JPS5825105B2 - Stabilization method for synthetic resins - Google Patents

Description

Detailed Description of the Invention The present invention is a polyvinyl chloride resin (hereinafter referred to as PvC), an acrylonitrile butadiene styrene resin (hereinafter referred to as ABS), or a blend polymer of the two, dialkyltin hiss (alkyl maleate) and/or Alternatively, the present invention relates to a method for stabilizing a synthetic resin, characterized in that bis(dialkyltin alkyl maleate) maleate and dialkyltin S.0-mercaptocarboxylate are added together.

PVC, ABS, or a blend of both polymers can be heated,
Because it is subject to deterioration due to light, a stabilizer is required to prevent deterioration during molding.

Particularly under harsh processing conditions, thermal deterioration is easy to occur, and in order to prevent this, metal soaps such as cadmium stearate, barium stearate, lead stearate, calcium stearate, zinc stearate, dialkyltin maleates, and dialkyltin mercaptides are used. Organotin compounds, such as, are used as stabilizers.

Among organotin-based stabilizers, dialkyltin bis(alkyl maleate) and bis(dialkyltin alkyl maleate) maleate have an excellent thermal stabilizing effect on the synthetic resin, and also provide excellent weather resistance to molded products. It has been known.

However, since these organotin compounds are generally liquids or solids with a low melting point, P
When added to VC, ABS, or a blend polymer of both, there is a drawback that the heat distortion temperature of the molded product decreases.

For this reason, when each is used alone, the amount of addition and use may be limited, and it has been desired to develop a method for suppressing the decrease in the heat distortion temperature Q of molded products using these organotin compounds. .

The present inventors have prepared PVC, ABS, or a blend polymer of both with dialkyltin bis(alkyl maleate).
As a result of research aimed at developing a method for suppressing the decrease in the heat distortion temperature of molded products when stabilizing using bis(dialkyltin alkyl maleate) maleate, we found that the general formula (1) dialkyltin bis(alkyl maleate) (wherein R1 and R2 are alkyl groups having 1 to 12 carbon atoms, and may be the same or different from each other.

R3 and R4 are an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 4 to 18 carbon atoms, and may be the same or different.

) and/or bis(dialkyltin alkyl maleate) maleate represented by the general formula (2) (wherein R5, R6, R7, and R8 are alkyl groups having 1 to 12 carbon atoms, and are the same as each other) It can also be different.

R9 and RIO are an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 4 to 18 carbon atoms, and may be the same or different.

) is 50 to 80% by weight, and dialkyltin S.0-mercaptocarboxylic acid salt represented by general formula (3) (in the formula, R'', R, and 12 are alkyl groups having 1 to 12 carbon atoms, and mutually may be the same or different.

m represents an integer of 1 or 2, and l represents an integer of 1 to 10.

) in a ratio of 50 to 20% by weight, PVC, ABS, or a blend polymer of both.
The present invention was completed by discovering that the object can be achieved by adding 1 to 10 parts by weight to 0 parts by weight.

To explain the present invention in more detail, the heat distortion temperature of the molded product in which the general formula (1) and/or (2) and the organotin compound represented by (3) are added to the synthetic resin in combination is , general formula (1) and/or (2), or (3
) is higher than the heat distortion temperature of the molded product to which the organotin-tin compound shown in (a) is added separately to the synthetic resin, which is predicted from the actually measured heat distortion temperature of the molded product to which the organotin-tin compound is added. The present invention was completed by discovering that it has the effect of suppressing a decrease in heat distortion temperature.

General formula (1) and/or (2y) outside the scope of the present invention
If the organic tin compound exceeds 80% by weight and the organic tin compound represented by general formula (3) is added at a ratio of less than 20% by weight, the effect of suppressing the reduction in the heat distortion temperature of the molded product may be insufficient. If the general formula (1) and/or Q-Shin 2) is added in a ratio of less than 50% by weight and the general formula (3) is added in a ratio of more than 50% by weight, the weather resistance of the molded product will deteriorate, which is preferable. do not have.

