JPS625189B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for stabilizing synthetic resins, and more specifically, the present invention relates to a method for stabilizing synthetic resins, and more specifically, vinyl chloride resin and acrylonitrile-butadiene-styrene copolymer resin (hereinafter,
This paper relates to a method for stabilizing a blend polymer with ABS resin (abbreviated as ABS resin). Generally, blend polymers of vinyl chloride resin and ABS resin (hereinafter abbreviated as PVC/ABS blend polymers) are exposed to high temperatures during molding, but their resistance to heat is extremely weak, so molded products are It loses its commercial value due to discoloration and decreased physical strength. Various heat stabilizers are used for this purpose.
Examples of these stabilizers include metal soaps, organic tin compounds, boron compounds, epoxy compounds, organic phosphorous esters, and hindered phenols. Among these, organotin sulfur-containing compounds, which are organotin compounds, are relatively good stabilizers, but even if this organotin sulfur-containing compound is used as a stabilizer, the blend polymer molded product will still be colored. loss of product value, etc.
It's not completely satisfying. On the other hand, as techniques disclosed regarding the stabilization of synthetic resins using boron compounds, there are
No. 48-10630, Japanese Patent Publication No. 125443-1971,
Although there are various publications such as JP-A-52-65545 and JP-A-53-111346, the techniques disclosed in these inventions are still insufficient under severe processing conditions.
When producing the boron compounds used in these inventions, a large amount of solvent is generally required and the reaction takes a long time, and many of the boron compounds mentioned above are viscous liquids that are difficult to handle. and
In addition, it has poor dispersibility in resins, and when the aforementioned boron compounds are solids, most of them are sticky glass-like solids that are difficult to crush, and they absorb moisture from the atmosphere. It has disadvantages such as being complicated to handle because it deteriorates in a short period of time. Taking these drawbacks into consideration, the inventors of the present invention have conducted extensive research and found that they can stabilize PVC/ABS blend polymers by using an organotin sulfur compound together with boric acid or boric anhydride. The present invention was completed based on the discovery that a synergistic effect unexpected from the stabilizing effect when used alone in the blend polymer is exhibited. That is, the present invention
When stabilizing the PVC/ABS blend polymer, (a) [In formula (1), R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, or a group in which the hydrogen bonded to carbon of these groups is substituted with a substituent. Y is
R ¹ or Z ¹ . Z ¹ is -SR ² groups, -S
(CH ₂ ) _p COOR ³ group, R ² and R ³ represent an alkyl group, alkenyl group, aralkyl group, cycloalkyl group or alkoxyalkyl group, p
is an integer of 1 or 2. X represents an oxygen atom or a sulfur atom, and m is 0 or 1. ]
This is a method of imparting excellent thermal stability to the blend polymer by adding an organotin sulfur-containing compound and (b) boric acid or boric anhydride in combination. To describe in detail the general formula (1), which is the organotin sulfur-containing compound used in the present invention, when R ¹ is an alkyl group, this alkyl group includes a linear alkyl group and a branched alkyl group, Examples include alkyl groups having 1 to 18 carbon atoms, and specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl,
Examples include groups such as octadecyl, and in the case of cycloalkyl groups, examples include cyclohexyl and cyclooctyl. When R ¹ is an aryl group, this aryl group means an aromatic monovalent group, and examples include aryl groups having 6 to 19 carbon atoms. Examples of ^substituents that can replace the hydrogen bonded to the carbon of the alkyl group, cycloalkyl group, and aryl group include the alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, and acyloxy group. , alkoxycarbonyl group,
