5 parts by weight. If the amount is less than 0.01 part by weight, no stabilizing effect is observed. If the amount exceeds 10 parts by weight, the color tone and mechanical strength of the resin are impaired. The polyvinyl alcohol used in the present invention includes 30 to 100% saponified vinyl acetate or a vinyl acetate component of a vinyl acetate-ethylene copolymer. The polyvinyl alcohol obtained by the saponification of vinyl acetate is preferably purified by a known method after the saponification. Those whose purification is insufficient are
Undesirable effects such as coloring of the obtained vinyl chloride resin composition by the residual alkali metal or the like are exerted. The amount of the polyvinyl alcohol to be added is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. The above addition amount is 0.0
If the amount is less than 1 part by weight, no stabilizing effect is observed. If the amount exceeds 5 parts by weight, the color tone and mechanical strength of the resin are impaired. The polymethyl methacrylate used in the present invention is not particularly limited, and those having a polymerization degree of 50 to 10,000 are used depending on the physical properties of the target hard vinyl chloride resin composition. If methyl methacrylate is 90% by weight or more in the polymer, it may be a copolymer with another monomer. The addition amount of the polymethyl methacrylate is used within a range that exhibits a modifying effect of the vinyl chloride resin and does not impair the characteristics of the resin, and is 0.05 to 10 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin. 0.1 to 5 parts by weight. If the amount is less than 0.05 part by weight, the effect of addition is not recognized. If the amount exceeds 10 parts by weight, the physical properties of the resin are impaired. The hard vinyl chloride resin composition of the present invention comprises a stabilizer, a phenolic antioxidant, a phosphorus antioxidant, a light stabilizer, an ultraviolet absorber, an antifogging agent, an antistatic agent and a flame retardant which are generally used. , A lubricant, a modifier, a reinforcing agent, a pigment, a foaming agent and the like can be used in combination. The hard vinyl chloride resin composition of the present invention may be mixed with another resin as long as its mechanical properties are not impaired. If it is in the range of parts by weight, a plasticizer may be added. As the stabilizer, well-known stabilizers can be used, and specifically, alkaline earth metal soaps such as calcium soap and barium soap, aluminum soaps, and organic metal salts such as organophosphate metal salts. , Metal oxides, metal hydroxides, metal carbonates, inorganic metal salts such as inorganic composite metal salts such as zeolites, barium chlorate, barium perchlorate, halogen peroxylates such as sodium perchlorate, β-diketone ,
Non-metallic stabilizers such as polyhydric alcohols and epoxy compounds are exemplified. Examples of the plasticizer include an ester plasticizer, an ether plasticizer, an epoxy plasticizer, and a phosphate plasticizer. As the plasticizer, ester plasticizers such as phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid and azelaic acid, and n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol, n-
Hexanol, isohexanol, n-heptanol,
Linear and branched alkyl alcohols alone such as isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol Further, polyester plasticizers such as an ester composed of a mixture and an ester of butanediol and adipic acid may be used. The epoxy plasticizer includes epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil,
Epoxy resins include epoxidized linseed oil fatty acid butyl, octyl epoxy stearate, epoxy triglyceride, epoxy isoglyceryl diisodecyl, and epoxy resins such as low molecular weight reaction product resin of epichlorohydrin and bisphenol A. Examples of the phosphate ester plasticizer include tricresyl phosphate, trixylenyl phosphate, monobutyl dixylenyl phosphate, and trioctyl phosphate. The phenolic antioxidant may be any of those commonly used, for example,
2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)-
Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4 '-Thiobis (6
-Tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,
2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-
Tert-butylphenyl) butyric acid] glycol ester, 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-
Sec-butyl-6-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-−２ (3-tert-butyl Butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) −5-
Methylphenyl) propionate]. The amount of the phenolic antioxidant to be added is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. As the phosphorus-based antioxidant, any of those usually used may be used, for example, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tert. Butyl-4-
(3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite,
Di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-
Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4 ′ -N-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl)
Butanetriphosphite, tetrakis (2,4-ditertbutylphenyl) biphenylenediphosphonite, 9.1
0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) -2-ethylhexyl phosphite and the like. Showa 5
And high molecular weight phosphorus compounds proposed in JP-A-7-192460. The amount of the phosphorus-based antioxidant to be added is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Parts by weight. As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2- such as hydroxy-4-methoxybenzophenone)
Hydroxybenzophenones; 2- (2-hydroxy-
5-methylphenyl) benzotriazole, 2- (2-
Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2
-Hydroxy-3-tert-butyl-5-methylphenyl)
-5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2- (3-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
And cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate. The amount of the ultraviolet absorber added is preferably 0.005 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. As the light stabilizer, for example, 2, 2,
6,6-tetramethyl-4-piperidyl stearate,
1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1, 2,
2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) butanetetracarboxylate, tetrates (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2
-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate,
1,6-bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate,
1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2 , 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,
6,6-tetramethyl-4-piperidyl) amino) -s
-Triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4
-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1 , 6,11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Hindered amine compounds such as piperidyl) amino) -s-triazin-6-ylamino] undecane. The amount of the light stabilizer is 100 vinyl chloride resin.
