JPH0456060B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the stabilization of synthetic resins, and more specifically,
This invention relates to a method for stabilizing a blend polymer of acrylonitrile-butadiene-styrene copolymer resin (hereinafter abbreviated as ABS) and vinyl chloride resin (hereinafter abbreviated as PVC). In general, there are two methods for making ABS flame retardant: adding bromine-based flame retardants and flame retardant aids such as antimony trioxide to ABS, and blending ABS with PVC. Currently, these materials tend to undergo thermal deterioration during molding, resulting in colored molded products and deterioration in physical properties. As thermal stabilizers for blend polymers of ABS and PVC, there are various metal soaps, organic tin compounds, boron compounds, epoxy compounds, organic phosphite esters, and hindered phenols. Among these, organotin sulfur-containing compounds, which are one of organotin compounds, are relatively good stabilizers;
Even when this organotin sulfur-containing compound is used as a stabilizer, the heat stabilizing effect is still insufficient, so there has been a need to develop a more excellent heat stabilizer. From this point of view, the present inventors have conducted intensive research on stabilizers with excellent thermal stabilizing effects for blend polymers of ABS and PVC, and have found that the weight ratio of ABS and PVC is 6:4 to 4:6. When stabilizing the blend polymer, (a) general formula (1) and/or general formula (2) [In formulas (1) and (2), R ¹ represents an alkyl group or an alkoxycarbonylalkyl group. Y is R ¹ or
^Z1 . Z ¹ represents -S(CH ₂ ) _P COOR ² group,
R ² represents an alkyl group or an alkoxyalkyl group, and p is an integer of 1 or 2. Z ² represents a sulfur atom or a -S(CH ₂ ) _r COO- group, and r is 1
or an integer of 2, l is an integer of 1 or 2, and n is an integer of 1 to 10. ] and (b) a maleate salt and/or a maleic acid monomer of a metal selected from the group consisting of Li, Na, K, Mg, Ca, Zn, Sr, Ba, and Sn. The present invention was completed by discovering that by adding an ester salt in combination, a synergistic effect that could not be expected from the thermal stabilizing effect when these additives were used alone in the blend polymer was achieved. ABS used in the present invention is a resin obtained by copolymerizing acrylonitrile, a conjugated diene compound, and a styrene compound. Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, Examples of styrene compounds include isoprene, etc.
Examples include styrene, α-methylstyrene, vinyltoluene, o-chlorostyrene, etc.
Specific examples of ABS include acrylonitrile/butadiene/styrene copolymer, acrylonitrile/butadiene/isoprene/styrene copolymer, acrylonitrile/butadiene/α-methylstyrene copolymer, and acrylonitrile/butadiene/styrene/α-methylstyrene copolymer. Examples include polymers. The PVC used in the present invention is a polymer resin of vinyl chloride monomer and a copolymer resin of vinyl chloride monomer and other monomers. Specific examples of PVC include vinyl chloride resin, vinyl chloride/vinyl acetate copolymer resin , vinyl chloride/ethylene copolymer resin, 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/butadiene Examples include copolymer resins and the like. When it comes to making ABS flame retardant, ABS and PVC are usually used.
are blended at a weight ratio of 6:4 to 4:6, with 1:1 being particularly frequently used. General formulas (1) and (2) which are organotin sulfur-containing compounds used to stabilize the blend polymer
To explain in detail, when R ¹ is an alkyl group, this alkyl group includes a linear alkyl group and a branched alkyl group, and examples include alkyl groups having 1 to 18 carbon atoms. Examples include groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, and the like. When R ¹ is an alkoxycarbonylalkyl group,
Examples include alkoxycarbonylalkyl groups having 4 to 7 carbon atoms, and specific examples include groups such as 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, and 2-butoxycarbonylethyl. Z ¹ is -SCH ₂ COOR ² groups or -SCH ₂ CH ₂
In the case of COOR ² groups, R ² can be an alkyl group or an alkoxyalkyl group having 1 to 18 carbon atoms,
Specific examples include methyl, ethyl, propyl,
Butyl, hexyl, octyl, isooctyl, 2
Mention may be made of groups such as -ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, methoxybutyl, ethoxybutyl and the like. Specific examples of the organotin sulfur-containing compound represented by the general formula (1) used in the present invention include, but are not limited to, the following. Monomethyltin tris (methylthioglycolate),
