JP3079342B2 - Stabilized non-toxic chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a safe chlorine-containing resin composition using a non-toxic stabilizer. More specifically, the present invention relates to a chlorine-containing resin composition having a low initial coloring property and a product having a high softening temperature in sheet molding by a calendar roll processing method.

[0002]

2. Description of the Related Art As a conventional technique relating to molding processing of a vinyl chloride resin, a plasticizer is added to lower the processing temperature to improve the initial coloring property, and molding is also performed. For this reason, molding is performed by adding epoxidized soybean oil. In order to prevent thermal decomposition during the molding process of the vinyl chloride resin, an invention using an organic tin compound and an organic compound in combination (Japanese Patent Publication No. 45-39176, Japanese Patent Publication No. 49-11258) and an organic tin maleate are disclosed. Invention using a combination of an organotin compound and an organotin mercaptide compound (Japanese Patent Publication No.
No. 20060) has already been disclosed.

[0003]

However, in the above-mentioned methods, in the sheet molding by the calendar roll processing method, any of those having inferior initial coloring property and having a high softening temperature of the molded sheet. Not obtained. On the other hand, if a plasticizer or epoxidized soybean oil is added, a new adverse effect of lowering the softening temperature occurs.

[0004]

The inventors of the present invention have made various investigations and found that when a non-toxic dioctyltin maleate polymer and an organic tin mercaptide are used in combination as a stabilizer for a resin composition. It has been found that the addition of a special phenolic antioxidant in which a tertiary butyl group is bonded only to one carbon atom adjacent to a hydroxyl group significantly improves the initial coloring property, and the present invention has been accomplished. By the way, if the phenolic antioxidant having a tertiary butyl group bonded only to one carbon atom adjacent to the hydroxyl group and the two stabilizers are used in combination, the heat stabilizing effect of the vinyl chloride resin is remarkable. In combination with a dioctyltin maleate polymer and the special phenolic antioxidant or a combination of an organic tin mercaptide and the special phenolic antioxidant. Confirmed that the desired effects of the present invention could not be obtained.

[0005] That is, the present invention relates to a chlorine-containing resin 100
(A) 0.1-3 parts by weight of a dioctyltin malate polymer as an additive based on 1 part by weight of methyl methacrylate / butadiene / styrene copolymer resin or 1-10 parts by weight of vinyl acetate / ethylene copolymer resin 0.1-3 parts by weight of an organotin mercaptide and (c) a phenolic antioxidant having a tertiary butyl group bonded only to one carbon atom adjacent to a hydroxyl group 0.01-
A non-toxic chlorine-containing resin composition containing 1.5 parts by weight.

[0006] Examples of the chlorine-containing resin stabilized by the present invention include, for example, vinyl halide homopolymers such as vinyl chloride resin and vinylidene chloride resin, and vinyl halide converted from vinyl acetate, ethylene, propylene, styrene, and the like. Isoprene, vinylidene chloride, maleic anhydride,
Copolymers formed by copolymerizing with one or more comonomers such as butadiene, methyl methacrylate, acrylonitrile, and dialkyl maleate, and post-chlorinated vinyl chloride resins.

[0007] The methyl methacrylate-butadiene-styrene copolymer resin or vinyl acetate.
Ethylene copolymer resin is used as an impact-strengthening agent, and when used in an amount of 1 to 10 parts by weight per 100 parts by weight of chlorine-containing resin, the effect of the resin is effectively exerted.

The dioctyltin maleate polymer constituting the additive of the present invention has a general formula [(C ₈ H ₁₇ ) _2]
It is a non-toxic organotin compound represented by SnOOCH = CHCOO-] n (n = 2-4).

Examples of the organotin mercaptide constituting the additive of the present invention include dimethyltin bis (isooctylmercaptoacetate), dimethyltinbis (2-ethylhexylmercaptoacetate), and monomethyltin tris (isooctylmercaptoacetate). Acetate), monomethyltin tris (2-ethylhexyl mercaptoacetate),
Dioctyltin bis (isooctylmercaptoacetate
G), dioctyltin bis (2-ethylhexylmercaptoacetate), monooctyltin tris (isooctylmercaptoacetate), monooctyltin tris (2-
Ethylhexyl mercapto A cetearyl - g), - g), alkylmercapto A cetearyl of dioctyltin bis (C ₁₀ -C ₁₆
Monooctyltintris (alkylmercapto A cetearyl of C ₁₀ -C ₁₆ - g), dilauryl tin bis (isooctyl mercapto A cetearyl - g), dilauryl tin bis (2-ethylhexyl mercapto A cetearyl - g), monolauryl tin tris (isooctyl Mercaptoacetate), monolauryl tin tris (2-ethylhexyl mercaptoacetate)
And di- or mono-organotin compounds.

The phenolic antioxidant according to the present invention having a tertiary butyl group bonded to only one carbon atom adjacent to a hydroxyl group includes, for example, butylated hydroxyanisone.
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3 -Methyl-6-tert-butylphenol), tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2'-thiobis (4
-Methyl-6-t-butylphenol) and the like.

Furthermore, a known non-toxic stabilizer such as a metal salt of an organic acid may be added to the chlorine-containing resin composition of the present invention.
Epoxy compounds, organic phosphites, ultraviolet absorbers, polyhydric alcohol compounds and the like can be added.
Further, if necessary, a lubricant, a pigment, a filler, an antistatic agent, a flame retardant, a processing aid, and a plasticizer can be used.

[0012]

EXAMPLES Next, the present invention will be described with reference to examples, where parts in the examples indicate parts by weight.

Example 1 100 parts by weight of a vinyl chloride resin (Geon 103EP-8 manufactured by Zeon Corporation) and an impact strengthening agent (Kaneace B-11)
A, manufactured by Kanegafuchi Chemical Co., Ltd.) 5 parts by weight, dioctyltin maleate polymer 1.0 part by weight, dioctyltin bis (isooctylmercaptoacetate) 1.0 part by weight, phenolic antioxidant A-J0 1 part by weight and 0.5 part by weight of a lubricant (WaxOP Hoechst) were blended, kneaded with two 8-inch rolls maintained at a temperature of 180 ° C., and 0.5 mm thick at 10 minute intervals. The sheet pieces were taken out and evaluated for initial colorability for 30 minutes. For the evaluation, YI (Yellow Index) was measured with a fully automatic colorimeter Color Ace TC-P3 (manufactured by Tokyo Denshoku Co., Ltd.). The results are shown in Table 1.

[Table 1] Note 1: TVS # 8813 manufactured by Nitto Kasei Corporation Note 2: Butylated hydroxyanisole Note 3: 2,2'-methylenebis (4-methyl-6-t-
Butylphenol) Note 4: 2,2'-methylenebis (4-ethyl-6-t-
Butylphenol) Note 5: 4,4'-butylidenebis (3-methyl-6-t
-Butylphenol) Note 6: Tris (2-methyl-4-hydroxy-5-t-)
Butylphenol) butane Note 7: 4,4'-thiobis (3-methyl-6-t-butylphenol) Note 8: 2,2'-thiobis (4-methyl-6-t-butylphenol) Note 9: Butylated hydroxytoluene * 10: 4,4'-dihydroxy-diphenylpropane-
2,2 'Note 11: 4-Hydroxymethyl-2,6-di-t-butylphenol

Example 2 100 parts by weight of vinyl chloride resin (Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.) and an impact strengthening agent (Kaneace B-52)
5 parts by weight, manufactured by Kanegafuchi Chemical Co., Ltd., impact enhancer (Soabrene C)
H Nippon Synthetic Chemical Co., Ltd.) 5 parts by weight, dioctyltin male
Topolymer, organotin mercaptide stabilizer AF, 0.1 part by weight of tris (2-methyl-4-hydroxy-5-t-butylphenol) butane and 0.5 part by weight of a lubricant (WaxOP Hoechst) were added. The mixture was kneaded with two 8-inch rolls maintained at a temperature of 180 ° C., and 0.5 mm-thick sheet pieces were taken out at 10-minute intervals, and the initial coloring property was evaluated for 30 minutes. . The evaluation was performed using a fully automatic colorimeter
YI (Yellow Index) was measured using a TC-P3 (manufactured by Tokyo Denshoku Co., Ltd.). The results are shown in Table 2.

