JPS6157338B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, monoalkyltin tris (monohydroxyalkyl mercaptide), monoalkyltin sulfide, and an alkali metal compound or alkaline earth metal compound are added to a chlorine-containing resin in combination, and their synergistic effect provides resistance to heat. The invention relates to a chlorine-containing resin composition stabilized by Halogen-containing resins tend to decompose due to heat during hot molding, resulting in coloring and, as a result, deterioration of the mechanical properties of the molded product. To prevent these, various additives such as metal soaps such as cadmium, lead, calcium, barium, and zinc, as well as organic tin compounds, organic phosphite esters, epoxy compounds, ultraviolet absorbers, and antioxidants are used alone. Or, at present, they are added in combination of several types and heat-molded. Among organotin compounds, in particular halogen-containing compounds stabilized with organotin sulfur-containing compounds, such as organotin mercaptides, organotin mercapto salts, organotin mercapto acid esters, organotin mercapto alcohol esters, organothiostannic acids, etc. The resin composition is
Although it has good transparency and initial thermal stability, it tends to adhere to the metal surface of the molding machine during molding, and as a result, it is forced to use a general lubricant, resulting in a loss of transparency and initial stability. Furthermore, it had bad odor, poor photostability, and was expensive. Techniques for improving these drawbacks have been disclosed. For example, in JP-A-52-130848 (US Pat. No. 4,043,957), a stabilizer containing a monoalkyltin alkyl mercaptide, a mercapto alcohol, a dialkyltin sulfide, and an inert diluent is added to a halogenated vinyl resin. describes a halogen vinyl resin stabilized by Japanese Unexamined Patent Publication No. 53-34847 (U.S. Patent No.
No. 3764571) includes organic tin mercapto acids, organic tin mercapto esters, organic tin sulfides, organic thiostannic acids, etc., alkaline earth metal oxides or hydroxides, and organic overbases of alkali metals or alkaline earth metal bases. It describes a stabilizer for halogen-containing resins that is used in combination with a metal compound selected from the group consisting of complexes. JP-A-53-135939 (US Pat. No. 4,118,371) describes the use of organotin mercaptoalkanol ester sulfides and polysulfides as stabilizers for halogen-containing resins. Furthermore, JP-A-52-38556 describes the use of an organic tin hydroxyalkyl mercaptan salt and calcium stearate in combination to stabilize vinyl chloride resin. However, even if the above-mentioned stabilizers were used, sufficient effects could not be achieved to obtain thermal stability, particularly initial thermal stability, and excellent processability. As a result of intensive research, the present invention etc. has been developed based on the following: (a) General formula (In the formula, R represents an alkyl group having 1 to 12 carbon atoms, and R ¹ represents an alkyl group having 8 to 18 carbon atoms.) ) monoalkyltin sulfides; and (c) alkali metal or alkaline earth metal carboxylates, thiocarboxylates, oxides, hydroxides, carbonates, carbonates, substituted carbonates, organic overbase complexes, and If at least one metal compound selected from the mixture is used in combination with a chlorine-containing resin, its synergistic thermal stabilizing effect will result in better initial thermal stability and processability than the organotin sulfur-containing stabilizer resin composition. The present invention was completed by discovering that a chlorine-containing resin composition having the following properties can be obtained. To describe the present invention in more detail, in monoalkyltin tris (monohydroxyalkyl mercaptide) represented by the above general formula,

