JPS5832645A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a stabilizer prepared by reacting an alkyltin compound with a mercapto ester or maleic acid (anhydride) in a halogen-containing resin. CONSTITUTION:(A) 100pts.wt. halogen-containing resin is incorporated with (B) 0.1-5pts.wt. stabilizer obtained by reacting (B) 1mol dialkyltin oxide expressed by formulaI(R is 1-12C alkyl) with (C) 0-1mol monoalkyltin compound consisting of a monoalkyltin oxide expressed by formula II or a monoalkyltin hydroxide expressed by formula III, and reacting (D) 1mol mercapto ester expressed by formula IV (R1 is 1-18C alkyl, etc.; n is 1 or 2) with (E) 0-0.5mol maleic acid (anhydride) at a molar ratio[(D+E)/(B+C)]of 0.95- 1.25 while removing the formed by-product after keeping the reaction mixture at 80-120 deg.C for 0.5-6hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful halogen-containing resin composition. This resin composition contains a special stabilizer for halogen-containing resins and has particularly excellent initial heat resistance.

Halogen-containing resins are susceptible to thermal deterioration caused by K, mainly through dehydrohalogenation reactions, during thermoforming, and therefore products processed from K-based halogen-containing resins are likely to suffer from problems such as thermal discoloration or a decline in mechanical properties. . In order to improve these shortcomings, a method is usually adopted to add so-called metal soap stabilizers such as lead, cadmium, calcium, barium or zinc salts of stearic acid or tin stabilizers such as alkyltin compounds. ing. Additionally, for these stabilizers, dialkyltin mercapto, dialkyltin malate polymers or dialkyltin bis(
Although the combination with monoalkyl malate (monoalkyl malate) is also widely used, it completely eliminates the drawback that under processing conditions that require severe temperatures, the resin becomes colored and the quality of the product deteriorates. The reality is that there is still no end to this, and at present we have not achieved anything that would fully satisfy us.

However, the present inventors have attempted to stabilize a halogen-containing resin that can sufficiently withstand even under harsh conditions.
0 parts by weight and 1 mole of dialkyltin oxide (b-1) represented by the general formula [wherein 8 in the formula is as described above]. ] or a monoalkyltin oxide represented by the general formula % formula % ( ) [However, R in the formula is as described above. ] Using 0-1 mol of a monoalkyltin compound (b-2), which is a monoalkyltin hydroxide, represented by the formula %, on the other hand, a mercaptoester (b-3) represented by the general formula % [ ]. 0 to 1 mol of maleic anhydride or maleic acid (b-4)
Q, using 5 mol, and ((b-5)+(b-4))
/'((b-1)+(b-2))=0.95~1.2
At a chemical equivalence ratio of 5, either (b-1) alone, or both this and (b-2), only (b-5), or this and (b-4). make both react,
However, the temperature for removing KM-forming substances is 80-120℃.
It has been found that a resin composition comprising 1 to 51 parts of [L] of 1 gB), which is obtained by first carrying out the process after holding α for 5 to 6 hours, has excellent heat resistance, especially initial heat resistance, The present invention has now been completed.

