JPS6411224B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for stabilizing a polymer obtained by blending a halogen-containing resin with a styrene resin. [Industrial Field of Application] The method of the present invention can be widely used in the field of molding polymers blended with styrenic resins for the purpose of improving the impact properties of halogen-containing resins. [Prior Art] Generally, halogen-containing resins have poor impact resistance, and styrene-based resins are blended as a reinforcing agent to improve impact resistance. However, although products molded using the blended polymer have improved impact strength, they have the disadvantage of poor thermal stability and weather resistance. Generally, in this field, an organotin maleate compound is added in combination to improve weather resistance, and an organotin sulfur-containing compound is added in order to further improve thermal stability to stabilize the blended polymer. The current situation is that [Problems to be Solved by the Invention] Although the organotin-sulfur-containing compound used to stabilize the above-mentioned blend polymer has an excellent thermal stabilizing effect, it has poor weather resistance. It is not often used in fields that require it, and is stabilized and molded only with organotin maleate compounds, which have excellent weather resistance, but as a result, the thermal stabilization effect is insufficient, so it is necessary to maintain weather resistance The development of a stabilizer with excellent thermal stabilization effects has been awaited. [Means for Solving the Problem] From this perspective, the present inventors have developed a blend polymer consisting of a halogen-containing resin and a styrene resin that takes advantage of the weather resistance of the organotin maleate compound and also has a thermal stabilizing effect. As a result of intensive research into stabilizers with
With respect to 100 parts by weight, (a) 0.1 to 10 parts by weight of an organotin maleate compound, (b) General formula (1) (In the formula, R is an alkyl group, a cycloalkyl group,
It represents an alkenyl group, an aralkyl group, a phenyl group, or an alkyl-substituted phenyl group, and R ¹ and R ² each represent a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ) 0.005 substituted mercaptopropionic acid
It has been found that by adding ~1 part by weight in combination, the thermal stability of the blended polymer is significantly improved due to the mutual effect, there is no decrease in weather resistance, and plate-out during molding can be prevented. Completed the invention. Examples of the halogen-containing resin used in the present invention include commonly used halogen-containing resins, such as vinyl chloride resin, vinyl bromide resin, vinylidene chloride resin, chlorinated ethylene resin, and chlorinated propylene resin. , post-chlorinated vinyl chloride resin, 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, Examples include vinyl chloride-ethylene-vinyl acetate copolymer resin. In the present invention, the styrene resin to be blended with the halogen-containing resin includes styrene and vinyl aromatic compounds such as α-substituted styrene such as α-methylstyrene, vinyltoluene, and nuclear-substituted styrene such as o-chlorostyrene. and other monomers copolymerizable with it, such as acrylonitrile, vinyl compounds such as acrylic acid and methacrylic acid and their esters, vinyl heterocyclic compounds such as vinylpyridine and vinylcarbazole, butadiene, 1 -Chlorbutadiene,
Examples include copolymers with monomers such as conjugated diene compounds such as 2-chlorobutadiene and isoprene, such as acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and methacrylic acid. Examples include ester-butadiene-styrene copolymers and blends of these resins. In the present invention, the blend ratio of the halogen-containing resin and the styrene-based resin varies depending on the purpose of the molded product, and the blend ratio varies depending on the purpose, but in general, the blend ratio of the halogen-containing resin and the styrene resin is 100%
The amount of styrene resin added is 3 to 3 parts by weight.
