TWI647273B - Modified polymeric material and mixture for preparing polymeric materials - Google Patents

Abstract

A modified polymeric material comprising a copolymer substrate and a composite stabilizer composition. The copolymer substrate comprises an acrylonitrile-butadiene-styrene copolymer. The composite stabilizer composition includes a hindered phenol antioxidant, a secondary antioxidant selected from the group consisting of a phosphorus-containing organic antioxidant, a sulfur-containing organic antioxidant, or a combination thereof, and at least one selected from the group consisting of Chemical Formula 1 to Chemical Formula 3 Sulfur-containing carboxylate. The invention also provides a mixture for preparing a polymeric material comprising acrylonitrile, butadiene, styrene, and a composite stabilizer composition as described above. The modified polymer material retains its impact strength after repeated recovery processes.

Description

Modified polymeric material and mixture for preparing polymeric materials

The present invention relates to a modified polymeric material, and more particularly to a modified polymerization of a composite stabilizer composition comprising a hindered phenolic antioxidant, a secondary antioxidant, and a specific sulfur-containing carboxylate. Materials, and a mixture for preparing polymeric materials.

Acrylonitrile butadiene styrene copolymer (ABS copolymer) has good impact resistance and chemical resistance, excellent electrical properties, and is easy to process, product size is stable, and manufacturing cost is low. It is widely used as a plastic for various household appliances and daily necessities, but ABS is likely to cause a decrease in its mechanical properties under the action of heat energy during recycling.

Accordingly, it is an object of the present invention to overcome the above-discussed shortcomings of the prior art by providing a modified polymeric material.

Thus, the modified polymeric material of the present invention comprises a copolymer substrate and a composite stabilizer composition. The copolymer substrate comprises an acrylonitrile-butadiene-styrene (ABS) copolymer. The composite stabilizer composition includes a hindered phenol antioxidant, a secondary antioxidant selected from the group consisting of a phosphorus-containing organic antioxidant, a sulfur-containing organic antioxidant, or a combination thereof, and at least one selected from the following Chemical Formula 1 to Chemical Formula 3 Sulfur-containing carboxylate. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]

In Chemical Formula 1, M ^q+ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ or Al ³⁺ , q represents 2 or 3, t represents an integer of 0 to 6, and R ¹¹ represents hydrogen or C ₁ to C ₁₈ alkyl, R ¹² represents a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ aromatic hydrocarbon group. In Chemical Formula 2, X ²¹ and X ²² each independently represent Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , and Y ²¹ and Y ²² each independently represent a C ₁ to C ₃₀ alkyl group or a C ₆ to The C ₁₈ arene group, a and b each independently represent an integer of 1 to 6. In Chemical Formula 3, X ³¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , and Y ³¹ represents a C ₁ to C ₃₀ alkyl group, a C ₆ to C ₁₈ aromatic hydrocarbon group or Wherein R ³³ represents a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ aromatic hydrocarbon group, and k represents an integer of 1 to 5.

Accordingly, it is another object of the present invention to provide a mixture for preparing a polymeric material comprising acrylonitrile, butadiene, styrene and a composite stabilizer composition as described above.

The effect of the present invention is that the modified polymeric material retains its impact strength after repeated recovery processes.

The contents of the present invention will be described in detail below:

Preferably, the content of the composite stabilizer composition is from 0.01 to 5.0 parts by weight based on 100 parts by weight of the total weight of the polymer substrate.

