JPS6245258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a blend resin (hereinafter referred to as a blend) of vinyl chloride resin (hereinafter referred to as PVC) or PVC and acrylonitrile butadiene styrene (hereinafter referred to as ABS) resin or methyl methacrylate butadiene styrene (hereinafter referred to as MBS) resin. Regarding the stabilization of PVC or blended resins, we can provide an excellent thermal stabilizing effect by adding three types of organic tin compounds in specific ratios to PVC or blend resins, and This provides a stabilization method with extremely low emissions. As is well known, PVC is subject to deterioration due to heat and light. To prevent these deteriorations, metal soaps such as lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, dibutyltin maleate polymer, dibutyltin bis(monoalkylmaleate) are used during the molding process. , dibutyltin bis(isooctyl mercaptoacetate), dibutyltin bis(2-ethylhexyl 3-mercaptopropionate), dibutyltin dilaurate, dioctyltin maleate polymer, dioctyltin bis(monoalkyl maleate), bis(dioctyltin Organotin stabilizers such as monoalkyl maleate) maleate, dioctyltin bis(isooctylmercaptoacetate), and dioctyltin dilaurate, as well as epoxy compounds, organic phosphite esters, and antioxidants are used. Among these, organotin stabilizers have excellent thermal stabilizing effects and are used when molding PVC or blended resins.
It is widely used especially when molding hard products that are subjected to harsh heating conditions. Furthermore, regarding organotin stabilizers, organotin maleate salts, organotin 3-
Mercaptopropionic acid ester salts, organic tin mercaptoacetic acid ester salts, and the like are widely used. Organic tin maleate salts are inexpensive and are the most commonly used, but they tend to damage the color of PVC or blended resin products and cause severe blistering on the product surface. Furthermore, during molding, resin additives and their decomposition products often migrate to the metal surface that is in contact with the resin without being compatible with the resin, and eventually adhere to the metal surface, which is called plate-out. Organic tin 3-mercaptopropionic acid ester salt has a good heat stabilizing effect, but plate-out and bubbling occur frequently. Organic tin mercaptoacetate salts cause less plate-out and blistering, but have poor thermal stabilization effects. If there is a lot of bubbling on the product surface, the effectiveness of printing ink and adhesives will be significantly reduced, and the surface of transparent products will turn white and cloudy, reducing transparency. In addition, in the case of lint products, the lint will fall and the product value will be greatly reduced. When plate-out occurs, the surface of the product becomes dirty, streaks appear, the extruded product becomes rough, and the resin tends to adhere to the processing machinery, making it necessary to stop work and greatly reducing work efficiency. do. In order to compensate for these drawbacks, resins are usually
By adding organic tin maleate salt and organic tin 3-mercaptopropionate salt, or organic tin maleate salt and organic tin mercaptoacetate salt together, the thermal stabilization effect is improved and plate-out and bubble-out are improved. I'm trying to suppress it, but I'm still not satisfied. That is, when an organic tin maleate salt and an organic tin 3-mercaptopropionate salt are added in combination, an improvement in the thermal stabilization effect is observed and the color of the product is not impaired, but plate-out and blistering are severe. on the other hand,
When an organotin maleate salt and an organotin mercaptoacetate salt are added in combination, the heat stabilization effect is not sufficiently satisfied and the color of the product is impaired. The present inventors have conducted extensive research to improve these drawbacks and have arrived at the present invention. That is, the inventors