Here, typical dialkyltin oxides (b-1) represented by the above general formula [■] include dimethyltin oxide, di-n-butyltin oxide, di-1-
Examples include butyltin oxide, di-n-octyltin oxide, di-1-octyltin oxide, etc. Representative monoalkyltin oxides represented by the above general formula (If) K are monomethyltin oxide, mono-
n-Butyltin oxide, mono-1-butyltin oxide, 7-n-octyltin oxide or mono-1-
There are octyltin oxides, etc., and the general formula [■] shown above is
Typical examples of monoalkyltinhydroxide represented by are monomethyltinhydroxide, mono-
Examples include n-butyltin hydroxide, mono-1-butyltin hydroxide, mono-n-octyltin hydroxide, and mono-1-octyltin hydroxide. ), the above-mentioned monoalkyltin oxide or monoalkyltinhydroxide (b-2) is 0 to 1 mol, preferably 0.
．． It is preferable to use violet in the range of 01 to n, s moles, and if more than 1 mole of violet is used in these monoalkyltin compounds (b-2), the long-term heat resistance of the resin may be poor. This is not preferable because it becomes - On the other hand, typical mercaptoesters (b-'s) represented by the general formula 0 shown above are methoxy thioglycolate Qs'f1''9-2-ethylhexyl cholate, lauryl thioglycolate, Thioglycolic acid oleyl ester, thioglycolic acid chlorohexyl ester, thioglycolic acid benzyl ester, β
-Mercaptopropionic acid methoxybutyl ester, β
-Mercaptopropion--2-ethylhexyl ester, β-mercaptopropionic acid-1-octyl ester, β-mercaptopropionic acid pentauryl ester, β
-mercaptopropionic acid oleyl ester, β-mercaptopropionic acid cyclohexyl ester or β-
Examples include benzyl mercaptopropionate ester.

And, for 1 mole of these mercaptoesters (b-3), the above-mentioned (anhydride) maleic acid (b'LL4)
is preferably used in the range of 0 to α5 mol, preferably α6 mol to α001. If the amount of maleic acid (anhydride) exceeds α5 mol, the resulting stabilizer should be stored for a long time. This is not preferable because it may cause precipitation.

When obtaining the stable part
The chemical equivalent ratio of /((b-1')+(b-2)) is α
The amount of raw materials to be used must be determined so that the inverse Kt25 is exceeded, and if α95 is less than i, it will take a long time in the r-filtering process during stabilizer production. Both of these methods are unfriendly, as they may cause problems with the odor of the stabilizer. Generally, when dialkyltin bis(mercaptoester) or dialkyltin bis(monoalkylmalate) is produced by reacting dialkyltin oxide with mercaptoester or monoalkylmalate as described above, by-produced water is used to produce these compounds. The mercaptoester or monoalkyl malate undergoes hydrolysis. Therefore, in order to prevent such a situation, the by-product water should be kept as low as possible and 1. It is said that a method of rapid removal is preferable.

However, each of the above (b-1) and (b-
2), <b-5) and (b-4), especially when reacting a system containing maleic anhydride, by such a method that quickly removes by-product water at a low temperature. If so, the filtration process may take a long time, and the color tone of the stabilizer itself deteriorates, and the K content increases as precipitates form over time.In addition, the heat resistance, especially the initial heat resistance, deteriorates. It becomes impossible to obtain an excellent halogen-containing resin composition, and according to the results of the research by the present inventors, these <b-1), (b-2), and (b-3)
When charging and reacting (b-4), 80
By-products should not be removed at all at temperatures below ℃ and for less than α5 hours, and it is preferable to remove by-products only after the reaction is maintained at 80 to 120℃ for α5 to 6 hours. By making the above (anhydrous)
Even when maleic acid is used, there are no inconveniences during the filtration process, and the resulting stabilizer itself has a good color tone.Moreover, this stabilizer does not form precipitates over time, making it extremely shelf-stable. It was found to have good stability.

This fact has not been known to those skilled in the art and is completely different from the general knowledge of those skilled in the art.

Furthermore, it was confirmed that the halogenated resin stabilized using the stabilizer obtained by the method described above, that is, the resin composition of the present invention, has excellent heat resistance, especially initial heat resistance.

As mentioned above, the conditions to be maintained without any removal of by-products should be α5 to 6 hours at 80 to 120°C. If the temperature is lower than 80°C, the reaction time will be extremely long and the raw brittle strength will be reduced.On the other hand, if the temperature is higher than 120°C, the formation of precipitates will be observed during storage, and Both of these are undesirable, as they may have a bad odor.