In the present invention, the hindered phenolic antioxidant may be, but not limited to, tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol ester (hereinafter referred to as antioxidant 1010). , Triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (abbreviated as antioxidant 245), 1,3,5-trimethyl -2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (abbreviated as antioxidant 1330), 1,3,5-tris(3,5-di-t-butyl -4-hydroxybenzyl)isocyanurate (abbreviated as antioxidant 3114), tris(butylcresolyl)butane (abbreviated as AO-30), 4,4'-butylidene bis(6-tert-butyl- 3-methylphenol) (abbreviated as AO-40), N , N '-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoid] oxime (referred to as antioxidant 1024), N , N '-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]hexanediamine (referred to as antioxidant 1098), 2,2'-methylene double -(4-methyl-6-tert-butylphenol) (abbreviated as antioxidant 2246), and 3,5-di-t-butyl-4-hydroxyphenylpropionic acid isooctyl ester (referred to as antioxidant 1135), 3 -(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester (referred to as antioxidant 1076), tris(4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl)isocyanuric acid (abbreviated as antioxidant 1790), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane [1,1,3-tris(2-methyl-4-hydroxy-5- tert- butylphenyl)butane, abbreviated as AO-30], 1,1-di(2-methyl-4-hydroxy-5-third 1,1-bis(2-methyl-4-hydroxy-5- tert- butylphenyl)butane (AO-40), p-cresol and dicyclopentadiene copolymer (Wingstay L for short) Or WL, CAS number is 68610-51-5), 2,4-dimethyl-6-(1-methylpentadecyl)-phenol [2,4-dimethyl-6-(1-methylpentadecyl)- Phenol], referred to as antioxidant 1141, CAS number 134701-20-5] or a combination thereof.

In the present invention, the phosphorus-containing organic antioxidant is at least one selected from the group consisting of Chemical Formula 4 to Chemical Formula 11 below. [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11]

In Chemical Formula 4 to Chemical Formula 10, R ⁴¹ to R ⁴³ , R ⁵¹ to R ⁵⁶ , R ⁶¹ to R ⁶⁵ , R ⁷¹ to R ⁷⁸ , R ⁸¹ to R ⁸⁶ , R ⁹¹ to R ⁹⁴ , and R ¹⁰¹ to R ¹⁰⁸ Each independently represents hydrogen, a third butyl group, an isopropylphenyl group or a C ₁ to C ₈ linear alkyl group; T represents a C ₁ to C ₁₈ hydrocarbon group or Wherein R ⁹⁵ to R ⁹⁷ each independently represent hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; and Z ⁷¹ , Z ⁷² , Z ⁸¹ and Z ⁹¹ each independently represent O, S, methylene or C ₂ to C ₄ alkyl.

Preferably, the phosphorus-containing organic antioxidant is, but not limited to, 3,9-bis(2,4-diisopropylphenylphenoxy)-2,4,8,10-tetraoxa-3. 9-Diphosphaspiro[5.5]undecane (referred to as antioxidant 9228), tris(2,4-di-t-butyl) phosphite phosphite (hereinafter referred to as antioxidant 168), distearyl pentaerythritol diya Phosphate (abbreviated as antioxidant 618), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (hereinafter referred to as antioxidant 626), 2,4,8,10-tetrabutyl- 6-[(2-Ethyl)oxy]-12 H -diphenyl [ d , g ][1,3,2]dioxaphosphorane (abbreviated as HP-10), 9,10-II Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (referred to as antioxidant 626), double ( 2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphate (referred to as PEP-36), tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenyl Tetrakis (2,4-di- tert- butylphenyl)-4,4'-biphenyldiphosphonite, abbreviated as P-EPQ, CAS number 119345-01-06] or a combination thereof.

In the present invention, the sulfur-containing organic antioxidant is at least one selected from the group consisting of Chemical Formula 12 to Chemical Formula 14 below. [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]

In Chemical Formula 12 to Chemical Formula 15, R ¹²¹ , R ¹³¹ to R ¹³² , R ¹⁴¹ to R ^{144 ,} and R ¹⁵¹ to R ¹⁵⁶ each independently represent a third butyl group, a cumyl group or a C ₆ to C ₁₈ linear alkane. base.

In a specific embodiment of the invention, the sulfur-containing organic antioxidant is S(CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ (hereinafter referred to as DL).