It is 100 parts by weight. The organotin maleate compounds used in the present invention include commonly used compounds,
For example, preferably general formulas (2) and (3) [In formulas (2) and (3), R ³ is an alkyl group, an alkenyl group,
Aralkyl group or alkoxyalkyl group, R ⁴
is an alkyl group having 1 to 12 carbon atoms, A is oxygen or a group represented by -OOCCH=CHCOO-, k is 0 or 1, and l is an integer of 1 to 10. ] and the like. Examples of the organotin maleate compounds represented by the above general formula (2) include the following. Dimethyltin bis(methyl maleate), dimethyltin bis(ethyl maleate), dimethyltin bis(isopropyl maleate), dimethyltin bis(butyl maleate), dimethyltin bis(hexyl maleate), dimethyltin bis(octyl) dimethyltin bis(isooctyl maleate), dimethyltin bis(2-ethylhexyl maleate),
Dimethyltin bis(decyl maleate), dimethyltin bis(dodecyl maleate), dimethyltin bis(tridecyl maleate), dimethyltin bis(octadecyl maleate), dimethyltin bis(oleyl maleate), dimethyltin bis(benzyl maleate) ate), dimethyltin bis(cyclohexyl maleate), dimethyltin bis(methoxybutyl maleate), dibutyltin bis(methyl maleate),
Dibutyltin bis(ethyl maleate), dibutyltin bis(propyl maleate), dibutyltin bis(isopropyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(amyl maleate), dibutyltin bis(hexyl maleate) ), dibutyltin bis(heptyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis(2-ethylhexyl maleate), dibutyltin bis(nonyl maleate), dibutyltin Bis(decyl maleate), dibutyltin bis(dodecyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(allyl maleate), dibutyltin bis(oleyl maleate) , dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dibutyltin bis(methoxybutyl maleate), dioctyltin bis(ethyl maleate), dioctyltin bis(propyl maleate), dioctyltin bis(propyl maleate) (isopropyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleate), dioctyltin bis(octyl maleate),
Dioctyltin bis(isooctyl maleate),
Dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(decyl maleate), dioctyltin bis(dodecyl maleate), dioctyltin bis(tridecyl maleate), dioctyltin bis(octadecyl maleate), dioctyltin bis( oleyl maleate), dioctyltin bis(benzyl maleate), dioctyltin bis(cyclohexyl maleate), dioctyltin bis(methoxybutyl maleate), dilauryltin bis(ethyl maleate), dilauryltin bis(isopropyl maleate) , dilauryltin bis(butyl maleate), dilauryltin bis(hexyl maleate), dilauryltin bis(octyl maleate), dilauryltin bis(isooctyl maleate), dilauryltin bis(2-ethylhexyl maleate, dilauryltin Bis(decyl maleate), dilauryltin bis(dodecyl maleate),
Dilauryltin bis (tridecyl maleate), dilauryltin bis (octadecyl maleate), dilauryltin bis (oleyl maleate), dilauryltin bis (benzyl maleate), dilauryltin bis (cyclohexyl maleate), dilauryltin bis (cyclohexyl maleate) methoxybutyl maleate), bis(dimethyltin methyl maleate) maleate, bis(dimethyltin ethyl maleate) maleate,
Bis(dimethyltin isopropyl maleate) maleate, bis(dimethyltin butyl maleate) maleate, bis(dimethyltin hexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin isooctyl maleate) maleate , bis(dimethyltin 2-ethylhexyl maleate) maleate, bis(dimethyltin decyl maleate) maleate,
Bis(dimethyltin dodecyl maleate) maleate, bis(dimethyltin tridecyl maleate) maleate, bis(dimethyltin octadecyl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, bis(dimethyltin benzyl maleate) maleate , bis(dimethyltin cyclohexyl maleate) maleate, bis(dimethyltin methoxybutyl maleate) maleate, bis(dibutyltin methyl maleate) maleate, bis(dibutyltin ethyl maleate) maleate, bis(dibutyltin propyl maleate)
Maleate, bis(dibutyltin isopropyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin amyl maleate) maleate, bis(dibutyltin hexyl maleate) maleate, bis(dibutyltin heptyl maleate) maleate, Bis(dibutyltin octyl maleate) maleate, bis(dibutyltin isooctyl maleate) maleate,