Examples include an alkylthio group, an arylthio group, an amino group, and a halogen atom. Examples of groups substituted with these substituents include:
Alkoxyalkyl group, aryloxyalkyl group, acylalkyl group, alkoxycarbonylalkyl group, halogenated alkyl group, hydroxyalkyl group, alkylthioalkyl group, arylthioalkyl group, alkylaryl group, halogenated aryl group, hydroxyaryl group, alkoxy Examples include an aryl group, an acylaryl group, an acyloxyaryl group, an alkoxycarbonylaryl group, an aminoaryl group, an alkoxyalkoxy group, an alkylthioalkoxy group, and an arylthioaryloxy group. Z ¹ is -SR ² groups, -SCH ₂ COOR ³ groups or -
In the case of SCH ₂ CH ₂ COOR ³ groups, R ² and R ³ have 1 or more carbon atoms
18 alkyl groups, aryl groups having 6 to 12 carbon atoms, or alkoxyalkyl groups, specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl, isooctyl, 2-
Ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, oleyl, cyclohexyl,
Mention may be made of groups such as cyclooctyl, phenyl, naphthyl, benzyl, propylbenzyl, methoxybutyl, ethoxybutyl and the like. Specific examples of the organotin sulfur-containing compound used in the present invention and represented by the general formula (1) include monomethyltin tris (butyl mercaptide), monomethyltin tris (octyl mercaptide), monomethyltin tris (dodecyl mercaptide), monobutyltin tris (butyl mercaptide), monobutyltin tris (octyl mercaptide), monobutyltin tris (dodecyl mercaptide), monobutyltin tris (octadecyl mercaptide), monooctyltin Tris (butyl mercaptide), monooctyltin tris (octyl mercaptide), monooctyltin tris (dodecyl mercaptide), monooctyltin tris (octadecyl mercaptide), monododecyltin tris (octyl mercaptide) ), dimethyltin bis(butyl mercaptide), dimethyltin bis(octyl mercaptide), dimethyltin bis(dodecyl mercaptide), dimethyltin bis(octadecyl mercaptide), dibutyltin bis(butyl mercaptide) ), dibutyltin bis(octyl mercaptide), dibutyltin bis(dodecyl mercaptide), dibutyltin bis(octadecyl mercaptide), dioctyltin bis(butyl mercaptide), dioctyltin bis(octyl mercaptide) ), dioctyltin bis (dodecyl mercaptide), dioctyltin bis (octyl mercaptide), didodecyltin bis (octyl mercaptide), monomethyltin tris (methylthioglycolate), monomethyltin tris (butylthioglycolate) , Monomethyltin Tris (methoxybutylthioglycolate), Monomethyltin Tris (hexylthioglycolate), Monomethyltin Tris (octylthioglycolate), Monomethyltin Tris (isooctylthioglycolate), Monomethyltin Tris (2-ethylhexyl) thioglycolate), monomethyltin tris (decyl thioglycolate), monomethyltin tris (dodecyl thioglycolate), monomethyltin tris (octadecyl thioglycolate), monomethyltin tris (oleyl thioglycolate), monomethyltin tris (cyclohexyl thioglycolate), Monobutyltin Tris (Methylthioglycolate), Monobutyltin Tris (Butylthioglycolate), Monobutyltin Tris (Methoxybutylthioglycolate), Monobutyltin Tris (Hexylthioglycolate), Monobutyltin Tris (Octyl thioglycolate), monobutyltin tris (isooctyl thioglycolate), monobutyltin tris (2-ethylhexyl thioglycolate), monobutyltin tris (decyl thioglycolate), monobutyltin tris (dodecyl thioglycolate),
Monobutyltin tris (octadecylthioglycolate), monobutyltin tris (oleyl thioglycolate), monobutyltin tris (benzylthioglycolate), monobutyltin tris (cyclohexylthioglycolate), monooctyltin tris (methylthioglycolate), Monooctyltin Tris (Butylthioglycolate), Monooctyltin Tris (Methoxybutylthioglycolate), Monooctyltin Tris (Hexylthioglycolate), Monooctyltin Tris (Octylthioglycolate), Monooctyltin Tris ( isooctylthioglycolate), monooctyltin tris(2-ethylhexylthioglycolate),
Monooctyltin tris (decyl thioglycolate), monooctyltin tris (dodecyl thioglycolate), monooctyltin tris (octadecyl thioglycolate), monooctyltin tris (oleyl thioglycolate), monooctyltin tris (benzyl thioglycolate), monooctyltin tris (cyclohexylthioglycolate), monododecyltin tris (octylthioglycolate), monobenzyltin tris (octylthioglycolate), 2-methoxycarbonylethyltin tris (octylthioglycolate) ), 2-
Ethoxycarbonylethyltin tris (isooctylthioglycolate), monomethyltin tris (methyl 3-mercaptopropionate), monomethyltin tris (butyl 3-mercaptopropionate), monomethyltin tris (methoxybutyl 3-mercaptopropionate),
mercaptopropionate), monomethyltin tris(hexyl 3-mercaptopropionate),