Monomethyltin tris (butylthioglycolate),
Monomethyltin tris (methoxybutylthioglycolate), monomethyltin tris (hexylthioglycolate), monomethyltin tris (octylthioglycolate), monomethyltin tris (isooctylthioglycolate), monomethyltin tris (2-ethylhexylthio) glycolate), monomethyltin tris (decylthioglycolate), monomethyltin tris (dodecylthioglycolate),
Monomethyltin Tris (Octadecylthioglycolate), Monobutyltin Tris (Methylthioglycolate), Monobutyltin Tris (Butylthioglycolate), Monobutyltin Tris (Methoxybutylthioglycolate), Monobutyltin Tris (Hexylthioglycolate), Monobutyltin tris (octylthioglycolate), monobutyltin tris (isooctylthioglycolate), monobutyltin tris (2-ethylhexylthioglycolate), monobutyltin tris (decylthioglycolate), monobutyltin tris (dodecylthioglycolate) monobutyltin tris (octadecylthioglycolate), monooctyltin tris (methylthioglycolate), monooctyltin tris (butylthioglycolate), monooctyltin tris (methoxybutylthioglycolate), monooctyltin tris (Hexylthioglycolate),
Monooctyltin tris (octylthioglycolate), monooctyltin tris (isooctylthioglycolate), monooctyltin tris (2-ethylhexylthioglycolate), monooctyltin tris (decylthioglycolate), monooctyltin tris (decylthioglycolate) Tris (dodecylthioglycolate), monooctyltin tris (octadecylthioglycolate), monododecyltin tris (octylthioglycolate), 2-methoxycarbonylethyltin tris (octylthioglycolate), 2-ethoxycarbonylethyltin Tris(isooctylthioglycolate), 2-butoxycarbonylethyltin tris(isooctylthioglycolate),
Monomethyltin tris((methyl 3-mercaptopropionate), monomethyltin tris(butyl 3-mercaptopropionate)
-mercaptopropionate), monomethyltin tris (methoxybutyl 3-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),
mercaptopropionate), monomethyltin tris (octadecyl 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(hexyl 3-mercaptopropionate),
mercaptopropionate), monobutyltin tris(octyl 3-mercaptopropionate),
Monobutyltin tris (isooctyl 3-mercaptopropionate), monobutyltin tris (2-
ethylhexyl 3-mercaptopropionate),
Monooctyltin tris (decyl 3-mercaptopropionate), monooctyltin tris (dodecyl 3-mercaptopropionate), monooctyltin tris (octadecyl 3-mercaptopropionate), monododecyltin tris (octyl 3-mercaptopropionate)
-mercaptopropionate), 2-ethoxycarbonylethyltin tris (octyl 3-mercaptopropionate), 2-methoxycarbonylethyltin tris (isooctyl 3-mercaptopropionate), dimethyltin bis(methylthioglycolate), Dimethyltin bis(butylthioglycolate), dimethyltin bis(methoxybutylthioglycolate), dimethyltin bis(hexylthioglycolate), dimethyltin bis(octylthioglycolate), dimethyltin bis(isooctylthioglycolate) ), dimethyltin bis(2-ethylhexylthioglycolate), dimethyltin bis(decylthioglycolate), dimethyltin bis(dodecylthioglycolate), dimethyltin bis(octadecylthioglycolate), dibutyltin bis(methylthioglycolate) ), dibutyltin bis(butylthioglycolate), dibutyltinbis(methoxybutylthioglycolate), dibutyltinbis(hexylthioglycolate), dibutyltinbis(octylthioglycolate), dibutyltinbis(isooctyl) thioglycolate), dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin bis(decylthioglycolate), dibutyltin bis(dodecylthioglycolate), dibutyltin bis(octadecylthioglycolate),
Dioctyltin bis(methylthioglycolate),
Dioctyltin bis(butylthioglycolate),
Dioctyltin bis(methoxybutylthioglycolate), dioctyltin bis(hexylthioglycolate), dioctyltin bis(octylthioglycolate), dioctyltin bis(isooctylthioglycolate), dioctyltin bis(2-ethylhexylthio) glycolate), dioctyltin bis(decylthioglycolate), dioctyltinbis(dodecylthioglycolate), dioctyltinbis(octadecylthioglycolate), didodecyltinbis(octylthioglycolate), bis(2-methoxycarbonyl) ethyl)tin bis(octylthioglycolate), bis(2-ethoxycarbonylethyl)tin bis(2-ethylhexylthioglycolate), bis(2-butoxycarbonylethyl)tin bis(isooctylthioglycolate), 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), dimethyltin bis(2-ethylhexyl 3-mercaptopropionate) pionate), dimethyltin bis(decyl 3-
mercaptopropionate), dimethyltin bis(dodecyl 3-mercaptopropionate), dimethyltin bis(octadecyl 3-mercaptopropionate), dibutyltin bis(methyl 3-mercaptopropionate), dibutyltin bis(butyl 3-mercaptopropionate), dibutyltin bis(methoxybutyl 3-mercaptopropionate), dibutyltin bis(hexyl 3-mercaptopropionate), dibutyltin bis(octyl 3-mercaptopropionate)
-mercaptopropionate), dibutyltin bis(isooctyl 3-mercaptopropionate),
Dibutyltin bis(2-ethylhexyl 3-mercaptopropionate), dibutyltin bis(decyl 3-mercaptopropionate), dibutyltin bis(dodecyl 3-mercaptopropionate),
Dibutyltin bis(octadecyl 3-mercaptopropionate), dioctyltin bis(methyl 3-mercaptopropionate)
mercaptopropionate), dioctyltin bis(butyl 3-mercaptopropionate), dioctyltin bis(methoxybutyl 3-mercaptopropionate), dioctyltin bis(hexyl 3-mercaptopropionate)