Preferably, the content of the hindered phenolic antioxidant ranges from 0.01 to 2.5 parts by weight based on 100% by weight of the total weight of the polymer substrate, and the content of the phosphorus-containing organic antioxidant or sulfur-containing organic antioxidant is 0.01 to 4.5 parts by weight.

Preferably, the composite stabilizer composition further comprises at least one of a benzofuranone antioxidant, an acrylate antioxidant, and an amine oxide antioxidant.

In the present invention, the benzofuranone-based antioxidant is represented by the following Chemical Formula 16. [Chemical Formula 16]

In Chemical Formula 16, R ¹⁶¹ to R ¹⁶⁴ each independently represent hydrogen, a C ₁ to C ₁₀ linear alkyl group or a branched alkyl group or , wherein R ¹⁶⁵ to R ¹⁶⁹ each independently represent hydrogen, hydroxy, a C ₁ to C ₁₀ linear alkyl group or a branched alkyl group. Wherein R ¹⁶¹¹ to R ¹⁶¹³ each independently represent a hydroxyl group, a C ₁ to C ₁₀ linear alkyl group or a branched alkyl group.

Preferably, the benzofuranone antioxidant is selected from the group consisting of xylyl dibutylbenzofuranone (hereinafter referred to as antioxidant HP-136) and 5-tert-butyl-3-(5). -T-butyl-2-hydroxyphenyl)benzofuran-2-( 3H )-one [5- tert- butyl-3-(5- tert- butyl-2-hydroxyphenyl) benzofuran-2-(3 H )-one, CAS number 214354-68-4], 3-[3,5-bis(1,1-dimethylethyl)-2-hydroxyphenyl]-5,7-bis (1, 1-dimethylethyl)-2(3 H )-benzofuranone {3-[3,5-bis(1,1-dimethylethyl)-2-hydroxyphenyl]- 5,7-bis (1,1 -dimethylethyl)-2( 3H )-benzofuranone, CAS number 210709-72-1} or a combination thereof.

In the present invention, the acrylate antioxidant is as shown in the following Chemical Formula 17. [Chemical Formula 17]

In Chemical Formula 17, R ¹⁷¹ to R ¹⁷⁵ each independently represent a C ₁ to C ₁₀ linear alkyl group or a branched alkyl group.

Preferably, the acrylate antioxidant is selected from the group consisting of 2-(2-hydroxy-3-t-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate Ester [2-(2-hydroxy-3- tert- butyl-5-methylbenzyl)-4-methyl-6- tert- butylphenyl acrylate, referred to as antioxidant GM], 2-{1-[2-hydroxy-3,5 - bis(2-methylbutan-2-yl)phenyl]ethyl}-4,6-bis(2-methylbutan-2-yl)phenyl acrylate {2-[1-(2-hydroxy) -3,5-di- tert- pentylphenyl)ethyl]- 4,6-di- tert- pentylphenyl acrylate, abbreviated as antioxidant GS} or a combination thereof.

In the present invention, the amine oxide-based antioxidant may be, but not limited to, bis(alkyl hydrogenated fat) amine oxide, bis(octadecyl)hydroxylamine (abbreviated as antioxidant FS042), or a combination thereof.

Preferably, the benzofuranone antioxidant is contained in an amount ranging from 0 to 0.5 parts by weight based on 100% by weight of the total of the polymer substrate, and the acrylate antioxidant is contained in an amount ranging from 0 to 0.5% by weight. The content of the amine oxide-based antioxidant is in the range of 0 to 1.0 part by weight.

Preferably, the copolymer substrate further comprises an acrylonitrile-styrene copolymer (AS).

Preferably, the modified polymeric material further comprises at least one of an antacid and a metal passivating agent.

The antacid helps to balance the pH of the modified polymeric material and allows the phosphorus-containing organic antioxidant or sulfur-containing organic antioxidant to be more readily compatible with the sulfur-containing carboxylate. More preferably, the antacid is a fatty acid salt. The fatty acid salt can be, but is not limited to, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, or a combination thereof.