Bis(dibutyltin 2-ethylhexyl maleate) maleate, bis(dibutyltin nonyl maleate) maleate, bis(dibutyltin decyl maleate) maleate, bis(dibutyltin dodecyl maleate) maleate, bis(dibutyltin tridecyl maleate) maleate, bis (dibutyltin octadecyl maleate) maleate, bis(dibutyltin allyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dibutyltin benzyl maleate) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis (dibutyltin methoxybutyl maleate) maleate, bis(dioctyltin ethyl maleate) maleate, bis(dioctyltin propyl maleate) maleate, bis(dioctyltin isopropyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, Bis(dioctyltin hexyl maleate) maleate, bis(dioctyltin octyl maleate) maleate, bis(dioctyltin isooctyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin decyl maleate) maleate , bis(dioctyltin dodecyl maleate) maleate, bis(dioctyltin tridecyl maleate) maleate, bis(dioctyltin octadecyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate,
Bis(dioctyltin cyclohexyl maleate)
Maleate, bis(dioctyltin methoxybutyl maleate) maleate, bis(dilauryltin ethyl maleate) maleate, bis(dilauryltin isopropyl maleate) maleate, bis(dilauryltin butyl maleate) maleate,
Bis(dilauryltin hexyl maleate) maleate, Bis(dilauryltin octyl maleate)
maleate, bis(dilauryltin isooctyl maleate, maleate, bis(dilauryltin 2-
ethylhexyl maleate) maleate, bis(dilauryltindecyl maleate) maleate,
Bis(dilauryltin dodecyl maleate) maleate, Bis(dilauryltin tridecyl maleate) maleate, Bis(dilauryltin octadecyl maleate) maleate, Bis(dilauryltin oleyl maleate) maleate, Bis(dilauryltin benzyl maleate) maleate , bis(dilauryltin cyclohexyl maleate) maleate, bis(dilauryltin methoxybutyl maleate) maleate, bis(dimethyltin thyl maleate) oxide, bis(dimethyltin butyl maleate) oxide, bis(dimethyltin isooctyl maleate) oxide , bis(dimethyltin benzyl maleate) oxide, bis(dibutyltin methyl maleate) oxide, bis(dibutyltin butyl maleate) oxide, bis(dibutyltin isooctyl maleate) oxide, bis(dibutyltin benzyl maleate) Oxide, bis(dioctyltin butyl maleate)
oxide, bis(dioctyltin isooctyl maleate) oxide, bis(dioctyltin benzyl maleate) oxide, bis(dilauryltin butyl maleate) oxide, bis(dilauryltin isooctyl maleate) oxide, bis(dilauryltin benzyl maleate) ate) oxide, and preferred examples include dibutyltin bis(methyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis(2-ethylhexyl maleate), Dibutyltin bis(tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dioctyltin bis( butyl maleate), dioctyltin bis(isooctyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(tridecyl maleate), dioctyltin bis(octadecyl maleate, dioctyltin bis(oleyl maleate) ate), dioctyltin bis(benzyl maleate), dioctyltin bis(cyclohexyl maleate), bis(dibutyltin methyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin isooctyl maleate) maleate,
Bis(dibutyltin 2-ethylhexyl maleate) maleate, bis(dibutyltin tridecyl maleate) maleate, bis(dibutyltin octadecyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dibutyltin benzyl maleate) ) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin isooctyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin tridecyl maleate) maleate,
Bis(dioctyltin octadecyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin cyclohexyl maleate) maleate, bis(sibutyltin methyl maleate) oxide, Bis(dibutyltin butyl maleate) oxide, bis(dibutyltin benzyl maleate) oxide,
Examples include bis(dioctyltin butyl maleate) oxide and bis(dioctyltin benzyl maleate) oxide. Examples of the organotin maleate compound represented by the general formula (3) include the following. dimethyltin maleate,
These include dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, and polymers thereof, and preferred examples include dibutyltin maleate, dioctyltin maleate, and polymers thereof. In the substituted mercaptopropionic acid represented by the general formula (1) used in the present invention, R in the formula is, for example, a straight or branched alkyl group having 1 to 22 carbon atoms, a cycloalkyl group, an alkenyl group, an aralkyl group, a phenyl group, an alkyl-substituted phenyl group substituted with an alkyl group having 1 to 12 carbon atoms,
R ¹ and R ² are hydrogen atoms, methyl groups, ethyl groups,