mercaptopropionate), dioctyltin bis(octyl 3-mercaptopropionate), dioctyltin bis(isooctyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate) (decyl 3-mercaptopropionate), dioctyltin bis(dodecyl 3-mercaptopropionate), dioctyltin bis(octadecyl 3-mercaptopropionate), didodecyltin bis(2-ethylhexyl 3-mercaptopropionate) , bis(2-methoxycarbonylethyl)tinbis(octyl 3-mercaptopropionate), bis(2-ethoxycarbonylethyl)tinbis(2-ethylhexyl 3-mercaptopropionate), and the like. Specific examples of the organotin sulfur-containing compound represented by general formula (2) include, but are not limited to, the following. Monomethyltin sulfide, monobutyltin sulfide, monooctyltin sulfide, monododecyltin sulfide, 2
-Methoxycarbonylethyltin sulfide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, didodecyltin sulfide, bis(2-methoxycarbonylethyl)tin sulfide, monomethyltin thioglycolate, monobutyltin thioglycolate, monooctyltin thio Glycolate, 2-methoxycarbonylethyltin thioglycolate, monomethyltin 3-
Mercaptopropionate, monobutyltin 3-mercaptopropionate, monooctyltin 3-mercaptopropionate, 2-methoxycarbonylethyltin 3-mercaptopropionate, dimethyltin thioglycolate, dibutyltin thioglycolate, dioctyl Tin thioglycolate, didodecyltin thioglycolate, bis(2-methoxycarbonylethyl)tin thioglycolate, dimethyltin 3-mercaptopropionate, dibutyltin 3
-Mercaptopropionate, dioctyltin 3-
Examples include mercaptopropionate, didodecyltin 3-mercaptopropionate, bis(2-methoxycarbonylethyl)tin 3-mercaptopropionate, and polymers thereof. Examples of metal salts of maleic acid used in the present invention include Li, Na, K, Mg, Ca, Zn, Sr, Ba,
Neutral salts, acidic salts, and basic salts of maleic acid metal salts of Sn can be mentioned. Examples of maleic acid monoester metal salts include maleic acid and aliphatic saturated alcohols, aliphatic unsaturated alcohols, aromatic Examples of the metal salts of monoesters with group alcohols include Li, Na, K, Mg, Ca,
Maleic acid monobutyl ester salt of Zn, Sr, Ba, Sn, maleic acid monobutyl ester salt, maleic acid monoisooctyl ester salt, maleic acid mono-2-ethylhexyl ester salt, maleic acid monolauryl ester salt, monostearyl maleate Examples include, but are not limited to, ester salts, maleic acid monooleyl ester salts, maleic acid monobenzyl ester salts, maleic acid monocyclohexyl ester salts, and maleic acid monomethoxybutyl ester salts. In addition, when carrying out the invention, a mixture of these can also be used. In the present invention, when stabilizing a blend polymer of ABS and PVC, an organic tin-containing sulfur compound and a metal salt of maleic acid,
The amount of the metal salt of maleic acid monoester to be added is not particularly limited and is determined appropriately depending on the purpose, but usually, based on 100 parts by weight of the blend polymer,
The purpose can be achieved by adding 0.1 to 6.0 parts by weight of an organotin sulfur-containing compound and 0.01 to 3.0 parts by weight of a metal salt of maleic acid and/or a metal salt of maleic acid monoester. The heat stabilizer used in this invention is ABS and PVC
The method of adding the heat stabilizer to the blended polymer may be carried out using conventionally known techniques. For example, the blended polymer and the heat stabilizer may be mixed using a Henschel mixer, a ribbon blender, a Banbury mixer, etc., or the organic tin A sulfur-containing compound and a metal salt of maleic acid and/or a metal salt of maleic acid monoester may be prepared in advance and mixed with the blend polymer using the above-mentioned mixer. For example, pigments, fillers,
Antistatic agents, plate-out prevention agents, surface treatment agents, lubricants, antifungal agents, processing aids, epoxy compounds,
Various metal soaps, boron compounds, organic phosphites, antioxidants, organic tin maleate compounds, etc. can be added. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. In these examples, parts mean parts by weight, and deterioration time is the time (minutes) until the sheet turns black.
It is. Example 1 50 parts of ABS [TOYORAKU 100 manufactured by Toray Industries, Inc.], 50 parts of PVC [Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.] and G-n-
A mixture of 2.0 parts of octyltin bis(isooctylthioglycolate) and the heat stabilizer shown in Table 1 was kneaded for 5 minutes using an 8-inch test roll adjusted to 155°C to form a 0.5 mm thick sheet. was created. Next, a 5 cm x 5 cm test piece was prepared from this sheet, and this test piece was sandwiched between glass plates and placed in a gear oven at 220°C to conduct a thermal stability test. The results are shown in Table 1. The degree of coloration indicates the color tone after 30 minutes.

