JPS6315948B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vinyl chloride resin composition stabilized against heat, which is formed by adding a sulfur-containing organotin compound or a sulfur-containing organotin compound in combination with an alkaline earth metal or zinc compound. Since halogen-containing resin is exposed to high temperatures during molding, it deteriorates due to heat and becomes discolored. To prevent this coloration, stabilizers such as metal soaps, organic tin compounds, epoxy compounds, and organic phosphite esters are used singly or in combination. Among these, organic tin compounds have an excellent thermal stabilizing effect, but in recent years, extrusion processing and calender processing have become larger in size, requiring higher temperatures and higher speeds, and injection molding processing has begun to mold larger products. As a result, the thermal stabilization effect of conventional organotin compounds has become insufficient. For this reason, there has been a strong demand for stabilizers with excellent thermal stabilizing effects. As a result of intensive research in order to obtain a vinyl chloride resin composition with excellent thermal stability, the present inventors achieved the objective and completed the first invention by adding a specific sulfur-containing organotin compound to vinyl chloride resin. . As a result of further research, it was discovered that a vinyl chloride resin composition containing the specific sulfur-containing organotin compound and an alkaline earth metal or zinc compound had excellent thermal stability. completed. That is, the first invention uses a vinyl chloride resin having the general formula (1). (In the formula, R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms,
Z is −S(CH ₂ ) _o COO−, −S(CH ₂ ) _o OOCCH=
CHCOO−, −S(CH ₂ ) _o OOCCH=CHCOO
(CH ₂ ) _o S- or -S (CH ₂ ) _o COOR ³ OOC (CH ₂ ) _o
It is a group represented by S-. n is an integer of 1 or 2,
R ³ is an alkylene group having 1 to 6 carbon atoms. ) to the organotin group represented by the general formula (2) (In the formula, R ⁴ is an alkyl group having 8 to 18 carbon atoms.) The present invention provides a vinyl chloride resin composition. The vinyl chloride resin composition of the first invention has excellent thermal stability, and is particularly excellent in initial coloring properties. The second invention is based on vinyl chloride resin, (a) general formula (1) (In the formula, R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms, and Z is -S(CH ₂ ) _o COO-, -S(CH ₂ ) _o
OOCCH=CHCOO−, -S(CH ₂ ) _o OOCCH=
CHCOO (CH ₂ ) _o S- or -S (CH ₂ ) _o
COOR ³ OOC(CH ₂ ) _o is a group represented by S-.
n is an integer of 1 or 2, and R ³ is an alkylene group having 1 to 6 carbon atoms. ) to the organotin group represented by the general formula (2) (In the formula, R ⁴ is an alkyl group having 8 to 18 carbon atoms.) At least one sulfur-containing organotin compound to which at least one hydroxyalkylthio group represented by the formula: (b) alkaline earth Carboxylate, thiocarboxylate, oxide, hydroxide of metal or zinc,
The present invention provides a stabilized vinyl chloride resin composition containing at least one metal compound selected from the group consisting of carbonates, carbonates, substituted carbonates, and organic overbase complexes. The vinyl chloride resin composition of the second invention includes a sulfur-containing organotin compound,
Due to the synergistic effect with alkaline earth metal or zinc compounds, it has excellent performance in initial coloring properties and long-term thermal stability. To describe in detail the sulfur-containing organotin compound used in the first invention and the second invention, the sulfur-containing organotin compound is an organotin compound having at least one hydroxyalkylthio group. General formula (1)
To explain in detail the organotin group shown in
R ¹ and R ² are alkyl groups such as methyl, butyl, hexyl, and octyl, and Z is -SCH ₂ COO-, -S(CH ₂ ) ₂ COO-, -S(CH ₂ ) ₂ OOCCH=CHCOO-, −S(CH ₂ ) ₂ OOCCH=CHCOO(CH ₂ ) ₂ S−, −SCH ₂ COO(CH ₂ ) ₂ OOCCH ₂ S−, −S(CH ₂ ) ₂ COO(CH ₂ ) ₂ OOC(CH ₂ ) ₂ S−, −SCH ₂ COO(CH ₂ ) ₄ OOCCH ₂ S−, −S(CH ₂ ) ₂ COO(CH ₂ ) ₄ OOC(CH ₂ ) ₂ S−, −SCH ₂ COO(CH ₂ ) ₆ OOCCH ₂ S- or a group such as -S(CH ₂ ) ₂ COO(CH ₂ ) ₆ OOC(CH ₂ ) ₂ S-. To explain in detail the hydroxyalkylthio group represented by general formula (2), R ⁴ has 8 to 18 carbon atoms.
Examples of hydroxyalkylthio groups are:

[Formula] or

[Formula] etc. The sulfur-containing organotin compound used in the first invention and the second invention has a hydroxyalkylthio group represented by the general formula (2) in at least one tin atom of the organotin group represented by the general formula (1). is a compound in which at least one of the following is bonded. That is, the compounds include compounds in which up to four hydroxyalkylthio groups are bonded to two tin atoms of the general formula (). When the number of hydroxyalkylthio groups is less than 4, there is no particular restriction on the type of group bonded to the remaining bond of the tin atom, but preferred examples include an alkoxycarbonylalkylthio group, an acyloxy group, an alkoxymaleoyloxy group, etc. be able to. Preferred examples of sulfur-containing organotin compounds include: etc. can be mentioned. Preferred carboxylates, thiocarboxylates, oxides, hydroxides, carbonates, carbonates, substituted carbonates, and organic overbase complexes of alkaline earth metals or zinc used in the second invention will be described in detail. Examples of metals include alkaline earth metals such as magnesium, calcium, strontium, barium, and zinc, and particularly preferred examples include magnesium, calcium, and barium. In addition, examples of carboxylic acid residues constituting alkaline earth metal or zinc carboxylates include:
Acetoxy, propionyloxy, butyryloxy, hexanoyloxy, octanoyloxy,
2-ethylhexanoyloxy, decanoyloxy, dodecanoyloxy, hexadecanoyloxy, octadecanoyloxy, docosanoyloxy, octadecenoyloxy, ricinoleyloxy, acryloyloxy, methacryloyloxy, crotonoyloxy, Acetoacetoxy, benzoyloxy, (oxalyldioxy) ^1/2 , (malonyldioxy) ^1/2 , (succinyldioxy) ^1/2 ,
(glutaryldioxy) ^1/2 , (adipoyldioxy)
^1/2 , (maleoyldioxy) ^1/2 , (phthaloyldioxy) ^1/2 , methoxymaleoyloxy, butoxymaleoyloxy, octyloxymaleoyloxy, isooctyloxymaleoyloxy, 2
-Ethylhexyloxymaleoyloxy, dodecyloxymaleoyloxy, tridecyloxymaleoyloxy, octadecyloxymaleoyloxy, octadecenyloxymaleoyloxy, cyclohexyloxymaleoyloxy, benzyloxymaleoyloxy, methoxyethyloxy maleoyloxy, butoxyethyloxymaleoyloxy, phenoxyethyloxymaleoyloxy, methoxybutyloxymaleoyloxy, 3,6-dioxadecyloxymaleoyloxy, [ethylenedioxy bis(maleoyloxy)] ] ^1/2 , [tetramethylenedioxy bis(maleoyloxy)] ^1/2 , cyclohexyloxyphthaloyloxy, octadecyloxyphthaloyloxy, and octadecyloxyadipoyloxy. Examples of alkaline earth metal or zinc carboxylates include bis(acetoxy)magnesium, bis(octanoyloxy)magnesium,
Bis(dodecanoyloxy)magnesium, bis(octadecanoyloxy)magnesium, bis(octadecenoyloxy)magnesium, bis(ricinoleyloxy)magnesium, bis(monooctadecyloxymaleoyloxy)magnesium, maleoyldi Oxymagnesium, bis(acetoxy)calcium, bis(octanoyloxy)calcium, bis(dodecanoyloxy)calcium, bis(octadecanoyloxy)calcium, bis(isooctadecanoyloxy)calcium, bis(octadecenoyl) oxy)calcium, bis(ricinoleyloxy)calcium, bis(monooctadecyloxymaleoyloxy)calcium, bis(octadecanoyloxy)strontium, bis(octanoyloxy)barium, bis(dodecanoyloxy)
Barium, bis(octadecanoyloxy)barium, bis(octadecanoyloxy)barium, bis(ricinoleyloxy)barium, bis(monooctadecyloxymaleoyloxy)barium, maleoyldioxybarium, bis(octanoyl) oxy)zinc, bis(octadecanoyloxy)zinc, bis(octadecenoyloxy)zinc, bis(monooctadecyloxymaleoyloxy)zinc, maleoyldioxyzinc, etc. Examples of thiocarboxylic acid residues constituting alkaline earth metal or zinc thiocarboxylate salts include acetylthio, propionylthio, butyrylthio, hexanoylthio, octanoylthio, 2-