The metal deactivator is capable of preventing degradation of the modified polymeric material. More preferably, the metal deactivator is selected from the group consisting of 1,2-bis[(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene {1,2-di[(3) ,5-di- tert- butyl-4-hydroxyphenyl)propionyl] hydrazide}, 2,2'-oxalyl bis[ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate] {2,2'-oxamido bis[ethyl 3-(3,5-di- tert- butyl-4-hydroxyphenyl) propionate]} or a combination thereof. Specific commercial products of the metal deactivator can be, but are not limited to, MD-1024, Naugard XL-1, Eastman inhibitor OABH.

Preferably, the antacid is present in an amount ranging from 0 to 1.5 parts by weight based on the total weight of the polymer substrate, and the metal deactivator is contained in an amount ranging from 0 to 1.0 part by weight.

Preferably, the mixture for preparing the polymeric material further comprises a dispersing agent which is coated on the periphery of the molecules of the antioxidant to prevent sedimentation of the antioxidant. The dispersant may be an ionic dispersant or a nonionic dispersant. More preferably, the dispersing agent can be, but not limited to, sodium dodecyl sulfate (SDS), disproportionated rosin potassium soap (K-25), polyvinyl alcohol (PVA). , octyl phenol ethoxylated (Panox 8610), octadecyl alcohol, polyalkyl glycol sulfate aqueous solution (2184).

Preferably, the mixture for preparing the polymeric material further comprises water.

Preferably, the mixture for preparing the polymeric material further comprises an anti-settling agent which forms a stent-like structure between the molecules of the antioxidant to prevent the antioxidant from settling.

The preparation method of the modified polymer material of the present invention is not particularly limited, such as, but not limited to, mixing the composite stabilizer composition with an ABS copolymer (post-stage processing method), or adding the composite stabilizer composition. After the reaction in ABS latex solution, coagulation and drying to form modified ABS rubber powder (pre-processing method), and subsequent processing to make modified ABS rubber particles, which can be followed by extrusion molding, injection molding, etc. Processing and forming methods.

The anterior processing method may be an emulsification processing method comprising the steps of: (a) placing the composite stabilizer composition in a reaction tank of a mixer and stirring uniformly; (b) heating to 100-150 ° C until the composite stabilizer After the composition is completely melted, the temperature is lowered to 60-95 ° C, and stirring is continued; (c) the dispersant is slowly added, and stirred at a high speed to uniformly mix; (d) further adding deionized water or anti-settling agent, so that After uniformly mixing, it is cooled to room temperature; (e) the resulting product is screened to remove foreign matter which may be generated during the processing; (f) finally added to the ABS emulsion for polymerization, and then coagulated and dried.

In the present invention, the pre-processing method may be a grinding process comprising the following steps: (a) placing deionized water, a dispersing agent, an antibacterial agent, an anti-settling agent, and an appropriate amount of glass beads in a reaction tank of the mixer and uniformly mixing; (b) further adding the composite stabilizer composition, continuously stirring in a room temperature water bath; (c) filtering the obtained product as a sieve; (d) finally adding it to the ABS latex solution for polymerization, and then coagulation And dry.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

In the chemicals used in the following examples, 1010 represents an antioxidant 1010; 168 represents an antioxidant 168; DL represents S(CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ ; and S1 represents (C ₁₂ H ₂₅ -S-CH ₂ CH ₂ COO) ₂ Ca; S2 represents _{(C 12 H 25 ─S─CH 2 CH} 2 COO) 3 Al; S3 represents ; S4 indicates ; HP-136 represents the antioxidant HP-136.