[Table 2] * 1: Dimethyltin bis (isooctylmercaptoacetate) * 2: Monomethyltin tris (isooctylmercaptoacetate) * 3: Dioctyltin bis (2-ethylhexylmercaptoacetate) * 4: Monooctyltin tris (isooctyl mercapto a cetearyl - g) Note 5: (alkylmercapto a cetearyl of C ₁₀ -C ₁₆ - g) dioctyltin bis Note 6: dilauryltin bis (2-ethylhexyl mercapto a cetearyl - g)

Example 3 100 parts by weight of a vinyl chloride resin (Geon 103EP-8D manufactured by Zeon Corporation) and an impact strengthening agent (Kaneace B-2)
2 Kanebuchi Chemical Co., Ltd.) 10 parts by weight, dioctyltin maleate polymer, organotin mercaptide stabilizer, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
DOP, epoxidized soybean oil, calcium stearate,
A mixture of zinc stearate, tris (nonylphenyl) phosphite and 0.5 part by weight of a lubricant (manufactured by WaxOP Hoechst) was kneaded with two 8-inch rolls maintained at a temperature of 180 ° C., and the kneading was carried out at intervals of 10 minutes. The sheet piece having a thickness of 0.5 mm was taken out from the above and evaluated for initial coloring property for 30 minutes.
For the evaluation, YI (Yellow Index) was measured with a fully automatic colorimeter Color Ace TC-P3 (manufactured by Tokyo Denshoku Co., Ltd.). In order to measure the softening temperature of each composition, the mixture was kneaded with a roll of 8 inches for 5 minutes while maintaining the temperature at 180 ° C., and a 0.5 mm-thick sheet piece was taken out. After pressing at 180 ° C. to a thickness of 1 mm, a sample for crash berg measurement was prepared, and the softening temperature was measured. The results are shown in Table 3.

[Table 3]

[0016]

As is clear from Table 1, a phenolic antioxidant having a tertiary butyl group bonded to only one carbon atom adjacent to a hydroxyl group was used as a dioctyltin maleate polymer and an organotin mercaptide type. When added in combination with the above stabilizer, a remarkable heat stabilizing effect is exerted on the chlorine-containing resin. Also, as shown in Table 2, dioctyltin maleate polymer is obtained.
It can be seen that the desired effects of the present invention cannot be obtained unless two kinds of stabilizers composed of a compound and an organotin mercaptide are used in combination. Further, according to Table 3, in the present invention, there is no adverse effect such as lowering of the softening temperature of the chlorine-containing resin which occurs when additives such as a plasticizer and epoxidized soybean oil are used. It effectively prevents initial coloring, and the resin composition is non-toxic.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 87:00) (56) References JP-A-63-182364 (JP, A) JP-A-54-138047 (JP, A) JP-A-4-359947 (JP, A) JP-A-4-359948 (JP, A) JP-A-4-202453 (JP, A) JP-B-47-18216 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 27 / 04,55 / 02 C08K 5 / 13,5 / 57

Claims (1)

(57) [Claims] 1. A contrast chlorine-containing resin 100 parts by weight of methyl methacrylate-butadiene-styrene copolymer resin or a vinyl acetate-ethylene copolymer resin 1 10 parts by weight, as an additive, (a) dioctyltin maleate polymer 0 0.1 to 3 parts by weight (b) 0.1 to 3 parts by weight of an organotin mercaptide and (c) a phenolic antioxidant having a tertiary butyl group bonded only to one carbon atom adjacent to a hydroxyl group 0.01-
A non-toxic chlorine-containing resin composition comprising 1.5 parts by weight.