Monomethyltin tris (octyl 3-mercaptopropionate), monomethyltin tris (isooctyl 3-mercaptopropionate), monomethyltin tris (2-ethylhexyl 3-mercaptopropionate), monomethyltin tris (decyl 3-mercaptopropionate) monomethyltin tris (dodecyl 3-mercaptopropionate), monomethyltin tris (octadecyl 3-mercaptopropionate), monomethyltin tris (oleyl 3-mercaptopropionate), monomethyltin tris (benzyl 3-mercaptopropionate), mercaptopropionate), monomethyltin tris (cyclohexyl 3-mercaptopropionate), monobutyltin tris (methyl 3-mercaptopropionate), monobutyltin tris (butyl 3-mercaptopropionate), monobutyltin tris (methoxy) butyl 3-mercaptopropionate), monobutyltin tris (hexyl 3-mercaptopropionate), monobutyltin tris (octyl 3-mercaptopropionate),
-mercaptopropionate), monobutyltin tris (isooctyl 3-mercaptopropionate), monobutyltin tris (2-ethylhexyl 3-mercaptopropionate), monooctyltin tris (decyl 3-mercaptopropionate), mono Octyltin tris (dodecyl 3-mercaptopropionate), monooctyltin tris (octadecyl 3-mercaptopropionate),
Monooctyltin tris (oleyl 3-mercaptopropionate), monooctyltin tris (benzyl 3-mercaptopropionate), monooctyltin tris (cyclohexyl 3-mercaptopropionate), monododecyltin tris (octyl 3-mercaptopropionate) mercaptopropionate), monobenzyltin tris(octyl 3-mercaptopropionate), 2-methoxycarbonylethyltin tris(octyl 3-mercaptopropionate), 2-
Ethoxycarbonylethyltin tris (isooctyl 3-mercaptopropionate), dimethyltin bis (methyl thioglycolate), dimethyl tin bis (butyl thioglycolate), dimethyl tin bis (methoxybutyl thioglycolate), dimethyl tin bis (hexyl thioglycolate), dimethyltin bis(octylthioglycolate), dimethyltin bis(isooctylthioglycolate), dimethyltin bis(2-ethylhexylthioglycolate), dimethyltin bis(decylthioglycolate), dimethyltin Bis(dodecylthioglycolate), dimethyltinbis(octadecylthioglycolate), dimethyltinbis(oleylthioglycolate), dimethyltinbis(benzylthioglycolate), dimethyltinbis(cyclohexylthioglycolate), dibutyltin Bis(methylthioglycolate), dibutyltin bis(butylthioglycolate), dibutyltin bis(methoxybutylthioglycolate), dibutyltin bis(hexylthioglycolate), dibutyltin bis(octylthioglycolate), dibutyltin Bis(isooctylthioglycolate), dibutyltinbis(2-ethylhexylthioglycolate), dibutyltinbis(decylthioglycolate), dibutyltinbis(dodecylthioglycolate), dibutyltinbis(octadecylthioglycolate) , dibutyltin bis(oleyl thioglycolate), dibutyltin bis(benzyl thioglycolate), dibutyltin bis(cyclohexyl thioglycolate), dioctyltin bis(methylthioglycolate), dioctyltin bis(butyl thioglycolate), Dioctyltin bis(methoxybutylthioglycolate), dioctyltin bis(hexylthioglycolate), dioctyltin bis(octylthioglycolate), dioctyltin bis(isooctylthioglycolate), dioctyltin bis(2-ethylhexylthio) glycolate), dioctyltin bis(decylthioglycolate), dioctyltinbis(dodecylthioglycolate), dioctyltinbis(octadecylthioglycolate), dioctyltinbis(oleylthioglycolate), dioctyltinbis(benzylthioglycolate) glycolate), dioctyltin bis(cyclohexylthioglycolate),
Didodecyltin bis(octylthioglycolate), bis(2-methoxycarbonylethyl)tinbis(octylthioglycolate), bis(2-
ethoxycarbonylethyl)tin bis(2-ethylhexylthioglycolate), dibenzyltin bis(octylthioglycolate), dimethyltin bis(methyl 3-mercaptopropionate), dimethyltin bis(butyl 3-mercaptopropionate) , dimethyltin bis(methoxybutyl 3-mercaptopropionate), dimethyltin bis(hexyl 3-mercaptopropionate), dimethyltin bis(octyl 3-mercaptopropionate), dimethyltin bis(isooctyl 3-mercaptopropionate) pionate), dimethyltin bis(2-ethylhexyl 3-mercaptopropionate),
Dimethyltin bis(decyl 3-mercaptopropionate), dimethyltin bis(dodecyl 3-mercaptopropionate), dimethyltin bis(octadecyl 3-mercaptopropionate), dimethyltin bis(oleyl 3-mercaptopropionate) ), dimethyltin bis(benzyl 3-mercaptopropionate), dimethyltin bis(cyclohexyl 3-mercaptopropionate), dibutyltin bis(methyl 3-mercaptopropionate), dibutyltin bis(butyl 3-mercaptopropionate) pionate), dibutyltin bis(methoxybutyl 3-mercaptopropionate), dibutyltin bis(hexyl 3-mercaptopropionate), dibutyltin bis(octyl 3-mercaptopropionate), dibutyltin bis(isooctyl 3-mercaptopropionate) -mercaptopropionate), dibutyltin bis(2-ethylhexyl 3-mercaptopropionate), dibutyltin bis(decyl 3-mercaptopropionate), dibutyltin bis(dodecyl 3-mercaptopropionate), dibutyltin Bis(octadecyl 3-mercaptopropionate), dibutyltin bis(oleyl 3-mercaptopropionate), dibutyltin bis(benzyl 3-mercaptopropionate),