On the other hand, if the reaction time is less than 15 hours, the color of the stabilizer will be poor, and precipitates may form during storage, and the initial resistance and heat resistance of vinyl chloride resin containing such stabilizers will deteriorate. Sometimes it's not enough. On the other hand, if the reaction time exceeds 6 hours, the productivity may be poor and the odor may also become worse, which is not preferable. Next, the amount of the stable NIB) is preferably in the range of α1 to 5 parts by weight based on 100 parts by weight of the halogen-containing resin (4). 0.1
If the amount is less than 5 parts by weight, the thermal stability effect may not be fully exhibited; on the other hand, if the amount exceeds 5 parts by weight, phenomena such as bloom may occur in the norogen-containing resin composition. , so both are unfavorable.

Other main components of the composition of the present invention, such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, polyvinyl bromide, polyvinyl fluoride, chlorinated Vinyl-vinyl acetate copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-maleate ester copolymer, vinyl chloride, ru-acrylate ester copolymer, vinyl chloride-methacrylate ester copolymer, vinyl chloride- Typical examples include vinyl acetate-ethylene copolymer and vinyl chloride-styrene-acrylonitrile copolymer.

In addition, for the composition of the device, light, calcium stearate, zinc stearate, barium stearate, dialkyltin malate polymer, dialkyltin bis(alkyl maleate), dialkyltin bis(alkyl thioglycolate), dialkyltin Bis(alkyl β-mercaptopropionate).

Known and conventional stabilizers such as dialkyltin thioglycolate polymers, epoxidized soybean oil or organic phosphite esters, antioxidants, or other necessary additives, such as plasticizers, pigments, blowing agents, antistatic agents, etc. Of course, fuels, processing aids, fillers, etc. can also be used.

Next, the present invention will be specifically explained using examples and proportional examples.

Reference Examples 1 to 10 (Example of breast preparation in (B)) 1/4 tube flask equipped with a stirrer, temperature 1 and cooling tube, 204 g (1 mol) of thioglycolic acid-2-ethylhexyl ester, β-mercaftprobionic acid −
2-ethylhexyl ester 149.59 (α692
mol) monohydric maleic acid 201α204 mol),')-n
- Add 49.8 g (α2 mol) of butyltin oxide and 28B,8,9 (α8 mol) of di-n-octyltin oxide and raise the temperature to -95°C, without removing any by-products at this point. The temperature was maintained at 90-95°C for 2.0 hours. Thereafter, by-products were removed by reducing the pressure at 90 to 98° C. and 15 mHg or less. After drying and filtering, the yield of the stabilizer taken out was 680 g'C:, the color was less than 1 as measured by the Gadner method, and the tin content was 17.0 g as measured by the atomic absorption method. It was 311% by weight. The above is Reference Example 1, except for changing the prescription in Table 1.
Various stabilizers were synthesized in the same manner as in Reference Example 1.

Reference Examples 11 to 15 (preparation examples of stabilizers for comparison), raw materials were added, the temperature was raised to 60 ° C., and pressure reduction was immediately started.
After setting it to 20smH9 or less at ℃, 90-98℃, 15
678 g of a comparative stabilizer was obtained in the same manner as in Reference Examples 1 to 10, except that the by-products were removed under conditions of wa Hg. The color of this stabilizer was measured by the Gadner method and was 5, and the tin content was measured by atomic absorption method and was 17.2% by weight. The above is Reference Example 11, and other control stabilizers were also prepared in the same manner as Reference Example 11, except that the formulation was changed to the one shown in Table 1.

It is clear from comparing the colors of the stabilizers thus obtained.
K. The color of the stabilizers of the present invention (obtained in Reference Examples 1 to 10) is less discolored than the stabilizers obtained by conventional methods such as Reference Examples 11 to 15, and there is almost no discoloration. I found out that it wasn't.

Reference Example 16 (Example of Storage Stability Test of Stabilizer) Reference Examples 1 to 1
0 and 15 kinds of stabilizers 95I obtained in Reference Examples 11 to 15! The storage stability of a stabilizer prepared by mixing Evosizer W-100ELJ (epoxy oil manufactured by Dainippon Ink & Chemicals) with 5 g of Evosizer W-100ELJ (epoxy oil manufactured by Dainippon Ink & Chemicals) at room temperature of 2!1~25℃ was observed for 3 months. It is shown in Table 2.