Ethylhexanoylthio, decanoylthio, dodecanoylthio, hexadecanoylthio, octadecanoylthio, docosanoylthio, octadecenoylthio, ricinoleylthio, acryloylthio, methacryloylthio, crotonoylthio, acetoacetylthio, benzoylthio, (oxalyldithio) ^1/2 , (malonyldithio) ^1/2 , (succinyldithio) ^1/2 , (glutaryldithio) ^1/2 , (adipoyldithio) ^1/2 , (maleoyldithio) ^1/2 , (phthaloyldithio) ^1/2 , methoxymaleoyldithio , butoxymaleoylthio, octyloxymaleoylthio, isooctyloxymaleoylthio, 2-ethylhexyloxymaleoylthio, dodecyloxymaleoylthio, tridecyloxymaleoylthio, octadecyloxymaleoylthio, octadecenyl Oxymaleoylthio, cyclohexyloxymaleoylthio, benzyloxymaleoylthio, methoxyethyloxymaleoylthio, butoxyethyloxymaleoylthio, butoxyethyloxymaleoylthio, phenoxyethyloxymaleoylthio, methoxybutyloxy Maleoylthio, 3,6-dioxadecyloxymaleoylthio, [ethylenedioxy bis(maleoylthio)] ^1/2 , [tetramethylenedioxy bis(maleoylthio)] ^1/2 , cyclohexyloxyphthaloylthio , octadecyloxyphthaloylthio and octadecyloxyadipoylthio. Examples of alkaline earth metal or zinc thiocarboxylate salts include bis(dodecanoylthio)magnesium, bis(octadecanoylthio)magnesium, bis(octadecenoylthio)magnesium, maleoyldithiomagnesium, bis(dodecanoylthio)calcium, Bis(octadecanoylthio)calcium, maleoyldithiocalcium, 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 alkaline earth metal or zinc carbonates and substituted carbonates include phenyloxy, methylphenyloxy, tert-butylphenyloxy,
Octylphenyloxy, nonylphenyloxy, chlorophenyloxy, hydroxyphenyloxy, naphthyloxy, methoxyphenyloxy, 3-methyl-4-isopropylphenyloxy and tert-butyl-methoxyphenyloxy, etc. . Examples of carbonates and substituted carbonates of alkaline earth metals or zinc include bis(phenyloxy)magnesium, bis(phenyloxy)calcium, bis(phenyloxy)barium, bis(octylphenyloxy)barium, bis(nonylphenyl). oxy)barium, bis(phenyloxy)zinc, etc. Examples of oxides, hydroxides or carbonates of alkaline earth metals or zinc are magnesium oxide, calcium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and calcium carbonate, zinc oxide, zinc hydroxide. etc. Organic overbased complexes of alkaline earth metals or zinc are oil-soluble metal salts commonly called basic salts, ultrabasic salts, overbased salts, highly basic dispersants, etc. Known as an additive. The manufacturing method of this organic overbase complex is described in U.S. Patent No. 2,616,924, U.S. Pat. In the process, aliphatic acid salts, cyclic aliphatic acid salts, and aromatic acid salts of metals are produced by direct method or double decomposition method using alcohol as a medium, and in the presence of surplus metal oxides or hydroxides. Blow carbon dioxide gas into the mixture to carbonate it to produce an organic overbase complex with a high metal content. Although there are many unknowns about the chemical structure of this complex, the above-mentioned carboxylic acid metal salt or thiocarboxylic acid metal salt, which is widely used to stabilize halogen-containing resins,
That is, it is clearly distinguished from bis(octadecanoyloxy)magnesium, maleoyldioxycalcium, bis(dodecanoyloxy)barium, bis(octadecanoylthio)magnesium, and the like. In other words, the organic overbase complex is
The basicity is expressed as "the number of bases equivalent to the number of mg of caustic potash in water", while the carboxylic acid metal salts such as bis(octadecanoyloxy)magnesium and maleoyldioxycalcium mentioned above have a basicity of 0. It is a neutral salt of 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 the metal ratio is defined as the total weight of metal divided by the weight of metal equivalent to the organic acid. According to the following, the metal ratio exceeds 1, and bis(octanoyloxy)magnesium, maleoyldioxycalcium, etc. have a metal ratio of 1. The amount of the sulfur-containing organotin compound used in the first invention to be added to the vinyl chloride resin, the combination ratio of the sulfur-containing organotin compound and the alkaline earth metal or zinc compound used in the second invention, and the vinyl chloride resin There is no particular restriction on the amount added, and it is determined as appropriate depending on the type of resin and the intended molded product.