[Formula] In the group, R ¹ has 8 to 18 carbon atoms, but those having less than 8 carbon atoms are undesirable because they are highly volatile and have a particularly strong odor. Further, those having carbon number greater than 18 are not preferable because the thermal stabilization effect is poor. To give an example of that group,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. Specific examples of monoalkyltin tris (monohydroxyalkyl mercaptide) used in the present invention include monomethyltin tris (monohydroxydecyl mercaptide), monomethyltin tris (monohydroxydodecyl mercaptide), and monomethyl. Tin Tris (monohydroxytetradecyl mercaptide), Monomethyltin Tris (monohydroxyhexadecyl mercaptide), Monomethyltin Tris (monohydroxyoctadecyl mercaptide), Monomethyltin Tris (monohydroxyeicosyl mercaptide), Mono-n-butyltin tris (monohydroxydecyl mercaptide), mono-n-butyltin tris (monohydroxydodecyl mercaptide), mono-n-butyltin tris (monohydroxytetradecyl mercaptide), mono -n-butyltin tris (monohydroxyhexadecyl mercaptide), mono-n-butyltin tris (monohydroxyoctadecyl mercaptide), mono-n-butyltin tris (monohydroxyeicosyl mercaptide), monohexyl Tin tris (monohydroxydecyl mercaptide), monohexyltin tris (monohydroxydodecyl mercaptide), monohexyltin tris (monohydroxytetradecyl mercaptide), monohexyltin tris (monohydroxyhexadecyl mercaptide), monohexyl Tin tris (monohydroxyoctadecyl mercaptide), monohexyltin tris (monohydroxyeicosyl mercaptide), mono-n-octyltin tris (monohydroxydecyl mercaptide), mono-n-octyltin tris (monohydroxy mono-n-octyltin tris (monohydroxytetradecyl mercaptide), mono-n-octyltin tris (monohydroxyhexadecyl mercaptide), mono-n-octyltin tris (monohydroxy octadecyl mercaptide), mono-n-octyltin tris (monohydroxyeicosyl mercaptide), mono-n-decyltin tris (monohydroxydecyl mercaptide), mono-n-decyltin tris (monohydroxydodecyl mercaptide), monododecyltin tris (monohydroxydecyl mercaptide), monododecyltin tris (monohydroxydodecyl mercaptide), monododecyltin tris (monohydroxytetradecyl mercaptide), and mixtures thereof. be. Preferably, mono-n-butyltin tris (monohydroxydodecyl mercaptide), mono-n-butyltin tris (monohydroxytetradecyl mercaptide), mono-n-butyltin tris (monohydroxyhexadecyl mercaptide). monohexyltin tris (monohydroxydodecyl mercaptide), monohexyltin tris (monohydroxytetradecyl mercaptide), monohexyltin tris (monohydroxyhexadecyl mercaptide), mono-n-octyltin tris (mono-n-octyltin tris) Hydroxydodecyl mercaptide), mono-n-octyltin tris (monohydroxytetradecyl mercaptide), mono-n-octyltin tris (monohydroxyhexadecyl mercaptide), and mixtures thereof. The alkyl group of the monoalkyltin sulfide used in the present invention has 1 to about 18 carbon atoms, and examples of the monoalkyltin sulfide include monomethyltin sulfide, monoethyltin sulfide, monopropyltin sulfide, and mono-n-butyltin sulfide. , monohexyltin sulfide, mono-n-octyltin sulfide, monodecyltin sulfide, monododecyltin sulfide, and polymers thereof. Particularly preferred examples include monomethyltin sulfide, mono-n-butyltin sulfide, mono-n-octyltin sulfide, and polymers thereof. Furthermore, among the alkali metal or alkaline earth metal compounds used in combination with monoalkyltin tris (monohydroxyalkyl mercaptide) and monoalkyltin sulfide (hereinafter referred to as organotin compounds) used in the present invention, Preferred examples include carboxylates, oxides, hydroxides, carbonates, and organic overbase complexes of the metal, and particularly preferred are carboxylates, hydroxides, and organic overbase complexes of the metal. Examples include complexes. There are no restrictions on the combination ratio and the amount added to the chlorine-containing resin, and should be determined appropriately depending on the purpose, but according to the research of the present inventors, preferably 100% of the chlorine-containing resin is used. For parts by weight,
Using 0.1 to 3.0 parts by weight of monoalkyltin tris (monohydroxyalkyl mercaptide) and monoalkyltin sulfide in a weight ratio of 1:1 to 10:1, and further adding the same amount of the total amount of the above organotin compounds. It is to use a metal compound in excess of the amount. If the ratio of the metal compound to the organotin compound is less than the same amount, the sustained thermal stability will be poor.