[ Post processing method]

<Examples 1-8 And comparative examples 1-6 >

According to the composition and proportion (parts by weight) of the composite stabilizer composition shown in Table 1 below, 100 parts by weight of ABS copolymer (purchased from Taihua Company, trade name AG15A1) and the composite stabilizer composition were respectively The mixture was uniformly mixed at ° C to obtain the modified polymer materials E1-E8 and CE1-CE6 of Examples 1-8 and Comparative Examples 1-6, respectively. In Table 1, "–" means not added. 【Table 1】  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Hindered Phenolic Antioxidants</td><td> Phosphorus Organic antioxidants or sulfur-containing organic antioxidants</td><td> sulfur-containing carboxylates</td><td> benzofuranone antioxidants</td></tr><tr><td> WL </td><td> 1010 </td><td> 168 </td><td> DL </td><td> S1 </td><td> S2 </td><td> S3 </ Td><td> S4 </td><td> HP-136 </td></tr><tr><td> Example 1 </td><td> 0.1 </td><td> – < /td><td> 0.1 </td><td> – </td><td> 0.04 </td><td> – </td><td> – </td><td> – </td ><td> – </td></tr><tr><td> Example 2 </td><td> – </td><td> 0.1 </td><td> 0.1 </td> <td> – </td><td> 0.04 </td><td> – </td><td> – </td><td> – </td><td> – </td></ Tr><tr><td> Example 3 </td><td> 0.1 </td><td> – </td><td> 0.1 </td><td> – </td><td> 0.03 </td><td> – </td><td> – </td><td> – </td><td> 0.01 </td></tr><tr><td> Example 4 </td><td> – </td><td> 0.1 </td><td> 0.1 </td><td> – </td><td> – </td><td> 0.04 </ Td><td> – </td><td> – </td><td> – </td ></tr><tr><td> Example 5 </td><td> – </td><td> 0.1 </td><td> – </td><td> 0.1 </td> <td> – </td><td> – </td><td> 0.04 </td><td> – </td><td> – </td></tr><tr><td> Example 6 </td><td> – </td><td> 0.1 </td><td> – </td><td> 0.1 </td><td> – </td><td> – </td><td> – </td><td> 0.04 </td><td> – </td></tr><tr><td> Example 7 </td><td> 0.005 </td><td> – </td><td> – </td><td> 0.01 </td><td> 0.001 </td><td> – </td><td> – </ Td><td> – </td><td> – </td></tr><tr><td> Example 8 </td><td> – </td><td> 0.6 </td ><td> 0.3 </td><td> – </td><td> 0.1 </td><td> – </td><td> – </td><td> – </td>< Td> – </td></tr><tr><td> Comparative Example 1 </td><td> 0.12 </td><td> – </td><td> 0.12 </td><td > – </td><td> – </td><td> – </td><td> – </td><td> – </td><td> – </td></tr> <tr><td> Comparative Example 2 </td><td> – </td><td> 0.12 </td><td> 0.12 </td><td> – </td><td> – < /td><td> – </td><td> – </td><td> – </td><td> – </td></tr><tr><td> Comparative Example 3 </ Td><td> 0.12 </td><td> </td><td> 0.11 </td><td> – </td><td> – </td><td> – </td><td> – </td><td> – </ Td><td> 0.01 </td></tr><tr><td> Comparative Example 4 </td><td> – </td><td> 0.2 </td><td> – </td ><td> – </td><td> 0.04 </td><td> – </td><td> – </td><td> – </td><td> – </td>< /tr><tr><td> Comparative Example 5 </td><td> – </td><td> – </td><td> 0.2 </td><td> – </td><td > 0.04 </td><td> – </td><td> – </td><td> – </td><td> – </td></tr><tr><td> Comparative Example 6 </td><td> – </td><td> – </td><td> – </td><td> 0.2 </td><td> – </td><td> 0.04 < /td><td> – </td><td> – </td><td> – </td></tr></TBODY></TABLE>

[ Front processing method - Grinding method]

