JPS6324540B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to heat-stabilized vinyl chloride resin compositions. The present inventor previously discovered vinyl chloride resin (hereinafter referred to as PVC).
We have found that 2-substituted-4,6-dithiol-s-triazine is effective as a heat stabilizer for the following methods: However, it is difficult to say that this is necessarily sufficient. Therefore, the present inventor has developed a method that solves the above problems.
As a result of repeated research to develop PVC compositions,
Per 100 parts by weight of PVC, general formula (In the formula, R is a hydrocarbon residue, M is hydrogen,
dithiol-s-triazine compounds represented by (alkali metal or alkaline earth metal)
0.01-5 parts by weight and zinc salt of organic acid () 0.01-5 parts by weight
10 parts by weight and hydrotalcite () 0.01-10
() and () per 100 parts by weight of vinyl chloride resin composition or vinyl chloride resin containing parts by weight.
0.01-5 parts by weight of the reaction product with ()0.01-5 parts by weight
The present invention was accomplished by discovering that a vinyl chloride resin composition containing 10 parts by weight achieves the intended purpose. In the present invention, R in parentheses includes alkyl groups such as methyl, ethyl, and butyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as propenyl, phenyl group, benzyl group, naphthyl group, methylphenyl, t-butylphenyl, etc. Examples include substituted phenyl groups. In addition, typical examples of M in parentheses include hydrogen,
Li, Na, K, 1/2Mg, 1/2Ca, 1/2Sr and 1/2Ba
can be mentioned. In addition, R-O-, RRN-, other than R-NH-,
If triazine compounds such as HS- are used, the object of the present invention will not be achieved. In addition, as the zinc salt of an organic acid, it is desirable to use one that acts as a lubricant for PVC and is compatible with PVC.From this point of view, as an organic acid residue,
C ₇ H ₁₅ ―, C ₁₁ H ₂₃ ―, C ₁₇ H ₃₅ ―, C ₁₇ H ₃₅ ―,
Preferred are alkyl groups having 7 or more carbon atoms such as C ₄ H ₉ --C ₆ H ₄ -- and C ₈ H ₁₇ --C ₆ H ₄ --, substituted phenyl groups, benzyl groups, and substituted cycloalkyl groups. Hydrotalcite () is a double salt of Mg and Al (hydrous basic carbonate, Mg/Al molar ratio 1 to 1).
10), for example, Mg ₄ Al ₂
(OH) ₁₂ CO ₃・3H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ CO ₃・
4H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ CO ₃・5H ₂ O, Mg ₆ Al ₂
(OH) ₁₆ Al ₂ (OH) ₁₆ CO ₃・4H ₂ O, etc.
It may be a synthetic product or a natural product. The amount used in () is 0.01 per 100 parts by weight of PVC.
~5 parts by weight, preferably 0.1 to 1.0 parts by weight.
If it is less than 0.01 parts by weight, the stabilizing effect will not be sufficient, and if it exceeds 5 parts by weight, not only will the stabilizing effect not improve any further, but it will have a negative effect on other physical properties. The usage amount of () is 0.01 to 100 parts by weight of PVC.
The amount is 10 parts by weight, preferably 0.5 to 5 parts by weight. 0.01
If it is less than 10 parts by weight, the stability effect will be insufficient, and if it exceeds 10 parts by weight, the processability will be poor. There is no particular restriction on the ratio of () and () used, but from the viewpoint of preventing thermal coloring, it is desirable to use equimolar amounts of both. The usage amount of () is 0.01 to 100 parts by weight of PVC.
The amount is 10 parts by weight, preferably 0.1 to 5 parts by weight.
If it is less than 0.01 part by weight, the stabilizing effect is insufficient;
If it exceeds 10 parts by weight, mixing processability becomes difficult. In the present invention, instead of using each of () and () alone, both are reacted in advance in a relatively low polar solvent such as a hydrocarbon or dioctyl phthalate, or in a resin sol such as a mixture of PVC and dioctyl phthalate. This can be used as a product obtained by The products may differ slightly depending on the ratio of () and () in this reaction, and structurally, (-OCOR' is an organic acid residue of ()) In other words, an equimolar reaction product of () and () is most effective. When the reaction product of () and () is used, the amount used is 0.01 to 5 parts by weight per 100 parts by weight of PVC. The points that can be speculated at present regarding the reasons why the present invention suppresses thermal coloring of PVC and improves the above-mentioned problems will be described below. When PVC is heated, Zipper-type dehydrochlorination occurs starting from abnormal structures such as allylic chlorine, tertiary chlorine, and single-head units contained in the PVC molecule, and color is thought to occur due to the growth of polyene chains. ing. Therefore, in order to suppress thermal coloring of PVC, it is necessary to stabilize the above thermally unstable abnormal structure and prevent Zipper dehydrochlorination. It seems important to completely stabilize the allylic chlorine structure. The purpose of the present invention is to stabilize this allylic chlorine by chemical treatment. That is, in the present invention, () is in the coexistence of (), or the reaction product of () and () is
Reacts with allyl chlorine in PVC It is introduced in a cross-linked structure such as , and suppresses zipper-like dehydrochlorination of PVC. However, since the zinc chloride produced by the above reaction significantly accelerates the dehydrochlorination decomposition of PVC, the reaction products of () and () or () and () alone cannot degrade PVC.
cannot suppress thermal coloring. In order to convert the zinc chloride produced there into a compound relatively unrelated to the dehydrochlorination reaction, it is necessary to coexist with an acid acceptor. is such that not only does not promote the decomposition of PVC, but also itself and the chloride produced do not impair the selective reaction of () or the reaction product of () and () with allyl chlorine. Must. Therefore, in the present invention, hydrotalcite () was selected as an acid acceptor having such requirements. In other words, () is as shown in Table 1.
It not only captures hydrochloric acid and zinc chloride, which promote thermal coloring of PVC, but also traps them in a nonionic state. This property is hardly observed in metal oxides or organic acid salts such as basic magnesium carbonate or barium stearate.

