JPS6324539B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to heat stabilized polyvinyl chloride compositions. The present inventor previously discovered polyvinyl chloride (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 ₁ and R ₂ are hydrocarbon residues, and M
is hydrogen, an alkali metal or an alkaline earth metal) 0.01 to 5 parts by weight of a zinc salt of dithiol-s-triazine () and 0.1 to 50 parts by weight of an alkali metal salt or an alkaline earth metal salt of an organic acid () The present invention has been accomplished by discovering that a polyvinyl chloride composition containing 100% of 100% of polyvinyl chloride achieves the intended purpose. The zinc salt of dithiol-s-triazine used in the present invention has the general formula (In the formula, R ₁ and M are the same as above. The two M's may be the same or different.) Dithiol-s-triazine () represented by the general formula (R ₂ COO) ₂ Zn ( (in which R ₂ is the same as above) is reacted with an organic acid zinc salt () represented by the formula () in a 1:1 molar ratio in a relatively low polar solvent such as a hydrocarbon or dioctyl phthalate. can be synthesized. In the synthesis of this compound, it is necessary to set the ()/() molar ratio to 1. If this is greater than 1 This results in a decrease in the coloring suppression effect, a decrease in transparency due to cloudiness of the product, and causes blooming and plate-out. On the other hand, if the molar ratio is less than 1, the zinc content will increase and zinc burning will become severe.
This is not preferable because the effect of suppressing coloring is reduced. ()
Since it is very difficult to separate () and () from the reaction product of () and (), it is necessary to strictly maintain the molar ratio to 1 in this respect as well. R ₁ in () and () includes alkyl groups such as methyl, ethyl, 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. Representative examples of M in () and () include hydrogen, Li, Na, K, 1/2Mg, 1/2Ca, 1/2Sr
and 1/2Ba. In addition, as (), R ₁ -NH- is R ₁ -O-,
When triazine compounds such as R ₁ R ₁ N-, HS- are used, only compounds of type () can be obtained even if the molar ratio with () and reaction conditions are considered, so the method of the present invention is difficult to obtain. The purpose is not achieved. In addition, () indicates the lubricant role of PVC, and
It is desirable to use something that is compatible with PVC, and from this point of view, R ₂ is C ₇ H ₁₅ —, C ₁₁ H ₂₃ —, C ₁₇ H ₃₅ —,
Alkyl groups with 7 or more carbon atoms, substituted phenyl groups, benzyl groups, and substituted cycloalkyl groups such as C ₁₇ H ₃₃ ―, C ₄ H ₉ ―C ₆ H ₄ ―, and C ₈ H ₁₇ ―C ₆ H ₄ ―, etc. etc. are preferable. () and R ₂ is CH ₃ -- and C ₂ H ₅ --
When using a low carbon number such as ()
It is not preferred because the yield is poor and a large amount of () is produced. The alkali metal salts and alkaline earth metal salts of organic acids used in the present invention include lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, barium salts, or strontium salts such as octylic acid, lauric acid, or stearic acid. Examples include. The usage amount of () is 0.01 to 100 parts by weight of PVC.
The amount is 5 parts by weight, preferably 0.1 to 1.0 parts by weight. 0.01
If it is less than 5 parts by weight, the stabilizing effect will not be sufficient;
If the amount exceeds 1 part by weight, the stabilizing effect will not be improved any further, and other physical properties will be adversely affected. The amount used in () is 0.1 to 50 per 100 parts by weight of PVC.
Parts by weight are preferably 0.5 to 5 parts by weight. If it is less than 0.1 parts by weight, the stability effect will be insufficient, and if it exceeds 50 parts by weight, processability will be poor. 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. In other words, () in the present invention reacts with allyl chlorine in PVC. A cross-linked structure such as is introduced to suppress zipper-like dehydrochlorination of PVC. However, since the zinc chloride produced by the above reaction significantly accelerates the dehydrochlorination decomposition of 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. Not only must it be such that it does not promote the decomposition of PVC, but it must also be such that both itself and the chloride produced do not impair the selective reaction of () with allyl chlorine. Therefore, in the present invention, an alkali metal salt or an alkaline earth metal salt of an organic acid is used as an acid acceptor having such requirements. In addition, the reactivity itself with allyl chlorine is However, since this compound also has a high reactivity with chlorine in the normal structure, the selectivity for allylic chlorine becomes lower, resulting in a lower thermal coloring suppressing effect. The PVC composition of the present invention may contain conventional additives, such as plasticizers such as dioctyl phthalate or fillers such as metal oxides and carbonates, as required. Next, the present invention will be explained with reference to examples. The number of doses of drug used is based on weight. In addition, the zinc salt of dithiol-s-triazine used in the examples is Reference Example 1.
-5. 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 white 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%,
Zn11.9%). Infrared absorption spectrum (KBr): 3350
(W), 3220 (W), 2970 (m), 2930 (S), 2850
(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} : _{N :} 11.21%, Zn13.09%). Infrared absorption spectrum (KBr): 3350 (W), 3200
(W), 2970 (m), 2925 (S), 2850 (m), 1610
(S), 1590(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. Reference Example 3 Add 0.02 mol (4.72 g) of AF and 0.02 mol (7.03 g) of zinc isooctylate to 200 ml of ethanol, react at 50°C for 5 hours, then remove the insoluble portion separately and distill off the ethanol. A pale yellow syrup was obtained. By thoroughly washing this with benzene and ether, a purified product is produced.