<Example 9-10 And Comparative Example 7-8 >

58 g of deionized water, 2 g of sodium dodecyl sulfate (SDS, dispersant), 0.1 g of antibacterial agent and appropriate amount of glass beads were respectively added to a 1 L mixer reaction tank, and then stirred at a high speed to uniformly mix. Further, they were mixed and prepared according to the composition and weight of the composite stabilizer as shown in the following Table 2, and then added to the reaction vessel, and stirring was continued for 24 hours in a room temperature water bath. The obtained product was sieved through a glass bead to obtain a uniformly dispersed polishing liquid of Examples 9-10 and Comparative Examples 7-8, respectively. In Table 2, "–" means not added. 【Table 2】  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Hindered Phenolic Antioxidants (g) </td><td > Sulfur-containing organic antioxidants (g) </td><td> Sulfur-containing carboxylates (g) </td></tr><tr><td> WL </td><td> 1010 </td ><td> DL </td><td> S1 </td><td> S2 </td></tr><tr><td> Example 9 </td><td> 17 </td> <td> – </td><td> 17 </td><td> 6 </td><td> – </td></tr><tr><td> Example 10 </td>< Td> – </td><td> 17 </td><td> 17 </td><td> – </td><td> 6 </td></tr><tr><td> Compare Example 7 </td><td> 20 </td><td> – </td><td> 20 </td><td> – </td><td> – </td></tr> <tr><td> Comparative Example 8 </td><td> – </td><td> 20 </td><td> 20 </td><td> – </td><td> – < /td></tr></TBODY></TABLE>

0.5 parts by weight of the polishing liquids of the above Examples 9-10 and Comparative Examples 7-8 were respectively added to 100 parts by weight of ABS latex liquid (composed of acrylonitrile, butadiene and styrene, acrylonitrile: butadiene: styrene) = 20 wt%: 50 wt%: 30 wt%, solid content of 40 wt%) Stirring uniformly. Further, 0.4 parts by weight of concentrated sulfuric acid was added to 2000 parts by weight of deionized water as a coagulant solution, and the temperature was raised to 90 ° C, and then the above-mentioned slurry containing ABS latex liquid was slowly dropped into the coagulant solution under rapid stirring. And maintaining the temperature at 90 ° C, after complete addition, the temperature was raised to 95 ° C and held for 15 minutes, filtered while hot, and washed with 2000 parts by weight of deionized water, and the obtained powder was dried in an oven at 60 ° C for 20 hours, respectively Modified ABS rubber powders of Examples 9-10 and Comparative Examples 7-8 were obtained.

The acrylonitrile-styrene copolymer (purchased from Chi Mei Industrial, trade name AS127) and the modified ABS rubber powder of the above Examples 9-10 and Comparative Examples 7-8 and calcium stearate were respectively 7:3:0.02. The weight ratios were mixed to obtain the modified polymer materials E9-E10 and CE7-CE8 of Examples 9-10 and Comparative Examples 7-8, respectively.

[ABS Test piece preparation]

The modified polymer materials E1-E10 and CE1-CE8 of the above Examples 1-10 and Comparative Examples 1-8 were respectively mixed and extruded by a twin-screw extruder (Taiwan Hongsheng Machinery Co., Ltd. test machine PSM20A) (the temperature was set to 190 to 230 ° C, screw rotation speed of 200 rev / min, feed rate of 6 rev / min), and then cooled, air dried, pelletized, dried to obtain modified ABS colloidal particles.

After the above-mentioned modified ABS colloidal particles were sufficiently dried, they were respectively ejected at 210 ° C by a vertical injection machine to obtain ABS test pieces having a size of 64 mm (length) × 12.7 mm (thickness) × 6.4 mm (width), and Leave for 24 hours.