As shown in the same table, the stabilizers provided for the compositions of the present invention (obtained in Reference Examples 1 to 10) had good storage stability, whereas those obtained in Reference Examples 11 to 15 had good storage stability. It has been found that the stabilizers prepared according to the conventional methods have poor storage stability due to the formation of precipitates.

Examples 1 to 15 and Comparative Examples 1 to 5 ゛Vinyl chloride 11
After blending 100 parts by weight of Ri II (p~800), 1 part by weight of stearic acid, and 1 part by weight of a stabilizer and mixing well, the mixture was kneaded for 5 minutes using an 8-inch roll with a surface temperature of 165°C to form a sheet with a thickness of α3M. It was created. A part of this sheet is cut off and 4 sheets are stacked to create a total pressure of 200kg at a temperature of 170℃.
A plate with a thickness of 2 mm was prepared by applying pressure for 5 minutes. The degree of coloring of the thus obtained press sheet was examined. The results are shown in Table 2.゛Examples 16 to 18 and Comparative Examples 6 to 8 100 parts by weight of vinyl chloride resin (p=800), 1 part by weight of stearyl alcohol, and 1 part by weight of stabilizer were blended and mixed well, and then 8 with a surface temperature of 165°C was mixed. The mixture was kneaded using an inch roll for 5 minutes to form a sheet having a thickness of 31111 mm. Next, this sheet was cut into a predetermined size, placed on an aluminum plate, and taken out at a predetermined time interval into a hot air aging tester at 185°C. observed by. The results are shown in Table 3.

Example 19 and Comparative Examples 9.10 100 parts by weight of vinyl chloride resin (p-700), 5 parts by weight of methyl methacrylate-butadiene-styrene copolymer, 3 parts by weight of polyethylene lubricant, 0.0 parts by weight of butyl stearate. A formulation consisting of 5 parts by weight and 2 parts by weight of stabilizer was heated at a rotation speed of 21/19 rpm and a temperature of 18
A roll heat resistance test was conducted at 5°C with a 6I/Tyrol set so that the sheet thickness was α5M,
The time until the sheet could no longer be removed from the roll surface (adhesion time) was used as a measure of its heat resistance. The results are shown in Table 4.

/ Table 3 The evaluation criteria are as follows.

1... No coloration 2... Extremely light yellow color 3...
Pale yellow 4... Yellow Color 5... Brown brown 4 Table 1) Mercapto stabilizer Examples 20 to 22 and Comparative Examples 11 to 1S vinyl chloride resin with tin content of 18.0% <p
-800), 1 part by weight of stearyl alcohol, and the amount of stabilizer listed in Table 5 were kneaded for 5 minutes on an 8-inch roll with a surface temperature of 165°C to form a sheet of α3 thickness. Created. Next, cut this sheet into a predetermined size, place it on an aluminum plate, and
The sheet was placed in a hot air aging tester at 85° C. and taken out at predetermined intervals [the static heat resistance of the sheet was observed based on the degree of coloration. The results are shown in the same table.

Table 5

Claims (1)

[Scope of Claims] For 1 mole of dialkyl tin oxide (b-1) represented by the general formula (B) and 100 parts by weight of the resin contained in (4) as the main components, the general formula [however, the formula The R inside is as described above. ] Monoalkyltin oxide or general 2R-8n = Q)
A monoalkyltin-based compound (b
-2) 00 to 1 mol, and on the other hand, maleic anhydride or maleic acid (b-4) 00 to 1 mol of mercaptoester (b-x) represented by the formula % (
Using α5 moles, and ((b-3)+(b-4))/
At a chemical equivalent ratio of ((b-1)+(b-2))-α95 to 1.25, the above-mentioned (b-1) alone or (b-
Reacting (b-5) alone or both (b-5) and (b-4) with both 1) and (b-2), provided that the by-product substances are removed at this time. to 80-120℃ (1
A halogen-containing resin composition comprising 1 to 5 parts by weight of a stabilizer α which is obtained only after holding for 5 to 6 hours.