Or general formula (1) for 100 parts by weight of blend resin (R ¹ and R ² in the formula are alkyl groups and may be the same or different. R ³ and R ⁴ are alkyl groups, substituted alkyl groups,
They are alkenyl groups and cycloalkyl groups and may be the same or different. m is 0
~5 numbers. ) of the general formula (2) (R ⁵ ) ₂ Sn(SCH ₂ CH ₂ COOR ⁶ ) ₂ (2) (where R ⁵ is an alkyl group) They can be the same or different. R ⁶ is an alkyl group,
Substituted alkyl group, aryl group, alkenyl group, cycloalkyl group, which may be the same as each other,
You can also do different things. ) Organotin 3-
0.5 to 1.5 parts by weight of mercaptopropionic acid ester salt and the general formula (3) (R ⁷ ) ₂ Sn (SCH ₂ COOR ⁸ ) ₂ (3) (in the formula, R ⁷ is an alkyl group, and they may be the same or the same). , or can be different. R ⁸ is an alkyl group, a substituted alkyl group, an aryl group, an alkenyl group, or a cycloalkyl group, and they can be the same or different.) We have found an excellent method for stabilizing PVC or blend resins that provides an excellent thermal stabilizing effect by adding 0.05 to 1.0 parts by weight of salt, and that causes very little plate-out and bubbling. Examples of R ¹ and R ² in general formula (1) include alkyl groups having 1 to 12 carbon atoms, and R ³ ,
Examples of ^R4 include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number having an alkoxy group, aryl group, or aralkyl group as a substituent. 3
~22 substituted alkyl groups can be mentioned. Specific examples of preferred groups include butyl and octyl as R ¹ and R ² , and butyl, octyl, 2-ethylhexyl, isooctyl, decyl, oleyl, cyclohexyl, methoxybutyl, and benzyl as R ³ and R ⁴ . Examples of the organotin maleate salt represented by the general formula (1) used in the present invention include dimethyltin bis(monolauryl maleate),
Dimethyltin bis (monooleyl maleate), dibutyltin bis (monobutyl maleate), dibutyltin bis (decyl maleate), dibutyltin bis (monobenzyl maleate), dibutyltin bis (monocyclohexyl maleate), dibutyltin bis (monooctyl maleate), dibutyltin bis(mono 2-ethylhexyl maleate), dibutyltin bis(monolauryl maleate), dibutyltin bis(monooleyl maleate), dibutyltin bis(mono 3-methoxybutyl maleate) ), dibutyltin bis(monobutoxyethyl maleate), dibutyltin bis(monophenylethyl maleate),
Dioctyltin bis(monobutyl maleate), dioctyltin bis(monobenzyl maleate), dioctyltin bis(mono-2-ethylhexyl maleate), dioctyltin bis(monoisooctyl maleate), dioctyltin bis(monobutoxyethyl) dioctyltin bis(monostearyl maleate), dilauryltin bis(monobutoxyethyl maleate), bis(dimethyltin monolauryl maleate) maleate, bis(dimethyltin monooleyl maleate) maleate, bis(dibutyl tin monobutyl maleate) maleate, bis(dibutyltin mono-2-ethylhexyl maleate) maleate, bis(dibutyltin monobenzyl maleate) maleate, bis(dibutyltin monocyclohexyl maleate) maleate,
Bis(dibutyltin monolauryl maleate) maleate, bis(dibutyltin monooleyl maleate) maleate, bis(dibutyltin monobutoxyethyl maleate) maleate, bis(dibutyltin mono-3-methoxybutyl maleate) maleate, bis( Dioctyltin monobutyl maleate)
Maleate, bis(dioctyltin monobenzyl maleate) maleate, bis(dioctyltin mono-2-ethylhexyl maleate) maleate, bis(dioctyltin monobutoxyethyl maleate) maleate, bis(dioctyltin monobutoxyethyl maleate) maleate, Examples include bis(dioctyltin monolauryl maleate) maleate, bis(dioctyltin monooleyl maleate) maleate, and bis(dilauryltin monobutoxyethyl maleate) maleate. Examples of R ⁵ in general formula (2) include alkyl groups having 1 to 12 carbon atoms, and examples of R ⁶ include alkyl groups having 1 to 18 carbon atoms, and 3 to 18 carbon atoms. alkenyl groups, cycloalkyl groups having 5 to 8 carbon atoms, aryl groups having 6 to 8 carbon atoms, and substituted alkyl groups having 3 to 22 carbon atoms having alkoxy groups, aryl groups, and aralkyl groups as substituents. Can be done. Specific examples of preferred groups include butyl, octyl as ^R5 , and as ^R6 ,