The amount is preferably from 0.001 to 5 parts by weight, more preferably from 0.05 to 3 parts by weight, based on parts by weight. Examples of the method for processing the rigid vinyl chloride resin composition of the present invention include extrusion, calendering, blow molding, pressing, powder molding, injection molding and the like. The hard vinyl chloride resin composition of the present invention can be used for building materials such as floor materials, ceiling materials, wall materials, window frames, corrugated sheets, rain gutters, automobile exterior materials, automobile interior materials, packing, gaskets, pipes, toys. The hard vinyl chloride resin composition can be used for any purpose as long as the hard vinyl chloride resin composition is usually used, such as daily necessities. The present invention will be described in more detail with reference to the following examples. However, the invention is not limited at all by these examples. Example 1 and Comparative Examples 1 to 7 Stabilizers of the type and amount shown in the following Table 1 were added to the following Basic Formulation 1 and blended with a Henschel mixer, and then 180 ° C. × 20 rpm × 0 Roll kneading was performed under a condition of 0.5 mm × 5 minutes to obtain a sheet as a hard vinyl chloride resin composition for a thermal stability test. The obtained sheet was subjected to the following thermal stability test and coloring test. The results are shown in Table 1 below. Thermal stability test: 190 ° C.
The time to blackening in a gear oven was evaluated at 10 minute intervals. Coloring test: 180 ° C. × 5 minutes × 1 mm
The yellowness of the Hunter of the sheet obtained by pressing was measured to evaluate the coloring property. Basic Formulation 1 Vinyl chloride resin 100 parts by weight MBS ^{* 1} 5 カ ル シ ウ ム Calcium carbonate 3 チ タ ン Titanium dioxide 6 亜 鉛 Zinc stearate 1.2 カ ル シ ウ ム Calcium stearate 1.0 〃 Dibenzoylmethane 0.02 ポ リ エ チ レ ン Polyethylene wax 0.5 Glycerin (mono / di) stearate 0.4 * 1: Impact modifier for vinyl chloride resin manufactured by Kanegafuchi Chemical Co., Ltd .: Kaneace FM (methyl methacrylate / butadiene / styrene resin) ] Examples 2 to 4 and Comparative Examples 8 to 9 In the same manner as in Example 1 except that the stabilizers of the types and amounts shown in the following [Table 2] were blended into the compound of the following Basic Formulation 2. Performed and evaluated. The results are shown in Table 2 below. Basic Formulation 2 Vinyl chloride resin 100 parts by weight Calcium carbonate 3 チ タ ン Titanium dioxide 5 ＭＢ MBS ^* 15 〃 PMMA ^{* 2} 0.5 〃 DHT-4A ^{* 3} 0.8 亜 鉛 Zinc stearate 0.5 ビ スDistearyl phosphate) zinc 0.5 〃 calcium stearate 0.7 Ａ AO-50 ^{* 5} 0.3 〃 stearoylbenzoylmethane 0.3 ポ リ エ チ レ ン polyethylene wax 0.5 〃 glycerin (mono / di) stearate 0.4 〃 * 5: Phenolic antioxidant manufactured by Asahi Denka Kogyo Co., Ltd .: ADK STAB AO-50 Stearyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Examples 6 to 8 and Comparative Examples 10 to 12 In the same manner as in Example 1 except that the stabilizers of the types and amounts shown in the following [Table 3] were added to the following basic compound 3, Performed and evaluated. The results are shown in Table 3 below. Basic Formulation 3 Vinyl chloride resin 100 parts by weight Titanium dioxide 0.3 〃 DHT-4A ^{* 3} 0.5 亜 鉛 Zinc stearate 0.5 カ ル シ ウ ム Calcium stearate 0.4 Ａ AO-50 ^{* 5} 0.1 〃 Benzoylmethane 0.1 〃 Polyethylene wax 0.5 グ リ Glycerin distearate 0.2 〃 From the above results, when polyvinyl alcohol and polymethyl methacrylate were added to a hard vinyl chloride resin stabilized with a zinc compound and hydrotalcite in combination (Examples 1 to 5), each was added alone. It is clear that a remarkable stabilizing effect can be obtained as compared with the case of performing (Comparative Examples 5, 7 to 9). When a polymethyl methacrylate was used as an impact modifier for a hard vinyl chloride resin composition stabilized with a zinc compound, hydrotalcites and polyvinyl alcohol (Examples 6 to 10). 8) shows a stabilizing effect, but no stabilizing effect is observed when the MBS resin is used (Comparative Example 12). It is clear that polymethyl methacrylate has a specific stabilizing effect among the impact modifiers. The rigid vinyl chloride resin composition of the present invention
It is excellent in coloring property and heat stability.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 33:12) (56) References JP-A-1-178543 (JP, A) JP-A-7-118473 (JP, A) JP-A-5-247297 (JP, A) JP-A-5-247296 (JP, A) JP-A-5-230309 (JP, A) JP-A-5-98105 (JP, A) JP-A-4-318047 (JP, A) JP-A-57-147552 (JP, A) JP-A-61-174270 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06

Claims (1)

(57) [Claims 1] 100 parts by weight of a vinyl chloride resin, 0.01 to 5 parts by weight of a zinc compound, and 0.0 of hydrotalcites
A hard vinyl chloride resin composition comprising 1 to 10 parts by weight, 0.01 to 5 parts by weight of polyvinyl alcohol, and 0.05 to 10 parts by weight of polymethyl methacrylate.