-mercaptopropionate), dibutyltin bis(cyclohexyl 3-mercaptopropionate), dioctyltin bis(methyl 3-mercaptopropionate), dioctyltin bis(butyl 3-mercaptopropionate)
-mercaptopropionate), dioctyltin bis(methoxybutyl 3-mercaptopropionate), dioctyltin bis(hexyl 3-mercaptopropionate), dioctyltin bis(octyl 3-mercaptopropionate), dioctyltin bis (isooctyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate), dioctyltin bis(decyl 3-mercaptopropionate),
Dioctyltin bis(dodecyl 3-mercaptopropionate), dioctyltin bis(octadecyl 3-mercaptopropionate), dioctyltin bis(oleyl 3-mercaptopropionate), dioctyltin bis(benzyl 3-mercaptopropionate) ), dioctyltin bis(cyclohexyl 3-mercaptopropionate), didodecyltin bis(2-ethylhexyl 3-mercaptopropionate), dibenzyltin bis(2-ethylhexyl 3-mercaptopropionate),
Bis(2-methoxycarbonylethyl)tin bis(octyl 3-mercaptopropionate), bis(2-ethoxycarbonylethyl)tin bis(2-
ethylhexyl 3-mercaptopropionate), bis[monomethyltin bis(methylthioglycolate)] sulfide, bis[monobutyltin bis(octylthioglycolate)] sulfide, bis[monoctyltin bis(2-ethylhexylthioglycolate)] ] Sulfide, bis[monomethyltin bis(methoxybutyl 3-mercaptopropionate)] sulfide, bis[monobutyltin bis(octyl 3-mercaptopropionate)] sulfide, bis[monooctyltin bis(decyl 3-mercaptopropionate)] pionate)] sulfide, bis[monomethyltin bis(methyl 3-mercaptopropionate)] oxide, bis[monobutyltin bis(2-ethylhexyl 3-mercaptopropionate)] oxide, bis[monoctyltin bis(oleyl 3-mercaptopropionate)] oxide, bis(dimethyltin methyl 3-mercaptopropionate) oxide, bis(dibutyltin methoxybutyl 3-mercaptopropionate) oxide,
Bis(dioctyltin 2-ethylhexyl 3-mercaptopropionate) oxide and the like. The boric acid or boric anhydride used in the present invention may be any of orthoboric acid, metaboric acid, tetraboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, and the like. When stabilizing the PVC/ABS blend polymer of the present invention, the amounts of the organic tin-containing sulfur compound and boric acid or boric anhydride added to the blend polymer are not particularly limited and are appropriately determined depending on the purpose, but usually, Sufficient effects are shown with 0.1 to 6 parts by weight of the organotin sulfur-containing compound and 0.01 to 2 parts by weight of boric acid or boric anhydride based on 100 parts by weight of the blended polymer. The stabilizer used in the present invention may be added to the PVC/ABS blend polymer using conventionally known techniques, such as mixing the resin and stabilizer with a Henschel mixer, ribbon blender, Banbury mixer, etc. Alternatively, the organotin sulfur-containing compound and boric acid or boric anhydride may be mixed in advance and then mixed with the resin using the above-mentioned mixer. In the present invention, metal soaps, epoxy compounds, ultraviolet absorbers, lubricants, pigments, fillers, etc. can be further added as necessary. Examples of PVC/ABS blend polymers used in the present invention include vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin, and vinyl chloride-propylene copolymer resin. , vinyl chloride-styrene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-acrylonitrile copolymer resin, vinyl chloride-styrene-acrylonitrile-
Examples include blend polymers of butadiene copolymer resins and acrylonitrile-butadiene-styrene copolymer resins. The present invention will be specifically explained below using Examples. In the examples, parts mean parts by weight. Example 1 Vinyl chloride resin [Geon103EP manufactured by Nippon Zeon Co., Ltd.
-8] 95 parts, ABS resin [Manufactured by Toray Industries, Inc.]
100] and 3 parts of the stabilizer shown in Table 1 were added and kneaded for 4 minutes using an 8-inch test roll adjusted to 170°C to produce a sheet with a thickness of 0.5 mm. The obtained sheet was cut, and test pieces were taken out at regular intervals from a gear type aging tester set at 180°C, and the degree of color deterioration was determined visually. The evaluations are shown in Tables 2 and 3 as follows: 1: Slight yellow, 2: Pale yellow, 3: Yellow, 4: Tan, 5: Brown, 6: Dark brown.