Octyl, 2-ethylhexyl, isooctyl,
Examples include decyl, oleyl, cyclohexyl, methoxybutyl, and benzyl. Examples of the organic tin 3-mercaptopropionate salt represented by the general formula (2) include dimethyltin bis(butyl 3-mercaptopropionate), dibutyltin bis(hexyl 3-mercaptopropionate), and dibutyltin bis(hexyl 3-mercaptopropionate). Bis(octyl 3-mercaptopropionate), dibutyltin bis(isooctyl 3-mercaptopropionate), dibutyltin bis(2-ethylhexyl 3-mercaptopropionate), dibutyltin bis(decyl 3-mercaptopropionate) ), dibutyltin bis(lauryl 3-mercaptopropionate), dibutyltin bis(stearyl 3-mercaptopropionate), dibutyltin bis(oleyl 3-mercaptopropionate), dibutyltin bis(cyclohexyl 3-mercaptopropionate) propionate), dioctyltin bis(octyl 3-mercaptopropionate), dioctyltin bis(isooctyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate), benzyl 3-mercaptopropionate), dioctyltin bis(phenyl 3-mercaptopropionate), dioctyltin bis(palmityl 3-mercaptopropionate), dioctyltin bis(propylbenzyl 3)
-mercaptopropionate), dioctyltin bis(oleyl 3-mercaptopropionate),
Examples include dilauryltin bis(3-methoxybutyl 3-mercaptopropionate). An example of R ⁷ in general formula (3) is 1 carbon number.
~12 alkyl groups can be mentioned, and examples of ^R8 include alkyl groups having 1 to 18 carbon atoms, and 3 to 18 carbon atoms.
Examples include alkenyl groups having 5 to 8 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, aryl groups having 6 to 8 carbon atoms, and substituted alkyl groups having 3 to 22 carbon atoms having alkoxy groups, aryl groups, and aralkyl groups as substituents. I can do it. Specific examples of preferred groups include butyl, octyl as R ⁷ and n-octyl, 2-ethylhexyl, isooctyl, decyl, oleyl, cyclohexyl, methoxybutyl, benzyl and the like as R ⁸ . Examples of organic tin mercaptoacetate salts represented by general formula (3) include dimethyltin bis(butylmercaptoacetate), dibutyltin bis(hexylmercaptoacetate), dibutyltin bis(octylmercaptoacetate), dibutyltin bis( isooctylmercaptoacetate), dibutyltinbis(2-ethylhexylmercaptoacetate), dibutyltinbis(decylmercaptoacetate), dibutyltinbis(laurylmercaptoacetate), dibutyltinbis(stearylmercaptoacetate), dibutyltinbis(cyclohexylmercaptoacetate) acetate), dibutyltin bis(phenylmercaptoacetate), dibutyltin bis(benzylmercaptoacetate), dibutyltin bis(3-
methoxybutylmercaptoacetate), dibutyltin bis(3-butoxybutylmercaptoacetate), dioctyltin bis(hexylmercaptoacetate), dioctyltin bis(octylmercaptoacetate), dioctyltin bis(isooctylmercaptoacetate), dioctyltin bis( 2-ethylhexylmercaptoacetate), dioctyltin bis(decylmercaptoacetate), dioctyltin bis(lauryl mercaptoacetate), dioctyltin bis(stearylmercaptoacetate), dioctyltin bis(phenylmercaptoacetate), dioctyltin bis(3- methoxybutylmercaptoacetate), dioctyltinbis(3-butoxybutylmercaptoacetate), dioctyltinbis(propylbenzylmercaptoacetate), dioctyltinbis(oleylmercaptoacetate), dilauryltinbis(cyclohexylmercaptoacetate), etc. can. Furthermore, to explain the proportions of organic tin compounds represented by general formulas (1), (2) and (3), the present invention
Organotin maleate salt represented by general formula (1) based on 100 parts by weight of PVC or blend resin
0.5 to 3.0 parts by weight and organic tin 3 represented by general formula (2)
- 0.5 to 1.5 parts by weight of a mercaptopropionic acid ester salt and 0.05 to 1.0 parts by weight of an organic tin mercaptoacetate salt represented by general formula (3) are added together, preferably one represented by general formula (1). 1.5 to 2.5 parts by weight of organic tin maleate salt and general formula (2)