6.8g was recovered. Analysis value: N12.4%, Zn15.0%
(Calculated value as C ₁₇ H ₂₂ O ₂ N ₄ S ₂ Zn: N: 12.62%,
Zn14.74%). Infrared absorption spectrum (KBr):
3300(W), 3100(W), 2960(S), 2920(S), 28
50
(m), 1610(S), 1590(S), 1570(S), 1520
(S), 1450 (S), 1420 (S), 1355 (S), 1320
(m), 1300 (m), 1290 (m), 1240 (m), 1220
(S), 1160 (m), 890 (m), 820 (W), 800 (W)
),
760 (m), 740 (m), 700 (W), 500 (W), 450 (
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 the reaction medium. Reference example 4 Add 0.02 mol (4.72 g) of AF and 0.01 mol (6.32 g) of zinc stearate to 120 ml of Solveso150,
After reacting at 80°C for 5 hours, the reaction mixture was separated and the resulting white powder was mixed with alcohol,
4.9 g of purified product was obtained by washing with Solveso 150 and ether. Analysis value: N20.9%,
Zn12.4% (calculated value as C ₁₈ H ₁₄ N ₈ S ₄ Zn: N:
20.91%, Zn12.20%). Infrared absorption spectrum (KBr): 3600 (W), 3350 (m), 3150 (m), 2960
(m), 1600 (S), 1560 (S), 1470-1530 (S),
1450(S), 1350(S), 1290(S), 1260(S), 12
Ten
(S), 1140(S), 1130(W), 900(W), 880(S)
),
820 (m), 770 (S), 740 (S), 700 (m), 680 (
S),
500 (m), 460 (m) cm ^-1 . Therefore, it can be seen that this product is a compound of the following formula. Reference Example 5 The AF used in Reference Example 1 was 0.022 mol (5.19
g) (AF/zinc stearate molar ratio 1.1) The same experiment as in Reference Example 1 was conducted to obtain 11.3 g of white powder. Analysis value: N10.63%,
Zn11.29%. Infrared absorption spectrum (KBr): 3600
(W), 3350 (W), 3150 (W), 2960 (W), 2920
(S), 2850 (S), 1620 (W), 1610 (S), 1560
(S), 1500-1540(S), 1490(S), 1450(S),
1400 (m), 1350 (S), 1280 (m), 1260 (m), 12
20
(S), 1210 (S), 1150 (m), 900 (W), 880 (S)
),
820 (m), 780 (S), 750 (m), 720 (m), 710 (
m),
680 (m), 560 (W), 460 (W) cm ^-1 . This product is found to be a mixture of Sample A and Sample D at a molar ratio of 9:1 from the elemental analysis values and the transparency test results of the mixture of this product and PVC. Example 100 parts of PVC, 40 parts of dioctyl phthalate, the indicated amount of zinc triazine salt, and 1.3 parts of barium stearate were mixed at 160°C for 5 minutes, and then pressed at 160°C for 5 minutes to make a sheet with a thickness of 0.5 mm. The degree of coloration and transparency were tested as follows. Degree of coloration...Put the PVC sheet between glass slides and place it in a gear oven at 170℃.
The degree of coloration was measured every 30 minutes using a Suga colorimetric color difference calculator. The effect of suppressing coloring was expressed as the time it took for the degree of coloring to reach 12%. Transparency...The transmittance (%) of light at 600 nm was measured for the PVC sheet. In addition, PVC sheets prepared in the same manner by adding 10 parts of FEF carbon to the above PVC mixture were immersed in water at 25°C for 72 hours, and the degree of white turbidity (blooming property) on the surface was determined by three levels: small, medium, and large. Evaluated in stages. In addition, 15 g of the same PVC mixture used for the color and transparency tests, with 1 part of watching red added, was added to a clean small laboratory roll for 170 g.
After mixing for 3 minutes and removing, 15 g of cleaning formulation (100 parts PVC, 40 parts dioctyl phthalate, 1.5 parts dibasic lead stearate, 2 parts tribasic lead sulfite, 10 parts silica and 20 parts calcium carbonate)
The mixture was mixed on the above roll at 180°C for 3 minutes, and the stabilizer adhering to the roll (in which the watchdog was occluded) was recovered. This cleaning formulation
Plate-out properties were evaluated by measuring the redness ΔE (%) of a 0.5 mm thick sheet prepared by pressing at 160° C. for 5 minutes using a color difference meter.
Since the ΔE of the cleaning formulation itself is 10.5%, a ΔE greater than this means more plateout. 【table】

Claims (1)

[Claims] 1. General formula per 100 parts by weight of polyvinyl chloride (In the formula, R ₁ and R ₂ are hydrocarbon residues, and M
is hydrogen, an alkali metal or an alkaline earth metal) 0.01 to 5 parts by weight of a zinc salt of dithiol-s-triazine () and 0.1 to 50 parts by weight of an alkali metal salt or an alkaline earth metal salt of an organic acid () 1. A heat-stabilized polyvinyl chloride composition comprising: