JPS6144103B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is characterized in that an organotin maleate compound and sorbic acid are added together to a chlorine-containing vinyl resin, and the chlorine-containing vinyl resin composition has extremely little plate-out during molding and has good thermal stability. It is related to. As is well known, chlorine-containing vinyl resins are subject to deterioration by heat and light. In order to prevent this resin from deteriorating, metal soaps such as lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, dialkyl tin maleate polymer, dialkyl tin bis(alkyl maleate) are used during the molding process. , bis(dialkyltin alkyl maleate) maleate, dialkyltin bis(S,S'-alkylmercaptocarboxylate) dialkyltin S,O-mercaptocarboxylate, organotin stabilizers such as dialkyltin fatty acid salts, epoxy compounds, Organic phosphites, antioxidants, etc. are used. Among these, organotin-based stabilizers have excellent thermal stabilizing effects, so vinyl chloride resin (hereinafter referred to as PVC), PVC and methyl methacrylate-butadiene-styrene copolymer (hereinafter referred to as MBS resin) are used.
When molding chlorine-containing resins such as blend resins of PVC and acronitrile-butadiene-styrene copolymer (hereinafter referred to as ABS resins), hard products are molded under particularly harsh heating conditions. It is widely used. Among organotin stabilizers, organotin maleate compounds such as organotin maleate polymers and organotin alkyl maleates are particularly frequently used. However, these chlorine-containing vinyl resins containing organotin maleate compounds have the drawback of causing a so-called plate-out phenomenon that contaminates the metal surface of a processing machine during molding. When plate-out occurs, it not only contaminates the product and impairs its appearance, but also reduces work efficiency due to the additional work required to remove the deposits, and further impedes the transparency of the product.
Problems caused by plate-out are extremely large, such as deterioration of lamination performance when processing laminate plates and the like, and deterioration of vapor deposition performance when processing vapor-deposited films. Patent No. 818934 (Japanese Patent Publication No. 818934) describes a method to prevent this drawback of plate-out occurrence.
38766), JP-A-50-132058, JP-A-51-7051
No., JP-A-51-20251, etc. are well known. In these methods, an organic tin maleate compound and phthalic acid, phthalic anhydride, phthalic acid monoester, 3-chlorophthalic anhydride, adipic acid, azelaic acid, stearic acid, etc. are added in combination. However, even with these methods, satisfactory results have not yet been obtained. The inventors of the present invention have conducted extensive research to improve these drawbacks, and have found that by adding an organotin maleate compound and sorbic acid together to a chlorine-containing vinyl resin, playout is extremely reduced.
A chlorine-containing vinyl resin composition with good thermal stability was discovered and the present invention was completed. Although there is no particular restriction on the combination ratio of the organotin maleate compound and sorbic acid, the preferred combination ratio is 2 sorbic acid to the organotin maleate compound.
~50% by weight. The preferred amount of the organotin maleate compound is 100% of the chlorine-containing vinyl resin.
The amount is 0.5 to 5 parts by weight. The organotin maleate compounds used in the present invention include dialkyltin maleate and its polymer, dialkyltin bis(alkyl maleate), and bis(dialkyltin monoalkyl maleate) maleate, and examples include dimethyltin maleate, Monomers and polymers such as dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, dimethyltin bis(butyl maleate), dimethyltin bis(isooctyl maleate), dimethyltin bis(lauryl maleate), dimethyltin bis(oleyl) dibutyltin bis(butyl maleate), dibutyltin bis(decyl maleate), dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin Bis(2-ethylhexyl maleate), dibutyltin bis(lauryl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(stearyl maleate),
Dibutyltin bis(3-methoxy maleate), dibutyltin bis(butoxyethyl maleate), dibutyltin ethyl maleate/benzyl maleate, dioctyltin bis(butyl maleate), dioctyltin bis(benzyl maleate), dioctyltin Bis(isooctyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(stearyl maleate), dioctyltin bis(3-methoxybutyl maleate), dilauryl Tin bis(butyl maleate) and bis(dimethyltin butyl maleate) maleate,
Bis(dimethyltin isooctyl maleate) maleate, bis(dimethyltin lauryl maleate)