As mentioned above, the chlorine-containing resin composition of the present invention, which has a small amount of stabilizer added and has high thermal stability and excellent processability, can be used for pipes, rain gutters, and corrugated plates that require high mechanical properties. It is ideal for molding industrial boards, etc. Alkali metal or alkaline earth metal carboxylates, thiocarboxylate salts used in the present invention,
To elaborate on oxides, hydroxides, carbonates, carbonates, substituted carbonates and organic overbase complexes, preferred examples of alkali metals or alkaline earth metals include lithium, sodium, potassium, magnesium, calcium, strontium, These include barium and zinc, with particularly preferred examples being magnesium, calcium and barium. Examples of carboxylic acid residues constituting the alkali metal or alkaline earth metal carboxylates include acetoxy, propionyloxy, butyryloxy, hexanoyloxy, octanoyloxy, 2-ethylhexanoyloxy, decanoyloxy, Dodecanoyloxy, hexadecanoyloxy, octadecanoyloxy, docosanoyloxy, octadecenoyloxy, ricinoleyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, acetoacetoxy, benzoyloxy, (oxalyldioxy)
〓, (malonyldioxy)〓, (succinyldioxy)〓, (glutaryldioxy)〓, (aziboyldioxy)〓, (maleoyldioxy)〓, (phthaloyldioxy)〓, methoxymaleoyl Oxy, butoxymaleoyloxy, octyloxymaleoyloxy, isooctyloxymaleoyloxy, 2-ethylhexyloxymaleoyloxy, dodecyloxymaleoyloxy, tridecyloxymaleoyloxy, octadecyloxymaleoyloxy, octadecyloxymaleoyloxy Nyloxymaleoyloxy, cyclohexyloxymaleoyloxy, benzyloxymaleoyloxy, methoxyethyloxymaleoyloxy, butoxyethyloxymaleoyloxy, phenoxyethyloxymaleoyloxy, methoxybutyloxymaleoyloxy, 3. 6-Dioxadecyloxymaleoyloxy, [ethylenedioxy bis(maleoyloxy)], [tetramethylenedioxy bis(maleoyloxy)], cyclohexyloxyphthaloyloxy, octadecyloxyphthaloyloxy and octadecyloxyaziboyloxy. Examples of alkali metal or alkaline earth metal carboxylates include bis(acetoxy)magnesium, bis(octanoyloxy)magnesium, bis(dodecanoyloxy)magnesium, bis(octadecanoyloxy)magnesium, bis(octadecanoyloxy)magnesium, Decenoyloxy)magnesium, bis(ricinoleyloxy)magnesium,
Bis(monooctadecyloxymaleoyloxy)magnesium, maleoyldioxymagnesium, bis(acetoxy)calcium, bis(octanoyloxy)calcium, bis(dodecanoyloxy)calcium, bis(octadecanoyloxy)calcium, bis( isooctadecanoyloxy)calcium, bis(octadecenoyloxy)calcium, bis(ricinoleyloxy)calcium, bis(monooctadecyloxymaleoyloxy)calcium, octadecanoyloxysodium, octadecanoyloxypotassium, Bis(octadecanoyloxy)strontium, bis(octanoyloxy)barium, bis(dodecanoyloxy)barium, bis(octadecanoyloxy)barium, bis(octadecenoyloxy)barium, bis(ricinoleyloxy) ) barium, bis(monooctadecyloxymaleoyloxy)barium, maleoyldioxybarium, bis(octanoyloxy)zinc, bis(octadecanoyloxy)zinc, bis(octadecenoyloxy)zinc, bis(monooctadecenoyloxy)zinc octadecyloxymaleoyloxy)zinc, maleoyldioxyzinc, etc. Examples of thiocarboxylic acid residues constituting thiocarboxylate salts of alkali metals or alkaline earth metals include acetylthio, propionylthio, butyrylthio, hexanoylthio, octanoylthio, 2-ethylhexanoylthio, decanoylthio, dodecanoylthio, and hexadecanoylthio. ,
Octadecanoylthio, docosanoylthio, octadecenoylthio, ricinoleylthio, acryloylthio, methacryloylthio, crotonoylthio, acetoacetylthio, benzoylthio, (oxalyldithio), (malonyldithio), (succinyldithio), (glutaryldithio) , (aziboyldithio)〓, (maleoyldithio)〓, (phthaloyldithio)〓, methoxymaleoylthio, butoxymaleoylthio, octyloxymaleoylthio, isooctyloxymaleoylthio, 2
-Ethylhexyloxymaleoylthio, dodecyloxymaleoylthio, tridecyloxymaleoylthio, octadecyloxymaleoylthio, octadecenyloxymaleoylthio, cyclohexyloxymaleoylthio, benzyloxymaleoylthio, methoxyethyloxy Maleoylthio, butoxyethyloxymaleoylthio, phenoxyethyloxymaleoylthio, methoxybutyloxymaleoylthio, 3,6-dioxadecyloxymaleoylthio, [ethylenedioxy bis(maleoylthio)] , [tetramethylenedioxy bis(maleoylthio)]