【table】

[Table] Example 2 50 parts of ABS [TOYORATSUKU 100 manufactured by Toray Industries, Inc.], 50 parts of PVC [Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.] [Table -
The mixture containing the heat stabilizer shown in 1) was kneaded for 5 minutes using an 8-inch test roll adjusted to 155°C to produce a sheet with a thickness of 0.5 mm. Thereafter, in the same manner as in Example 1, the sheet was sandwiched with glass and placed in a gear oven at 220°C to conduct a thermal stability test. The results are shown in Table 2. The degree of coloration indicates the color tone after 30 minutes.

【table】

【table】

[Table] Example 3 50 parts of ABS [TOYORATSUKU 100 manufactured by Toray Industries, Inc.], 50 parts of PVC [Geon 103EP-8 manufactured by Nippon Zeon Co., Ltd.] [Table -
The mixture containing the heat stabilizer shown in item 3) was kneaded for 5 minutes using an 8-inch test roll adjusted to 155°C to produce a sheet with a thickness of 0.5 mm. Thereafter, in the same manner as in Example 1, the sheet was sandwiched with glass and placed in a gear oven at 220°C to conduct a thermal stability test. The results are shown in Table 3, and the degree of coloration indicates the color tone after 40 minutes.

【table】

【table】

Claims (1)

[Claims] 1. When stabilizing a blend polymer consisting of an acrylonitrile-butadiene-styrene copolymer resin and a vinyl chloride resin in a weight ratio of 6:4 to 4:6, (a) general formula and/or general formula [In the formula, R ¹ represents an alkyl group or an alkoxycarbonylalkyl group. Y is R ¹ or Z ¹ . ^Z1 represents ^a -S( _CH2 ) _PCOOR2 group, ^R2 represents an alkyl group or an alkoxyalkyl group, and p is an integer of 1 or 2. Z ² represents a sulfur atom or -S(CH ₂ ) _r COO- group, r is 1 or 2
l is an integer of 1 or 2, and n is an integer of 1 to 10. ] and (b) a maleate salt and/or a maleic acid monomer of a metal selected from the group consisting of Li, Na, K, Mg, Ca, Zn, Sr, Ba, and Sn. A method for stabilizing a blend polymer characterized by adding an ester salt in combination.