JPS6353215B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to highly heat and light stabilized halogen-containing resin compositions without initial coloration. Lead-based stabilizers have a stabilizing effect on vinyl chloride resin against thermal deterioration and are widely used. However, vinyl chloride resins containing lead-based stabilizers have drawbacks such as initial discoloration during processing and insufficient light stability of the product. Furthermore, recently, even higher thermal stability under harsh temperature conditions has been required. In particular, when vinyl chloride resin products are used outdoors, a whitening phenomenon called yoking occurs, causing the surface of the product to lose its luster, which significantly impairs its product value, posing a problem. To prevent this phenomenon, dialkyltin maleate stabilizers such as dialkyltin maleate polymers and dialkyltin maleate esters and dialkyltin carboxylate stabilizers are used in combination, but dialkyltin maleate stabilizers are difficult to process. In some cases, the dialkyl tin carboxylate stabilizer imparts tackiness to the vinyl chloride resin, which is undesirable, and the dialkyl tin carboxylate stabilizer cannot sufficiently prevent the yoking phenomenon. As a result of research to improve the above-mentioned drawbacks, the inventors of the present invention found that the use of a specific mono-organotin compound in combination with a lead-based stabilizer can prevent initial coloring and provide excellent thermal stability and photostability. I found it. That is, in the present invention, when stabilizing a halogen-containing resin with a lead-based stabilizer, the general formulas (), (),
() and () RSnX ₃ () [RSn(OOCCH=CHCOO) _1.5 ] _o () [In the formulas (), (), () and (), R is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a 2-carbalkoxyethyl group, and X is a group -OOC-R', a group -OOCCH= CHCOOR″ (in the formula
R′ represents an alkyl group, hydroxyalkyl group, alkenyl group, aralkyl group, aryl group, or substituted aryl group; R″ represents an alkyl group, alkoxyalkyl group, alkenyl group, or aralkyl group);
This is a stabilized halogen-containing resin composition characterized by adding one or more monoorganotin compounds selected from the group represented by the following formula: n is an integer of 1 to 100. Examples of the monoorganotin compounds represented by the above general formulas (), (), () and () include monomethyltin trioctoate, monomethyltin trilaurate, monomethyltin tristearate, monomethyltin triricinolate, and monomethyltin tris (Benzyl Maleate), Monomethyl Tin Tribenzoate, Mono Butyl Tin Trilaurate, Mono Butyl Tin Tristearate, Mono Butyl Tin Trimontanate, Mono Butyl Tin Tris (12-Hydroxy Stearate), Mono Butyl Tin Tris (Cetyl Maleate), Mono Butyl Tin Tris (Stearyl) monobutyltin tris(butoxyethyl maleate), monobutyltin tris(t-butylbenzoate), bis[monobutyltin bis(benzyl maleate)] oxide, monobutyltin maleate polymer, bis(monobutyltin distearate) malate , monooctyltin tristearate, monooctyltin tribehenate, monooctyltin trimontanate, monooctyltin tris(12-hydroxystearate), monooctyltin triricinolate, monooctyltin triolate, monooctyltin tris( cetyl maleate), monooctyltin tris(oleyl maleate), bis(monoctyltin distearate) oxide, monooctyltin maleate polymer, 2-carbomethoxyethyltin trilaurate, 2-carbobutoxyethyltin tristearate, 2-carbobutoxyethyltin tristearate Examples include butoxyethyltin tribehenate, 2-carbobutoxyethyltin triolate, and the like. Examples of lead-based stabilizers used to stabilize halogen-containing resins include lead white, basic lead silicate, basic lead sulfate, dibasic lead sulfate, tribasic lead sulfate, basic lead sulfite, Dibasic lead phosphite, silica gel co-precipitated lead silicate, dibasic lead phthalate,
tribasic lead maleate, normal lead salicylate,
Examples include lead stearate, dibasic lead stearate, lead laurate, lead octylate, lead 12-hydroxystearate, lead behenate, and the like. Examples of the halogen-containing resins stabilized by the present invention include vinyl halide homopolymers such as vinyl chloride resin, vinyl bromide resin, and vinylidene chloride resin, as well as vinyl halides such as vinyl acetate, vinyl propionate, butyric acid, etc. Vinyl, vinylidene chloride, styrene, ethylene, propylene,
Methyl methacrylate, dialkyl fumarate,
or one of the comonomers such as malate and the like.
Mention may be made of copolymers such as those formed by polymerizing a species or two or more species. It is also applicable to mixtures of halogen-containing resins and impact-improving resins such as acrylonitrile-butadiene-styrene resins, methyl methacrylate-butadiene-styrene resins, vinyl acetate-ethylene copolymer resins, or chlorinated polyethylene resins. The stabilized halogen-containing resin composition of the present invention usually includes 1 to 7 parts by weight, preferably 2 to 5 parts by weight, of a lead-based stabilizer and 0.001 to 5 parts by weight of a monoorganotin compound, based on 100 parts by weight of the halogen-containing resin. , preferably 0.1 to 2 parts by weight. A lead-based stabilizer and a mono-organotin compound may be used in one package. Furthermore, in addition to these stabilizers, known stabilizers such as metal soaps, other organotin stabilizers, epoxy compounds, organic phosphite esters,
Aminocrotonic acid ester, α-phenylindole, phenolic antioxidant, and ultraviolet absorber can be added. Pigments, fillers, antistatic agents, lubricants, flame retardants, and processing aids can also be used as required. According to the present invention, by adding a monoorganotin compound to a halogen-containing resin stabilized with a lead-based stabilizer, the thermal stability of the resin can be increased and the initial coloration can be improved. Furthermore, even if the resin is used outdoors for a long time, no yoking phenomenon occurs and the surface does not lose its luster. Examples will now be illustrated, where parts represent parts by weight. Example 1 Vinyl chloride resin (Geon103Ep-8, Nippon Zeon)
100 parts Tribasic lead sulfate 1.5〃 Lead stearate 1.5〃 Monoorganotin compound shown in Table 1 below 0.5〃 A mixture consisting of each of the above compositions was tested on a test roll.
The mixture was kneaded at 190°C for 3 minutes to form a sheet with a thickness of 0.5 mm. After cutting each sheet into 2cm x 2cm size
It was placed in a gear aging tester at 190°C, taken out after a certain period of time, and subjected to a thermal stability test. Results first
Shown in the table. In addition, the evaluation of thermal stability in the table is expressed in numbers and is as follows. 1...Colorless 2...Yellow 3...Brown 4...
Blackish brown 5...Black