【table】

【table】

【table】

【table】

[Table] Example 2 Vinyl chloride resin [Geon103EP manufactured by Nippon Zeon Co., Ltd.]
-8) 50 parts, ABS resin [Toyoratsuku manufactured by Toray Industries, Inc.]
A mixture of 50 parts of 100 and the stabilizer shown in Table 4 was mixed with an 8-inch test roll adjusted to 170°C.
The mixture was kneaded for a minute to produce a sheet with a thickness of 0.5 mm. The obtained sheet was cut and placed on a glass plate at 205℃.
Thermal stability was tested in the same manner as in Example 1 using a gear type aging tester set to
It was shown to. The evaluation criteria are the same as in Example 1.

【table】

【table】

[Table] Example 3 Vinyl chloride resin [Geon103EP manufactured by Nippon Zeon Co., Ltd.]
-8] 50 parts, ABS resin [Toyoratsuk manufactured by Toray Industries, Inc.
100] 50 parts, di-n-octyltin bis(isooctylthioglycolate) shown in Table-7 (Table-7
A compound containing boric acid (in Table 7, abbreviated as A) and boric acid (in Table 7, abbreviated as B) was made into a sheet under the same operating conditions as in Example 2, and the thermal stability of this sheet was determined under the same operating conditions as in Example 2. was tested. The results are shown in Table-7. The evaluation criteria are the same as in Example 1.

[Table] * Comparative example

Claims (1)

[Claims] 1. When stabilizing a blend polymer of vinyl chloride resin and acrylonitrile-butadiene-styrene copolymer resin, (a) general formula [In the formula, R ¹ is an alkyl group, a cycloalkyl group,
Indicates an aryl group or a group in which the hydrogen bonded to carbon of these groups is substituted with a substituent. Y is R ¹
Or Z ¹ . Z ¹ is -SR ² groups, -S
(CH ₂ ) _p COOR ³ group, R ² and R ³ represent an alkyl group, alkenyl group, aralkyl group, cycloalkyl group or alkoxyalkyl group, p
is an integer of 1 or 2. X represents an oxygen atom or a sulfur atom, and m is 0 or 1. ]
A method for stabilizing the resin, which comprises adding an organotin-sulfur-containing compound represented by the formula (b) in combination with boric acid or boric anhydride.