Phenyl group, and preferred examples of such compounds are methylmercaptopropionic acid, ethylmercaptopropionic acid, propylmercaptopropionic acid, butylmercaptopropionic acid, hexylmercaptopropionic acid, octylmercaptopropionic acid, 2-ethylhexylmercapto. Propionic acid, isooctylmercaptopropionic acid, decylmercaptopropionic acid, dodecylmercaptopropionic acid, tetradecylmercaptopropionic acid, hexadecylmercaptopropionic acid, octadecylmercaptopropionic acid, oleylmercaptopropionic acid, phenylmercaptopropionic acid, p- Methylphenylmercaptopropionic acid, o-methylphenylmercaptopropionic acid, p-nonylphenylmercaptopropionic acid, p-tert-butylphenylmercaptopropionic acid, benzylmercaptopropionic acid, cyclohexylmercaptopropionic acid, butylmercapto α- Methylpropionic acid, hexylmercapto α-methylpropionic acid, octylmercapto α-methylpropionic acid, 2-ethylhexylmercapto α-methylpropionic acid, isooctylmercapto α-methylpropionic acid, decylmercapto α-methylpropionic acid, dodecylmercapto α -Methylpropionic acid, tridecylmercapto α-methylpropionic acid, tetradecylmercapto α-methylpropionic acid, hexadecylmercapto α-methylpropionic acid, octadecylmercapto α-methylpropionic acid, oleylmercapto α-methylpropionic acid, phenyl Mercapto α-methylpropionic acid, p-methylphenylmercapto α-methylpropionic acid, o-methylphenylmercapto α-methylpropionic acid, p-nonylphenylmercapto α-methylpropionic acid, p-tertiarybutyl phenyl Mercapto α
-Methylpropionic acid, benzylmercapto α-methylpropionic acid, cyclohexylmercapto α-methylpropionic acid, butylmercapto β-methylpropionic acid, octylmercapto β-methylpropionic acid, dodecylmercapto β-methylpropionic acid, tetradecylmercapto β- Methylpropionic acid, hexadecylmercapto β-methylpropionic acid, octadecylmercapto β-methylpropionic acid, dodecylmercapto β-phenylpropionic acid, benzylmercapto β-phenylpropionic acid, dodecylmercapto α-ethylpropionic acid, dodecylmercapto β-phenylpropionic acid Particularly preferred examples include dodecylmercaptopropionic acid, octadecylmercaptopropionic acid, dodecylmercapto α-methylpropionic acid, and octadecylmercapto α-methylpropionic acid. In the present invention, for 100 parts by weight of a blend polymer of a halogen-containing resin and a styrene resin,
If the amount of the organic tin maleate compound added is less than 0.1 part by weight, the thermal stabilizing effect will be small, and if the amount exceeds 10 parts by weight, the expected thermal stabilizing effect will not be observed, and the amount is preferably 0.5 to 5.0 parts by weight. If the added amount of the substituted mercaptopropionic acid represented by the general formula (1) is 0.005 parts by weight or less, no additive effect will be observed, and if the amount exceeds 1 part by weight, the heat stabilizing effect will be caused. The amount is preferably 0.01 to 0.5 parts by weight. The method for adding the stabilizer used in the present invention to the polymer blend of the halogen-containing resin and the styrene resin may be carried out by a conventionally known technique. The mixture may be mixed using a ribbon blender, a Banbury mixer, etc., or an organotin maleate compound and a substituted mercaptopropionic acid represented by the general formula (1) may be mixed in advance and mixed with the blend polymer using the above-mentioned mixer. You can. Further, in addition to these stabilizers, known stabilizers such as dialkyltin fatty acid salts, metal soaps, organic phosphorus compounds, etc. can be used in combination. Furthermore, if necessary, plasticizers, lubricants, antioxidants, pigments, fillers, processing aids, etc. can be added. [Examples and Effects] The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In the examples, parts refer to parts by weight. Example 1 Vinyl chloride resin [Geon 103Ep manufactured by Nippon Zeon Co., Ltd.
-8] 100 parts, 5 parts of methacrylic acid ester-butadiene-styrene copolymer [Kane Ace B-28 manufactured by Kanekabuchi Chemical Co., Ltd.], and 3 parts of di-n-butyltin maleate polymer [Table-1] A compound containing 0.02 part of the stabilizer shown in 1 was kneaded for 5 minutes using an 8-inch test roll adjusted to 170°C to produce a sheet with a thickness of 0.5 mm. Next, create a 3cm x 5cm test piece from this sheet, place this test piece in a gear oven adjusted to 190℃, and measure the time (minutes) until the test piece deteriorates (becomes black or blackish brown). did. In addition, 5 test pieces of 5 cm x 5 cm were made from a 0.5 mm sheet, and these 5 test pieces were stacked and heated at 200℃ and 30Kg/ ^cm2 .