Maleate, bis(dimethyltin oleyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin isooctyl maleate) maleate, bis(dibutyltin 2
-ethylhexyl maleate) maleate, bis(dibutyltinbenzyl maleate) maleate,
Bis(dibutyltin cyclohexyl maleate) maleate, bis(dibutyltin lauryl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dibutyltin butoxymaleate) maleate, bis(dibutyltin 3-
Methoxybutyl maleate) maleate, bis(dioctyltinbutyl maleate) maleate,
Bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin butoxyethyl maleate) maleate, bis(dioctyltin lauryl maleate) maleate, bis(dioctyltin oleyl maleate) ) maleate, bis(dilauryltin butyl maleate) maleate, methyl octyltin bis(isooctyl maleate), methyl lauryltin bis(butyl maleate), dibutyltin butyl maleate, benzyl maleate, etc. . The chlorine-containing vinyl resin used in the present invention includes PVC, post-chlorinated vinyl chloride resin, and vinyl chloride as main components, and ethyl acrylate,
Examples include copolymers with one or more of acrylonitrile, styrene, vinyl acetate, isobutylene, ethylene vinyl acetate, etc., and blend resins with PVC and impact reinforcing agents (e.g., ABS resin, MBS resin), etc. I can do things. Known stabilizers other than those used in the present invention, such as metal soaps, organic tin sulfur compounds, organic tin fatty acid salts, epoxidized soybean oil, epoxy resins, organic phosphites, antioxidants, ultraviolet absorbers, etc. Can be used together. In addition, pigments, fillers, foaming agents, antistatic agents, lubricants,
Flame retardants, processing aids, etc. can also be used together. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight. Example 1 Plate-out test PVC [Geon 103 Ep-8 manufactured by Zeon Corporation]
100 parts, 2.0 parts of dibutyltin maleate polymer (degree of polymerization P = 3.5), 0.1 part of the compound shown in [Table-1]
and red pigment [#8040 red, manufactured by Dainichiseika Co., Ltd.]
After mixing 1.0 part, it was heated to 180℃ using a test roll for 10 minutes.
After kneading for a minute, the sheet was removed. After this, the playout material adhering to the roll is removed using PVC [Geon 103
Ep Nippon Zeon Co., Ltd.] 100 parts, DOP (dioctyl phthalate) 25 parts, titanium white [TA-100, Fuji Titanium Co., Ltd.] 2.0 parts, dibutyltin dilaurate 1.0 parts, cadmium stearate 0.3 parts resin A cleaning sheet was prepared by wiping the composition while kneading it. Then, playout was determined based on the degree of red coloring of the cleaning sheet. In addition, the state of playout after kneading for 20 minutes was also observed. These results are shown in Table-
1]. The playout numbers in Table 1 indicate the following conditions. No playout (cleaning sheet is milky white)...1 Slight playout (cleaning sheet is pale pink...2) Slightly more playout (cleaning sheet is pink...3) A lot of playout (cleaning sheet is red)
…4 Thermal stability test 100 parts of PVC [Geon 103 Ep-8], 2.0 parts of dibutyltin maleate polymer (p=3.5) and [Table-
After mixing 0.1 part of the compound shown in 1], the mixture was kneaded using a test roll at 165°C for 5 minutes to produce a sheet with a thickness of 0.5 mm. After cutting this sheet into a size of 3 cm x 6 cm, the sheet was placed in a gear type aging tester preheated to 190°C to evaluate thermal stability. The sheet is taken out at regular intervals, and the degree of color deterioration of the sheet is observed with the naked eye, and the color of the sheet is determined as colorless...A Yellow brown...C Yellow...B Black Color...D [Table-1] It was shown to.

[Table] Example 2 To 100 parts of PVC (Geon 103 Ep-8), 2.0 parts of dibutyltin maleate polymer (p=3.5) and sorbic acid were added in a range of 0.01 to 0.5 parts. Playout and thermal stability tests were conducted in the same manner as described above. These results are shown in [Table 2].

[Table] Example 3 100 parts of PVC [Geon 103 Ep-8] was combined with 2.0 parts of the stabilizer shown in Table 3, 0.1 part of sorbic acid, and 0.3 part of Hoechstwax OP (manufactured by Hoechst AG, West Germany) as a lubricant. Playout and thermal stability tests were conducted in the same manner as in Example 1. These results are shown in [Table 3].

[Table] Stabilizers (a) to (d) in [Table 3] indicate the following. Stabilizer (a) Dioctyltin maleate polymer (P
=2.7) (b) Dibutyltin bis(butyl maleate) (c) Bis(dimethyltin benzyl maleate) maleate (d) Bis(dioctyltin methoxybutyl maleate) maleate.

Claims (1)

[Claims] 1. A chlorine-containing vinyl resin composition comprising a combination of an organotin maleate compound and sorbic acid added to a chlorine-containing vinyl resin.