1.0 to 1.5 parts by weight of an organic tin 3-mercaptopropionate salt represented by formula (3) and 0.1 to 1.0 parts by weight of an organic tin mercaptoacetate salt represented by general formula (3) are added together. More specifically, when the proportion of these organotin compounds represented by general formulas (1), (2), and (3) is out of the scope of the present invention, that is, organotin maleic acid represented by general formula (1) When 0.5 to 3.0 parts by weight of the ester salt and 0.5 to 1.5 parts by weight of the organotin 3-mercaptopropionic acid ester salt represented by the general formula (2) are used together, the organotin mercaptoacetic acid represented by the general formula (3) If ester salt is used in excess of 1.0 parts by weight, the heat stabilization effect will not be improved, and the coloring in the initial and middle stages will be poor and the color of the product will be impaired. In addition, when used in combination at less than 0.05 part by weight, plate-out and bubbling occur frequently. When 0.5 to 3.0 parts by weight of an organotin maleate salt represented by the general formula (1) and 0.05 to 1.0 parts by weight of an organotin mercaptoacetate salt represented by the general formula (3) are used together, ) Organotin 3-
If more than 1.5 parts by weight of mercaptopropionic acid ester salt is used together, plate-out and bubbling will increase. In addition, if they are used together in an amount less than 0.5 parts by weight, the heat stabilizing effect will not be improved, and the coloring in the initial and middle stages will be poor, damaging the color of the product. 0.5 to 1.5 parts by weight of organic tin 3-mercaptopropionic acid ester salt represented by general formula (2) and general formula
The organic tin mercaptoacetate salt shown in (3) is
If 0.05 to 1.0 parts by weight of organotin maleate salt represented by general formula (1) is used in excess of 3.0 parts by weight, the color of the product may be impaired and plate-out or blistering may occur. There will be more. Also, 0.5
If used together in less than parts by weight, the thermal stabilization effect will not improve. In carrying out the stabilization method of the present invention, in addition to the three organotin compounds used in the present invention, known stabilizers such as dialkyltin fatty acid salts, epoxidized soybean oil, epoxy resins, organophosphorous esters, Oxidizing agents, ultraviolet absorbers, etc. can be used together. In addition, pigments, fillers, blowing agents,
Antistatic agents, lubricants, flame retardants, processing aids, etc. can also be used together. When carrying out the stabilization method of the present invention, there are no particular restrictions on the processing method, and the processing method may be any conventional method, such as injection, extrusion, or blowing of a resin composition obtained by mixing each component in a super mixer, Banbury mixer, kneader, etc. Can be processed using molding methods such as , calendar, etc. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight. In addition, in the test items in the table, the "'" on the right side of the numbers for the coloring state of the sheets indicates "minutes." Example 1 After mixing the resins and stabilizers shown in [Table 1] and [Table 2], the mixture was kneaded using a test roll at 160°C for 5 minutes to produce a sheet with a thickness of 0.5 mm. After cutting this sheet into a size of 3cm x 6cm,
The material was placed in a gear type aging tester heated to 180°C and taken out at regular intervals for a thermal stability test. The results are shown in [Table 3] and [Table 4]. In the table,
The following symbols represent the coloring state of the sheet. ◎Colorless〇Yellow△Brown×Black Example 2 In addition to the resin and stabilizer shown in [Table-1] and [Table-2], a red pigment [#8040 Red, manufactured by Dainichiseika Co., Ltd.]
After mixing 1.0 part, it was heated to 160℃ using a test roll for 25 minutes.