According to the research of the present inventors, in the first invention, the sulfur-containing organotin compound is preferably 0.1 to 2.0 parts by weight per 100 parts by weight of the vinyl chloride resin, and in the second invention, the sulfur-containing organotin compound is preferably 0.1 to 2.0 parts by weight. The weight ratio of the organotin compound and the metal compound is preferably 1:1 to 1:10,
The amount added is preferably 0.1 to 1.0 parts by weight of the sulfur-containing organotin compound and 0.3 to 3.0 parts by weight of the metal compound relative to 100 parts by weight of the vinyl chloride resin. The vinyl chloride resin compositions of the first invention and the second invention can be prepared by mixing the resin and the stabilizer using a known mixing method, for example, a mixer such as a Henschel mixer, a kneader, a Banbury mixer, or a ribbon blender. It can be obtained by The vinyl chloride resin compositions of the first invention and the second invention can contain an epoxy compound, an organic phosphite, a polyhydric alcohol, an ultraviolet absorber, a pigment, a plasticizer, a lubricant, etc., as necessary. Examples of epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil,
These include epoxidized safflower oil, 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,
These include 4'-isopropylidene diphenol phosphite, bis(nonylphenyl)hydrodiene phosphite and (stearyl)pentaerythrityl diphosphite. Examples of polyhydric alcohols include 1,3-butanediol, 1,4-butanediol, triethylene glycol, dipropylene glycol, polypropylene glycol,
These include trimethylolmethane, 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, aliphatic esters, polyhydric alcohol esters, epoxies, polyesters, and other alkyl esters. These include sulfonic 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,
These include rice bran wax, montan wax, and amide-based lubricants. Examples of vinyl chloride resins used in the first and second inventions include vinyl chloride resins, copolymer resins mainly composed of vinyl chloride, such as vinyl chloride-vinyl acetate copolymer resins, and vinyl chloride-ethylene copolymer resins. , 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 Polymer 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 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, vinyl chloride-acrylonitrile- Mainly contains butadiene-styrene copolymer resin, vinyl chloride-methyl methacrylate-butadiene-styrene copolymer resin, vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin, chlorinated ethylene resin, chlorinated propylene resin, vinyl acetate resin, etc. Resin, butadiene resin, isobutylene resin, ethylene resin, propylene resin, styrene resin, acrylic resin, urethane resin, ethylene-vinyl acetate copolymer resin, ethylene-propylene copolymer resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene-styrene Examples include polymer blends with copolymer resins and methacrylonitrile-butadiene-styrene copolymer resins. Next, the fact that the vinyl chloride resin compositions of the first invention and the second invention have excellent thermal stability will be specifically explained using examples. In the Examples, parts mean parts by weight, and the stabilizers used in the Examples are shown below and indicated with code numbers in the Examples.