[Table] Next, the present invention will be explained by examples. The reaction products of () and () used in the Examples were prepared according to Reference Examples 1 and 2. In the reference example, the nitrogen analysis was carried out by the Kjeldahl method, and the zinc analysis was carried out by the gravimetric method. Reference example 1 6- in 200ml of high boiling point hydrocarbon (Solveso150)
After adding 0.02 mol (4.72 g) of anilino-1,3,5-triazine-2,4-dithiol (AF) and 0.02 mol (12.64 g) of zinc stearate and reacting at 80°C for 5 hours, the reaction mixture were separated at 50°C, and the resulting amorphous powder was mixed with ethanol,
It was thoroughly washed with Solveso 150 and ether to remove unreacted substances. Yield of amorphous powder produced is 9.9g
It was hot. Analysis value: N9.7%, Zn11.4%
(Calculated value as C ₂₇ H ₄₂ N ₄ O ₂ S ₂ Zn: N9.54%,
Zn11.19%). Infrared absorption spectrum (KBr):
3350 (W), 3220 (W), 2970 (m), 2930 (S), 28
50
(S), 1610(S), 1570(S), 1500-1550(S),
1460(S), 1400(S), 1380(m), 1280(m), 12
30
(S), 1160 (m), 875 (m), 820 (m), 770 (m)
),
745 (m), 720 (m), 710 (m), 680 (m), 500 (
W),
460 (W) cm ^-1 . Therefore, it can be seen that the product is a compound of the following formula. Note that similar results were obtained when tetrahydrofuran, polyethylene glycol, or dioctyl phthalate was used instead of Solveso 150 as a reaction solvent. Reference example 2 AF0.02 mol (4.72g) in 200ml of Solveso150
and 0.02 mol (9.27 g) of zinc laurate,
8.2 g of white powder was obtained in the same manner as in Reference Example 1. Analytical _{values :} N11.1%, Zn12.9% (calculated values _{as C21H30O2N4S2Zn} : _N11.21 %, Zn13.09%). Infrared absorption spectrum (KBr): 3350 (W), 3200 (W),
2970 (m), 2925 (S), 2850 (m), 1610 (S), 15
90
(S), 1570 (S), 1520 (S), 1455 (S), 1410
(S), 1370 (S), 1330 (m), 1300 (m), 1280
(m), 1240 (m), 1225 (S), 1160 (m), 880 (
m),
820 (m), 800 (W), 765 (m), 740 (m), 720 (
m),
700 (W), 500 (W), 450 (W) cm ^-1 . Therefore, it can be seen that the product is a compound of the following formula. Example 100 parts by weight of PVC (degree of polymerization 1050), 50 parts by weight of dioctyl phthalate, the indicated triazine compound and acid acceptor were mixed at 160°C for 5 minutes, and the mixture was pressed at 160°C for 3 minutes to a thickness of 0.5 mm. It was made into a sheet. Place this between two glass slides,
It was subjected to a thermal coloring test in a gear oven at 170°C. The results are shown in Table 2.

[Table] From the above table, it can be seen that when the additives of the present invention are used, thermal coloring of PVC (especially initial coloring that changes to pale orange) is significantly suppressed. In addition, the sheet made from the composition of the present invention had excellent transparency.

Claims (1)

[Claims] 1. General formula per 100 parts by weight of vinyl chloride resin (In the formula, R is a hydrocarbon residue, and M is hydrogen, an alkali metal, or an alkaline earth metal.) 0.01 to 5 parts by weight of a dithiol-s-triazine compound (), a zinc salt of an organic acid ()
0.01-10 parts by weight and hydrotalcite ()
A heat-stabilized vinyl chloride resin composition containing 0.01 to 10 parts by weight. 2 General formula per 100 parts by weight of vinyl chloride resin (In the formula, R is a hydrocarbon residue, and M is hydrogen, an alkali metal, or an alkaline earth metal.) A reaction product of a dithiol-s-triazine compound () represented by the following formula and a zinc salt of an organic acid ()
0.01-5 parts by weight and hydrotalcite ()
A heat-stabilized vinyl chloride resin composition containing 0.01 to 10 parts by weight.