In the present invention, the organic tin compound represented by the general formula (1) and/or (2) and the general formula (3) is added in the ratio of 1 to 10 parts by weight to 100 parts by weight of PVC, ABS, or a blend polymer of both. Add part by weight.

If the amount added is less than 1 part by weight, the prevention of thermal deterioration of the resin will be insufficient, and if it exceeds 10 parts by weight, a thermal stabilizing effect corresponding to the amount added will not be obtained, making it impractical (and the heat distortion temperature It is also less effective in suppressing the decline in

The preferred amount added is 3 to 5 parts by weight.

Examples of the dialkyltin bis(alkyl maleate) represented by the general formula (1) used in the present invention are east dimethyltin bis(butyl maleate), dimethyltin bis(hexyl maleate), dimethyltin his(2-ethyl hexyl maleate), dimethyltin bis(octyl maleate),
Dimethyltin bis(inoctyl maleate), dimethyltin bis(decyl maleate), dimethyltin bis(dodecyl maleate), dimethyltin bis(tridecyl maleate), dimethyltin bis(tetradecyl maleate), dimethyltin bis( stearyl maleate), dimethyltin bis(oleyl maleate), dimethyltin bis(benzyl maleate), dimethyltin bis(cyclohexyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(hexyl maleate), Dibutyltin bis(2)
-ethylhexyl maleate), dibutyltin (octyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin hiss(decyl maleate), dibutyltin bis(dodecyl maleate), dibutyltin bis(tridecyl maleate), Dibutyltin bis(tetradecyl maleate), dibutyltin bis(stearyl maleate)
, dibutyltin bis(oleyl maleate), dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleate),
Dioctyltin bis(2-ethylhexyl maleate),
Dioctyltin bis(octyl maleate, dioctyltin bis(isooctyl maleate), dioctyltin bis(
decyl maleate), dioctyltin bis(dodecyl maleate), dioctyltin bis(tridecyl maleate)
, dioctyltin bis(tetrazocum maleate), dioctyltin bis(stearyl maleate), dioctyltin bis(oleyl maleate), dioctyltin hiss(benzyl maleate), dioctyltin bis(cyclohexyl maleate), dilauryltin Hiss (butyl maleate)
, dilauryltin bis(hexyl maleate), dilauryltin hiss(2-ethylhexyl maleate), dilauryltin hiss(octyl maleate), dilauryltin bis(
dilauryltin bis(isooctyl maleate), dilauryltin bis(decyl maleate), dilauryltin bis(dodecyl maleate), dilauryltin bis(tridecyl maleate), dilauryltin bis(tetradecyl maleate), dilauryltin bis(stearyl maleate) , dilauryltin hiss(
dilauryltin bis(oleyl maleate), dilauryltin bis(benzyl maleate), dilauryltin bis(cyclohexyl maleate), etc. Preferred examples include dibutyltin bis(butyl maleate), dibutyltin bis(
hexyl maleate), dibutyltin bis(hexyl maleate), dibutyltin hiss(2-ethylexyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis( decyl maleate), dibutyltin hiss (dodecyl maleate), dibutyltin bis() ') 7' syl maleate), dibutyltin hiss (tetradecyl maleate)
, dibutyltin bis(stearyl maleate), dibutyltin hiss(oleyl maleate), dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dioctyltin bis(butyl maleate),
Dioctyltin bis(hexyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(inoctyl maleate), dioctyltin bis(tesil maleate), dioctyltin bis(dote) syl maleate), dioctyltin bis(tridecyl maleate), dioctyltin bis(tetradecyl maleate), dioctyltin bis(stearyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate) ), dioctyltin bis(cyclohexyl maleate), and the like.