These include cyclohexyloxyphthaloylthio, octadecyloxyphthaloylthio, and octadecyloxyadipoylthio. Examples of thiocarboxylate salts of alkali metals or alkaline earth metals include bis(dodecanoylthio)magnesium, bis(octadecanoylthio)magnesium, bis(octadecenoylthio)magnesium, maleoyldithiomagnesium, bis(dodecanoylthio)calcium. , bis(octadecanoylthio)calcium, maleoyldithiocalcium, octadecanoylthiosodium, octadecanoylthiopotassium, bis(octadecanoylthio)strontium, bis(dodecanoylthio)barium, bis(octadecanoylthio)barium , maleoyldithiobarium, bis(dodecanoylthio)zinc, bis(octadecanoylthio)zinc and maleoyldithiozinc. Examples of the carbolic acid residues and substituted carbolic acid residues constituting the carbonates and substituted carbonates of alkali metals or alkaline earth metals include phenyloxy, methylphenyloxy, tert-butylphenyloxy, octylphenyloxy, and nonylphenyloxy. enyloxy, chlorophenyloxy, hydroxyphenyloxy, naphthyloxy, methoxyphenyloxy, 3-methyl-4-isopropylphenyloxy and tert-butyl-methoxyphenyloxy. Examples of alkali metal or alkaline earth metal carbonates and substituted carbonates include bis(phenyloxy)magnesium, bis(phenyloxy)calcium, bis(phenyloxy)barium, bis(octylphenyloxy)barium and bis(nonylphenyloxy). barium (enyloxy), etc. Examples of oxides, hydroxides or carbonates of alkali metals or alkaline earth metals include magnesium oxide, calcium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate and calcium carbonate. . For organic overbased complexes of alkali metals or alkaline earth metals, basic salts, superbased salts,
It is an oil-soluble metal salt commonly referred to as an overbased salt or a highly basic dispersant, and is known as an oil additive. Regarding the manufacturing method of this organic overbase complex, US Pat.
No. 3242079; Special Publication No. 50842, Special Publication No. 1977-
Although it is described in the specification and publication of No. 48161, the general manufacturing method uses alcohol etc. as a medium in an organic solvent and uses a direct method or metathesis method to produce metal aliphatic acid salts, cycloaliphatic acid salts, and aromatic acid salts. Manufacture family acid salts,
Furthermore, carbon dioxide gas is blown into the excess metal oxide or hydroxide to convert it into carbonate, thereby producing an organic overbase complex with a high metal content. Although there are many unknowns about the chemical structure of this complex, the aforementioned metal carboxylic acid salts or metal thiocarboxylic acids, which are widely used to stabilize halogen-containing resins, include bis(octadecanoyloxy)magnesium, maleoyl It is clearly distinguished from dioxycalcium, bis(dodecanoyloxy)barium, bis(octadecanoylthio)magnesium, etc.
In other words, the organic overbase complex has a basicity expressed as "the number of bases corresponding to the number of mg of caustic potassium per gram of the sample", while the above-mentioned bis(octadecanoyloxy)magnesium, maleoyldioxycalcium The carboxylic acid metal salts such as the following are neutral salts with a basicity of 0. Stated another way, an organic overbased complex is a metal complex that contains more metal than the chemical equivalent of the organic acid it contains, and is defined as the metal ratio, which is the total weight of the metal divided by the equivalent weight of the metal to the organic acid. Accordingly, the metal ratio exceeds 1, and bis(octadecanoyloxy)magnesium, maleoyldioxycalcium, etc. have a metal ratio of 1. Preferred metals for organic overbase complexes of alkali metals or alkaline earth metals include magnesium, calcium, and barium, and examples of the organic overbase complexes include overbased magnesium sulfonate, overbased calcium sulfonate, etc. , overbased substituted calcium carbonate, overbased barium sulfonate, overbased substituted barium carbonate, and the like. To give a specific example,
ECA5087 (Exxon Chem), Bryton M400
(Witoco Chem), Lubrizol 56, 58, 70, 74,
76, 78, 79, 2110 (Lubrizol), Lubrizol 2105
(Lubrizol), O, S, 40182 (Lubrizol),
PARANOX.30 (Exxon Chem), HIT EC E631
(Japan Cooper), SULFOL Ba30N, MB, HB
(Matsumura Petroleum Research Institute), Lubrizol 2106 (Lubrizol)
etc. The chlorine-containing resin composition of the present invention can be prepared by mixing the resin and the stabilizer using a known mixing method, for example, using a mixer such as a Henschel mixer, a super mixer, a kneader, a Banbury mixer, a ribbon blender, or a crusher. It can be obtained by Further, the chlorine-containing resin composition of the present invention can be molded into a desired molded product by known molding methods such as extrusion molding, injection molding, calendar molding, and blow molding. The chlorine-containing resin composition of the present invention may optionally include:
For example, metal soaps, epoxy compounds, organic phosphites, polyhydric alcohols, ultraviolet absorbers, pigments,
It can contain plasticizers, foaming agents, antistatic agents, lubricants, flame retardants, processing aids, fluorescent agents, antifogging agents, and the like. Examples of metal soaps include aluminum laurate, aluminum stearate, aluminum ricinoleate, tin octylate, tin stearate and tin ricinoleate. Examples of epoxy compounds include epoxidized soybean oil, epoxidized linseed oil,
Epoxidized castor oil, epoxidized safflower oil,
These include epoxidized linseed oil fatty acid butyl ester, epoxy octyl stearate, and epoxidized polybutadiene. Examples of organic phosphites include triphenyl phosphite, diphenyl hydrogen phosphite, monophenyl dihydrogen phosphite, tris(nonylphenyl) phosphite, 2-tert-butyl-α-(3-tert-butyl- 4-hydroxyphenyl)-p-cumenylbis(p-nonylphenyl) phosphite, hydrogenated 4,4'-isopropylidene diphenol phosphite, bis(nonylphenyl)hydrodiene phosphite and (stearyl)pentaerythrityl diphosphite, etc. It is. Examples of polyhydric alcohols include 1,3-butanediol, 1,4-butanediol, triethylene glycol, dipropylene glycol, polypropylene glycol, trimethylolmethane,
These include trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, sorbitol, and partial esters of these polyhydric alcohols and carboxylic acids. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based and substituted acrylonitrile-based ultraviolet absorbers. Examples of pigments include titanium oxide, carbon black and red iron. Examples of plasticizers include phthalate esters, aliphatic dibasic acid esters, phosphoric esters, hydroxy polycarboxylic esters, fatty acid esters, polyhydric alcohol esters, epoxies, polyesters, and other alkyl sulfones. These include acid esters and chlorinated paraffins, and can be used in appropriate amounts depending on the purpose. Examples of lubricants include hydrocarbon wax, higher alcohol, higher fatty acid, higher fatty acid ester, rice bran wax,
These include Montan wax and amide lubricants. Examples of chlorine-containing resins used in the present invention include vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin, chlorinated ethylene resin, chlorinated propylene resin, chlorinated rubber, hydrochloric acid rubber, and vinyl chloride-vinyl acetate copolymer resin. , vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-styrene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-butadiene copolymer resin, vinyl chloride-maleic acid copolymer resin , vinyl chloride-methacrylonitrile copolymer resin, vinyl chloride-α-methylstyrene copolymer resin, vinyl chloride-acrylic acid copolymer resin, vinyl chloride-vinyl alcohol copolymer resin, vinyl chloride-chlorinated ethylene copolymer resin, Vinyl chloride-styrene-acrylonitrile copolymer resin, vinyl chloride-styrene-butadiene copolymer resin, vinyl chloride-styrene-vinylidene chloride copolymer resin, vinyl chloride-vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate-styrene copolymer resin These include polymer resins, vinyl chloride-acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride-methyl methacrylate-butadiene-styrene copolymer resins, and the like. Furthermore, vinylidene chloride resin, chlorinated vinyl chloride resin, chlorinated ethylene resin, chlorinated propylene resin, vinyl acetate resin, butadiene resin, isobutylene resin, ethylene resin, propylene resin, styrene resin, acrylic resin, urethane resin, ethylene-vinyl acetate Examples include polymer blends of vinyl chloride resins with copolymer resins, ethylene-propylene copolymer resins, styrene-acrylonitrile copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, methacrylonitrile-butadiene-styrene copolymer resins, etc. can. Next, the present invention will be explained with examples. In the examples, parts mean parts by weight, and the stabilizers used in the examples are shown in Table 1, and their code numbers are shown in Table 2 onwards.