[Table] ｜
｜
OH
OH

[Table] ｜
｜
SCH ₂ CH ₂ COOC ₈ H
₁₇ SCH ₂ CH ₂ COOC ₈ H ₁₇

[Table] Example 1 Vinyl chloride resin [Geon manufactured by Nippon Zeon Co., Ltd.]
103EP] Add the stabilizer shown in Table 1 to 100 parts,
After thorough mixing, the mixture was kneaded for 4 minutes using a test roll heated to 160°C to produce a sheet with a thickness of 0.5 mm. This sheet was cut to a size of 3 cm x 6 cm to prepare a sample, and the sample was placed in a gear type aging tester preset to 180° C. zero ambient temperature to test thermal stability. The test pieces were taken out at regular intervals, and the degree of coloration was visually examined, and the evaluation criteria were quantified into 1: colorless, 2: pale yellow, 3: yellow, 4: pale brown, 5: brown, and 6: black, and are shown in Table 1.

【table】

【table】

[Table] No. 1 to No. 16 are examples, and No. 17 to No. 20 are comparative examples. Example 2 Vinyl chloride resin [Geon manufactured by Nippon Zeon Co., Ltd.]
103EP] Add the stabilizer shown in Table 2 to 100 parts,
After thorough mixing, a sheet was prepared under the same operating conditions as in Example 1, and a thermal stability test was conducted. The results are shown in Table-2. The evaluation criteria are the same as in Example 1.

【table】

【table】

[Table] No. 21 to No. 43 are examples, and No. 44 to No. 51 are comparative examples. Example 3 Vinyl chloride resin [Geon manufactured by Nippon Zeon Co., Ltd.
103EP] 100 parts, methacrylnitrile-butadiene-styrene copolymer resin [Kane Ace B-12 manufactured by Kanebuchi Chemical Co., Ltd.] 10 parts, titanium oxide [TA-100 manufactured by Fuji Titanium Industries Co., Ltd.] 0.5 parts, polyethylene wax Thoroughly mix 1.0 part of Tsukusu [HIWATUKUSU 405MP manufactured by Mitsui Petrochemical Co., Ltd.] with the stabilizer shown in Table 3, and extrude the mixture using a 40 mm extruder (dice temperature: 190°C, cylinder temperature: 160-180°C,
A pipe with an outer diameter of about 8 mm and an inner diameter of about 6 mm was formed at a screw rotation speed of 15 rpm, a length ratio of L/D = 22, and a compression ratio of 3.5:1), and the degree of coloration of the pipe was examined. The results are shown in Table 3.

【table】

【table】

[Table] Nos. 52 to 64 are examples, and Nos. 65 to 73 are comparative examples.

Claims (1)

[Claims] 1. Vinyl chloride resin, general formula (1) (In the formula, R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms,
Z is -S(CH ₂ ) _o COO-, -S-(CH ₂ ) _o OOCCH
=CHCOO-, -S-( _CH2 ) _o OOCCH=CHCOO
(CH ₂ ) _o -S- or -S (CH ₂ ) _o COOR ³ OOC
(CH ₂ ) _o It is a group represented by S-. n is 1 or 2
The integer R ³ is an alkylene group having 1 to 6 carbon atoms. ) to the organotin group represented by the general formula (2) (In the formula, R ⁴ is an alkyl group having 8 to 18 carbon atoms.) It is characterized by adding at least one sulfur-containing organotin compound to which at least one hydroxyalkylthio group represented by the following formula is bonded. A vinyl chloride resin composition. 2 In vinyl chloride resin, (a) General formula (1) (In the formula, R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms, and Z is -S(CH ₂ ) _o COO-, -S-(CH ₂ ) _o
OOCCH=CHCOO-, -S-( _CH2 ) _o OOCCH
=CHCOO( _CH2 ) _o -S- or -S( _CH2 ) _o
COOR ³ OOC(CH ₂ ) _o is a group represented by S-.
n is an integer of 1 or 2, and R ³ is an alkylene group having 1 to 6 carbon atoms. ) to the organotin group represented by the general formula (2) (In the formula, R ⁴ is an alkyl group having 8 to 18 carbon atoms.) At least one sulfur-containing organotin compound to which at least one hydroxyalkylthio group represented by the formula: (b) alkaline earth Carboxylate, thiocarboxylate, oxide, hydroxide of metal or zinc,
1. A vinyl chloride resin composition, characterized in that it contains at least one metal compound selected from the group consisting of carbonates, carbonates, substituted carbonates, and organic overbase complexes.