Examples of bis(dialkyltin alkyl maleate) maleate represented by general formula (2) include bis(dimethyltin butyl maleate) maleate, his(dimethyltin hexyl maleate) maleate, and bis(dimethyltin hexyl maleate) maleate.
dimethyltin 2-ethylhexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate,
Bis(dimethyltin octyl maleate) maleate, Bis(dimethyltin tetradecyl maleate) maleate, His(dimethyltin dodecyl maleate) maleate, His(dimethyltin tridecyl maleate) maleate, Bis(dimethyltin tetradecyl maleate) maleate , bis(dimethyltin stearyl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, bis(dimethyltin benzyl maleate) maleate, bis(
dimethyltin cyclohexyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(
dibutyltin hexyl maleate) maleate, bis(cyphthyltin 2-ethylhexyl normal maleate) maleate,
his(cyphtyltin octyl maleate) maleate, bis(dibutyltin octyl maleate) maleate,
His(cyphthyltin tesyl maleate) maleate, bis(dibutyltin dotesyl maleate) maleate, bis(
dibutyltin tridecyl maleate) maleate, bis(
Dibutyltin tetradecyl maleate) maleate, bis(siphthyltin stear 1J lumaleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dibutyltin benzyl maleate) maleate, His(
Dimethyltin cyclohexyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin hexyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin octyl maleate) maleate, bis (dioctyltin octyl maleate) maleate, bis(dioctyltin decyl maleate) maleate, his(dioctyltin dodecyl maleate) maleate, bis(dioctyltin tridecyl maleate) maleate, bis(dioctyltin tetradecyl maleate) maleate, Bis(dioctyltin stearyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, his(dioctyltin cyclohexyl maleate) maleate, bis(dilauryltin butyl maleate) maleate, Bis(dilauryltin hexyl maleate) maleate, bis(dilauryltin 2-ethylhexyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin tesyl maleate) maleate, Bis(dilauryltin dodecyl maleate) maleate, His(dilauryltin tritesyl maleate) maleate, Bis(dilauryltin tetradecyl maleate) maleate, Bis(dilauryltin stearyl maleate) maleate, Bis(dilauryltin oleyl maleate) Maleate, bis(dilauryltin benzyl maleate) maleate, bis(dilauryltin cyclohexyl maleate) maleate, etc., and preferred examples include bis(dibutyltin butyl maleate) maleate and bis(dibutyltin hexyl maleate). maleate, bis(dibutyltin2)
-ethylhexyl maleate) maleate, bis(dibutyltin octyl maleate) maleate, bis(dibutyltin octyl maleate) maleate, bis(dibutyltin tecyl maleate) maleate, his(dibutyltin dotecyl maleate) maleate, bis(dibutyl Tin tridecyl maleate) maleate, bis(dibutyltin tetradecyl maleate) maleate, bis(dibutyltin stearyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(cyphthyltin penzyl maleate) maleate, bis (dibutyltin cyclohexyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin hexyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(
Dioctyltin octyl maleate) maleate, bis(
Dioctyltin isooctyl maleate) maleate, bis(dioctyltin tetradecyl maleate) maleate, bis(dioctyltin dotesyl maleate) maleate, bis(dioctyltin tritecyl maleate) maleate, bis(dioctyltin tetradecyl maleate) maleate, Bis(dioctyltin stearyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate 1. Bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin cyclohexyl maleate)
Maleate, etc. can be mentioned.

Examples of dialkyltin 5-o-mercaptocarboxylate represented by general formula (3) include dimethyltin 5-O-thioglycolate, dibutyltin S
・0-thioglycolate, dioctyltin S・0-thioglycolate, dilauryltin S・O-thioglycolate, dimethyltin S・0-3-mercaptopropionate, dibutyltin S・〇-3 -methylcaptopropionate, dioctyltin S.0-3-mercaptopropionate, dilauryltin S.0-3-mercaptopropionate, and the like.

In the present invention, a lubricant, an antioxidant, an ultraviolet ray absorber, a filler, a pigment, etc. may be added as necessary.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

In this example, parts mean parts by weight.

Furthermore, the effect of suppressing the decrease in heat distortion temperature was determined by the method described below.