After kneading for a minute, the sheet was removed. After this, PVC
(Geon103Ep manufactured by Zeon Corporation) 100 copies, DOP
(dioctyl phthalate) 25 parts, titanium white [TA
-100, manufactured by Fuji Titanium Co., Ltd.] 2.0 parts, dibutyltin dilaurate 1.0 parts, cadmium stearate 0.3
After kneading on a roll for 1 minute, the sheet was taken out and plate-out was determined based on the degree of red coloring of the sheet (hereinafter abbreviated as cleaning sheet). The results are shown in [Table 3] and [Table 4]. In the table, plate out is indicated by the following symbol. 〇The cleaning sheet appears milky white. (Plate out does not occur.) ×The cleaning sheet appears pink to red. (Plate-out occurs.) Example 3 In addition to the resins and stabilizers shown in [Table-1] and [Table-2], carbon black [#600B, Mitsubishi Chemical Industries, Ltd.]
Co., Ltd.] After mixing 0.5 parts, use a test roll to
The mixture was kneaded at ℃ for 5 minutes to prepare a sheet with a thickness of 0.5 mm. After cutting this sheet into a size of 3.0 cm x 6.0 cm, 5 sheets were stacked and pressed at 180° C. and 20 kg/cm ² for 20 minutes. This press plate was placed in a gear-type aging tester preheated to 120°C and taken out after 60 minutes, and the state of bubbling on the press plate surface was determined. The results are shown in [Table 3] and [Table 4]. In the table, balloons are indicated by the following symbols. 〇There are almost no bubbles observed on the surface of the press plate. × Bubbling is observed on the entire surface of the press plate. Example 4 After mixing the resins shown in [Table 5], [Table 6], and [Table 7] with a stabilizer, the mixture was kneaded using a test roll at 160°C for 3 minutes. This sheet was cut into 4cm x 4cm pieces, placed on a 5cm x 5cm glass plate, placed in a gear aging tester preheated to 210℃, and taken out at regular intervals for a thermal stability test. Ivy. The results are shown in [Table-8], [Table-9], [Table-
10]. In the table, the coloring state of the sheet is indicated by the following symbols. ◎Pale yellow to yellow 〇Yellow orange△Pale brown × Blackening Example 5 Add 1.0 part of red pigment #8040 Red to the resin and stabilizer shown in [Table-5], [Table-6], and [Table-7]. The mixture was mixed and plateout was determined in the same manner as in Example 2. The results are shown in [Table-8], [Table-9], and [Table-10]. Example 6 0.5 part of carbon black #600B was further mixed with the resin and stabilizer shown in [Table-5], [Table-6], and [Table-7], and the state of bubbling was determined in the same manner as in Example 3. did. The results are shown in [Table-8], [Table-9], and [Table-10].

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Claims (1)

[Claims] 1 General formula for 100 parts by weight of vinyl chloride resin or a blend resin of vinyl chloride resin and acrylonitrile-butadiene-styrene resin or methyl methacrylate-butadiene-styrene resin (R ¹ and R ² in the formula are alkyl groups, and can be the same or different. R ³ and R ⁴ are an alkyl group, a substituted alkyl group, an alkenyl group, a cycloalkyl group, They may be the same or different from each other. m is a number from 0 to 5.) Organotin maleic acid ester salt 0.5 to 3.0
Parts by weight and general formula (2) (R ⁵ ) ₂ Sn (SCH ₂ CH ₂ COOR ⁶ ) ₂ (In the formula, R ⁵ is an alkyl group and may be the same or different. R ⁶ is an alkyl group, substituted alkyl group, aryl group, alkenyl group, cycloalkyl group, which may be the same or different from each other.) 0.5~
1.5 parts by weight and the general formula (R ⁷ ) ₂ Sn (SCH ₂ COOR ⁸ ) ₂ (in the formula, R ⁷ is an alkyl group and may be the same or different from each other. R ⁸ is an alkyl group, substituted alkyl group, aryl group, alkenyl group, cycloalkyl group, which may be the same or different from each other. A method for stabilizing vinyl chloride resin or its blend resin.