[Table] Example 2 Vinyl chloride resin (Geon103Ep) 100 parts Impact strengthener (Kane Ace B-12, manufactured by Kaneka Co., Ltd.)
5〃 Basic lead sulfite 1 〃 Dibasic lead stearate 0.5〃 Lead stearate 1 〃 Mono-organotin compound shown in Table 2 below 0.3〃 A mixture consisting of the above composition was tested on a test roll.
The mixture was kneaded at 190°C and the time required for the sheet to decompose and turn black was measured. The results are shown in Table 2.

[Table] Example 3 Vinyl chloride resin (Geon103Ep-8) 100 parts Impact strengthener (Kane Ace B-12) 10 Filler (Whiten SB, manufactured by Shiraishi Calcium Co., Ltd.)
3 Tribasic lead sulfate 1 Dibasic lead phosphite 0.5 Lead stearate 1.5 Processing aid (PA-20, manufactured by Kaneka Co., Ltd.) 1 Monoorganotin compound shown in Table 3 below 1 Above Thermal stability of the formulation consisting of the following composition was measured using a Brabender plastograph under the following conditions. Model: Brabender. Type PLV-151 Roller mixer type 50 Number of revolutions: 60 rpm. Set temperature: 200°C Filling amount: 62 g The results are shown in Table 3.

【table】

[Table] Example 4 Vinyl chloride resin (Geon103Ep-8) 100 parts Impact strengthener (Kane Ace B-12) 5 Filler (Shiraishika CCR, manufactured by Shiraishi Calcium Co., Ltd.)
5 〃 Tribasic lead sulfate 2 〃 Lead stearate 1 〃 Monoorganotin compound shown in Table 4 below 0.5 〃 A mixture consisting of each of the above compositions was kneaded using a test roll at 190°C for 3 minutes to a thickness of 0.5 mm. I created a sheet. This sheet was cut into a size of 5 cm x 15 cm, two sheets were stacked on top of each other, and pressed at 170° C. and 30 kg/cm ² for 20 minutes. A weather resistance test was conducted on each of the obtained pressed sheets using a sunshine weather meter, and the time required for the surface of the sheet to lose its luster was observed. The results are shown in Table 4.

【table】

【table】

【table】

Claims (1)

[Claims] 1. In stabilizing a halogen-containing resin with a lead-based stabilizer, general formulas (), (), () and () RSnX ₃ () [RSn(OOCCH=CHCOO) _1.5 ] _o () [In the formulas (), (), () and (), R is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a 2-carbalkoxyethyl group, and X is a group -OOC-R', a group -OOCCH= CHCOOR″ (in the formula
R′ represents an alkyl group, hydroxyalkyl group, alkenyl group, aralkyl group, aryl group, or substituted aryl group; R″ represents an alkyl group, alkoxyalkyl group, alkenyl group, or aralkyl group);
1. A stabilized halogen-containing resin composition characterized by adding one or more monoorganotin compounds selected from the group represented by the following formula: n is an integer of 1 to 100.