[ Izod impact strength test]

According to ASTM D256, the ABS test piece is tested for impact strength. The thickness of the ABS test piece is about 10.2 mm below the notch and the notched impact strength test is carried out at 23 ° C. The impact tester model is GOTECH-GT-7045-HML. The size of the chamfering machine is GOTECH-7016-A3), and the above-mentioned modified ABS colloidal particles are repeatedly subjected to the above-mentioned heating, extrusion, cooling, air drying, pelletizing, drying processing steps, and then the ABS test piece is ejected. For each of the examples and the comparative examples, three test pieces were tested, and the average results are shown in Table 3 below. 【table 3】  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Repeat processing times</td><td> 0 </td><td> 2 </ Td><td> 4 </td><td> 6 </td><td> 8 </td><td> 10 </td></tr><tr><td> </td><td > Izod impact strength (kg-cm/cm) </td></tr><tr><td> Example 1 </td><td> 20 </td><td> 20 </td>< Td> 20 </td><td> 19.94 </td><td> 19.7 </td><td> 19.14 </td></tr><tr><td> Example 2 </td><td > 20 </td><td> 20 </td><td> 20 </td><td> 19.98 </td><td> 19.84 </td><td> 19.26 </td></tr> <tr><td> Example 3 </td><td> 20 </td><td> 20 </td><td> 19.96 </td><td> 19.96 </td><td> 19.62 < /td><td> 19.02 </td></tr><tr><td> Example 4 </td><td> 20 </td><td> 20 </td><td> 19.94 </ Td><td> 19.96 </td><td> 19.46 </td><td> 19.2 </td></tr><tr><td> Example 5 </td><td> 20 </td ><td> 20 </td><td> 19.72 </td><td> 19.48 </td><td> 19.3 </td><td> 18.56 </td></tr><tr><td > Example 6 </td><td> 20 </td><td> 19.92 </td><td> 19.82 </td><td> 19.78 </td><td> 19.5 </td><td > 18.62 </td></tr><tr><td> Example 7 </td><td> 20 </td><td> 19.82 </td><t d> 19.76 </td><td> 19.44 </td><td> 19.24 </td><td> 18.34 </td></tr><tr><td> Example 8 </td><td > 20 </td><td> 20 </td><td> 20 </td><td> 19.98 </td><td> 19.88 </td><td> 19.72 </td></tr> <tr><td> Example 9 </td><td> 22 </td><td> 22 </td><td> 21.98 </td><td> 21.96 </td><td> 21.96 < /td><td> 21.36 </td></tr><tr><td> Example 10 </td><td> 22 </td><td> 22 </td><td> 21.98 </ Td><td> 21.91 </td><td> 21.58 </td><td> 20.98 </td></tr><tr><td> Comparative Example 1 </td><td> 20 </td ><td> 19.02 </td><td> 18.72 </td><td> 17.58 </td><td> 16.54 </td><td> 16.06 </td></tr><tr><td > Comparative Example 2 </td><td> 20 </td><td> 19.74 </td><td> 19.12 </td><td> 17.94 </td><td> 17.3 </td><td > 16.62 </td></tr><tr><td> Comparative Example 3 </td><td> 20 </td><td> 19.5 </td><td> 18.84 </td><td> 17.72 </td><td> 16.74 </td><td> 16.42 </td></tr><tr><td> Comparative Example 4 </td><td> 20 </td><td> 19.16 </td><td> 18.54 </td><td> 17.44 </td><td> 17.24 </td><td> 16.08 </td></tr><tr><td> Comparative Example 5 < /td><td> 20 </td><td> 19.42 </td><td> 19.22 </td><td> 17.78 </td ><td> 17.18 </td><td> 16.48 </td></tr><tr><td> Comparative Example 6 </td><td> 20 </td><td> 19.3 </td> <td> 18.86 </td><td> 17.34 </td><td> 17.08 </td><td> 16.12 </td></tr><tr><td> Comparative Example 7 </td>< Td> 22 </td><td> 21.16 </td><td> 20.66 </td><td> 19.09 </td><td> 18.06 </td><td> 17.8 </td></tr ><tr><td> Comparative Example 8 </td><td> 22 </td><td> 21.63 </td><td> 20.85 </td><td> 19.29 </td><td> 19.12 </td><td> 18.51 </td></tr></TBODY></TABLE>

It can be clearly seen from the above Table 3 that the ABS test pieces of Examples 1-10 can maintain the impact strength of 91.7-98.6% after 10 repeated processing steps (compared to the non-repeating process), and most of them can be The ABS test piece of Comparative Example 1-8 maintained only 80.3-84.1% of impact strength after 10 repeated processing steps, and most of them were only 82.4% or less.