For example, the measured value of the heat distortion temperature of the molded article of the synthetic resin composition to which the organotin compound represented by the general formula (1) and/or (2) (referred to as stabilizer A) is added is a, the stabilizer A
and an organotin compound represented by general formula (3) or a commonly used dialkyltin sulfide (referred to as stabilizer E)
Let e be the measured value of the heat distortion temperature of the molded product of the synthetic resin composition to which is added.

If e is higher than a, when a stabilizer consisting of X weight % of stabilizer A and (lOO-X) weight % of stabilizer E is added in the same proportion as stabilizer A or stabilizer E, The calculated value of the predicted heat distortion temperature is based on the measured temperature difference (e
- Composition ratio of stabilizer A to a)
Since it decreases by X(e-a)(□), it is calculated as (e −,1 100100).

If the measured value was higher than the calculated value, it was determined that there was an effect of suppressing the decrease in heat distortion temperature.

Example I PVC (Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.)
), ABS (Toyoshiku Co., Ltd.) Toyolac 100), and 100 parts of a blend polymer of both were added 4 parts each of stabilizers A, B, C1D, and E having the compositions shown in Table 1, and the temperature was adjusted to 160°C. 3 with two 8-inch rolls
The mixture was kneaded for a minute to produce a sheet with a thickness of 0.5 mm.

Eight of the obtained sheets were stacked and pressed at 185°C for 10 minutes to produce a press plate with a thickness of 3.5 mvt, and a 15 mm
The sample was made to have a size of 15 x 15 mm.

Using a heating deformation tester (newly manufactured by Toyo Seiki Co., Ltd.), the needle diameter was 1.1 mm in a silicone oil bath. Load 2kg, temperature increase rate 1℃/m
The temperature at which 0.1 mrn needle was applied to the sample under the conditions of - was measured as the heat distortion temperature, and the results are shown in Table 2.

As is clear from the results in Table 2, it can be seen that the present invention suppresses the decrease in heat distortion temperature.

Example 2 30 parts of PVC (Geon 103 EP-8) and A
Stabilizers A, D, E, F, and G having the compositions shown in Table 3 were added to 70 parts of the blended polymer (BS()Yoratsuku 100).
A sample was prepared under the same operating conditions as in Example 1 by adding 4 parts each of lH, I and J, and the heat distortion temperature was measured.

The results are shown in Table 4. As is clear from the results in Table 4, it can be seen that the present invention suppresses the decrease in heat distortion temperature.

Example 3 30 copies of PVC (Geon 103 EP-8) and AB
6 parts and 8 parts of the stabilizer used in Examples 1 and 2 were added to 70 parts of the blended polymer (S () Yoratsuku 100), samples were prepared under the same operating conditions as in Example 1, and the heat distortion temperature was measured. .

The results are shown in Table-5.

As is clear from the results in Table 5, it can be seen that the present invention suppresses the decrease in heat distortion temperature.

Claims (1)

[Claims] 1. Vinyl chloride resin, acrylonitrile, butadiene,
Dialkyltin bis(alkyl maleate) represented by the general formula (1) (wherein R1 and R2 have 1 carbon number) is added to 100 parts by weight of the styrene resin or a blend polymer of both.
~12 alkyl groups, which may be the same or different from each other. R3 and R4 are an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 4 to 18 carbon atoms, and may be the same or different. )and. or bis(dialkyltin alkyl maleate) maleate represented by the general formula (2) (wherein R5, R6, R7, and R8 are alkyl groups having 1 to 12 carbon atoms, and may be the same as each other). R9 and RIO are an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 4 to 18 carbon atoms, and may be the same or different from each other. ) is 50 to 80% by weight, and a dialkyltin S.0-mercaptocarboxylic acid salt represented by the general formula (3) (in the formula, R11 and R12 are alkyl groups having 1 to 12 carbon atoms, and are the same as each other) m is an integer of 1 or 2, and l is an integer of 1 to 10. A method for stabilizing a synthetic resin, characterized by adding parts by weight.