The color tone was observed when pressed for 20 minutes. In addition, the plate-out property was evaluated by observing the amount of deposits on the roll after kneading with a test roll for 5 minutes.
This was done using A, B, and C below. A: Almost no plate out is observed. B: Slight plate out is observed. C: Significant plate-out is observed. The results are shown in [Table 1]. As can be seen from [Table 1], the combined use of the organotin maleate polymer of the present invention and substituted mercaptopropionic acid improves the thermal stabilization effect and also greatly improves the plate-out property.

[Table] Example 2 Vinyl chloride resin [Geon 103Ep manufactured by Nippon Zeon Co., Ltd.]
-8] 100 parts, acrylonitrile-butadiene-
A mixture of 40 parts of styrene copolymer [Toughflex TFX-410, manufactured by Mitsubishi Monsanto Chemical Co., Ltd.] and the stabilizer shown in [Table 2] was prepared using an 8-inch roll adjusted to 170°C in the same manner as in Example 1. A sheet with a thickness of 0.5 mm was prepared. Next, create a 3cm x 5cm test piece from this sheet, place this test piece in a gear oven adjusted to 190℃, and measure the time (minutes) until the test piece deteriorates (becomes black or blackish brown). did. In addition, 5 test pieces of 5 cm x 5 cm were made from a 0.5 mm sheet, and these 5 test pieces were stacked and heated at 200℃ and 30Kg/ ^cm2 .
The color tone was observed when pressed for 20 minutes. Weather resistance was evaluated by pressing a 0.5 mm sheet to create a 5 cm x 15 cm test piece, and using a Sunshine Weather Meter manufactured by Suga Test Instruments Co., Ltd.
It was placed in a WEL-SON-DC mold and the time until deterioration (blackening) was measured. The results are shown in [Table 2]. 〔table-
2], it was found that the thermal stabilizing effect of organotin maleate compounds alone is small, and that organotin sulfur-containing compounds have excellent thermal stabilizing effects but poor weather resistance. It can be seen that the combined use of substituted mercaptopropionic acid and substituted mercaptopropionic acid produces a remarkable mutual effect of thermal stabilization, and maintains the weather resistance of the organotin maleate compound.

[Table] Example 3 Vinyl chloride resin [Geon 103Ep manufactured by Nippon Zeon Co., Ltd.
-8] 100 parts, methacrylic acid ester-butadiene-styrene copolymer [BTA manufactured by Kureha Chemical Industry Co., Ltd.
-s] 60 parts, titanium white 1 part, and the stabilizer shown in [Table 3] were added and the mixture was adjusted to 170℃ 8
A 0.5 mm sheet was produced using an inch roll in the same manner as in Example 1. Next, create a 3cm x 5cm test piece from this sheet, place this test piece in a gear oven adjusted to 190℃, and measure the time (minutes) until the test piece deteriorates (becomes black or blackish brown). did. In addition, 5 test pieces of 5 cm x 5 cm were made from a 0.5 mm sheet, and these 5 test pieces were stacked and heated at 200℃ and 30Kg/ ^cm2 .
The color tone was observed when pressed for 20 minutes. The results are shown in [Table 3]. It can be seen that the thermal stabilization effect is excellent due to the mutual effect of the organotin maleate compound of the present invention and the substituted mercaptopropionic acid.

【table】

Claims (1)

[Scope of Claims] 1. (a) 0.1 to 10 parts by weight of an organotin maleate compound, (b) General formula (In the formula, R is an alkyl group, a cycloalkyl group,
It represents an alkenyl group, an aralkyl group, a phenyl group, or an alkyl-substituted phenyl group, and R ¹ and R ² each represent a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. ) 0.005 substituted mercaptopropionic acid
A method for stabilizing the blend polymer, characterized by adding 1 part by weight in combination.