【table】

【table】

[Table] Example 1 Vinyl chloride resin Geon103EP [Nippon Zeon Co., Ltd.]
After mixing 100 parts of the stabilizer shown in Table 1 with the stabilizer shown in Table 1, the mixture was kneaded with a test roll at 170°C for 5 minutes to give a thickness of 0.5 mm.
After cutting this sheet into a size of 3 cm x 6 cm, it was placed in a gear type aging tester that had been preheated to 190°C and taken out at regular intervals to conduct a thermal stability test. . The results are shown in Table-1. The degree of coloration of the sheet was expressed by the following numerical value and was used as a standard for evaluating thermal stability.

【table】

【table】

[Table] Example 2 Vinyl chloride resin Geon103EP [Nippon Zeon Co., Ltd.]
After mixing 100 parts of the additives shown in Table 1 and 1.5 parts of polyethylene wax, it was mixed with 100 parts of the
Knead for 5 minutes at ℃ to make a sheet with a thickness of 0.5 mm. After cutting this sheet into 3 cm x 6 cm size, put it in a gear type aging tester preheated to 210 ℃ and test it at regular intervals. The sample was taken out and its thermal stability was evaluated in the same manner as in the examples.

【table】

【table】

Claims (1)

[Claims] 1 (a) General formula (In the formula, R represents an alkyl group having 1 to 12 carbon atoms, and R ¹ represents an alkyl group having 8 to 18 carbon atoms.) Monoalkyltin tris (monohydroxyalkyl mercaptide) shown in (b) Monoalkyltin sulfides and (c) alkali metal or alkaline earth metal carboxylates, thiocarboxylates, oxides, hydroxides, carbonates, carbonates, substituted carbonates, organic overbase complexes, and compounds thereof A chlorine-containing resin composition comprising a chlorine-containing resin and at least one metal compound selected from the following. 2 General formula The chlorine-containing resin composition according to claim 1, wherein R in the formula is monoalkyltin tris (monohydroxyalkyl mercaptide), which is an alkyl group having 4 to 8 carbon atoms. 3. The chlorine-containing resin composition according to claim 1 or 2, wherein the metal compound is an alkali metal or alkaline earth metal carboxylate, hydroxide, or organic overbase complex. 4 Monoalkyltin tris (monohydroxyalkyl mercaptide) and monoalkyltin sulfide were mixed in a ratio of 1:1 to 100 parts by weight of chlorine-containing resin.
Claim 1, 2 or 3 uses 0.1 parts by weight to 3.0 parts by weight at a weight ratio of 10:1 to 10:1, and further uses 0.1 parts to 3.0 parts by weight of a metal compound. chlorine-containing resin composition.