In summary, the modified polymer material of the present invention can maintain its impact strength after repeated recovery processing, so that the object of the present invention can be achieved.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.

Claims (10)

A modified polymeric material comprising: a copolymer substrate comprising an acrylonitrile-butadiene-styrene copolymer; and a composite stabilizer composition comprising: a hindered phenolic antioxidant selected from the group consisting of a secondary antioxidant containing a phosphorus-containing organic antioxidant, a sulfur-containing organic antioxidant, or a combination thereof, and a sulfur-containing carboxylate selected from at least one of Chemical Formula 1 to Chemical Formula 3 below, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In Chemical Formula 1, M ^q+ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ or Al ³⁺ , q represents 2 or 3, t represents an integer of 0 to 6, and R ¹¹ represents hydrogen or C ₁ to C ₁₈ alkyl, R ¹² represents a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ aromatic hydrocarbon group, and in Chemical Formula 2, X ²¹ and X ²² each independently represent Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , Y ²¹ and Y ²² each independently represent a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ aromatic hydrocarbon group, and a and b each independently represent an integer of 1 to 6, and in Chemical Formula 3, X ³¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , Y ³¹ represents a C ₁ to C ₃₀ alkyl group, a C ₆ to C ₁₈ aromatic hydrocarbon group or Wherein R ³³ represents a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ aromatic hydrocarbon group, and k represents an integer of 1 to 5. The modified polymeric material of claim 1 wherein the copolymer substrate further comprises an acrylonitrile-styrene copolymer. The modified polymer material according to claim 1, wherein the composite stabilizer composition further comprises at least one of a benzofuranone antioxidant, an acrylate antioxidant, and an amine oxide antioxidant. The modified polymeric material of claim 3, wherein the benzofuranone antioxidant is selected from the group consisting of xylylene dibutyl benzofuranone, 5-tert-butyl-3- ( 5-t-butyl-2-hydroxyphenyl)benzofuran-2-(3 H )-one, 3-[3,5-bis(1,1-dimethylethyl)-2-hydroxybenzene 5-[7,7-bis(1,1-dimethylethyl)-2( 3H )-benzofuranone or a combination thereof. The modified polymeric material of claim 3, wherein the acrylate antioxidant is selected from the group consisting of 2-(2-hydroxy-3-t-butyl-5-methylbenzyl)-4 -methyl-6-t-butylphenyl acrylate, 2-{1-[2-hydroxy-3,5-di(2-methylbutan-2-yl)phenyl]ethyl}-4, 6-bis(2-methylbutan-2-yl)phenyl acrylate or a combination thereof. A mixture for preparing a polymer material, comprising: acrylonitrile; butadiene; styrene; and a composite stabilizer composition, comprising: a hindered phenolic antioxidant selected from the group consisting of phosphorus-containing organic antioxidants, sulfur-containing a secondary antioxidant of an organic antioxidant or a combination thereof, and a sulfur-containing carboxylate selected from at least one of Chemical Formula 1 to Chemical Formula 3 below, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In Chemical Formula 1 to Chemical Formula 3, M ^q+ , q, t, R ¹¹ , R ¹² , X ²¹ , X ²² , Y ²¹ , Y ²² , a, b, X ³¹ and Y ³¹ are as defined in Claim 1 . A mixture for preparing a polymer material as described in claim 6 further comprising a dispersing agent. The mixture for preparing a polymer material according to claim 7, wherein the dispersing agent is sodium lauryl sulfate. The mixture for preparing a polymeric material according to claim 6 further comprising water. The mixture for preparing a polymeric material according to claim 6 further comprising an anti-settling agent.