TW201708347A - Modified polymer material and composite stabilizer composition having good color stability and process stability in the processing and forming process - Google Patents

Abstract

A modified polymeric material comprising a polymer base material selected from the group consisting of an olefin-based polymer, an ethylene/vinyl acetate copolymer or a combination thereof, and a composite stabilizer composition, wherein the composite stabilizer composition comprises a phosphorus-containing organic antioxidant selected from at least one of chemical formula 1 to chemical formula 8 and a sulfur-containing carboxylate selected from at least one of chemical formula 9 to chemical formula 12. By using the composite stabilizer composition, the modified polymer material has good color stability and process stability in the processing and forming process.

Description

Modified polymer material and composite stabilizer composition

The present invention relates to a modified polymeric material, and more particularly to a olefinic polymer or ethylene/permeate through a composite stabilizer composition comprising a specific phosphorus-containing organic antioxidant and a sulfur-containing carboxylate compound. A modified polymeric material modified with a vinyl acetate copolymer.

Polymer substrates, such as olefin-based polymers and ethylene/vinyl acetate copolymers, have excellent chemical stability, mechanical strength, electrical insulation, and dimensional stability of products, and are non-toxic and easy to process, and thus are widely used. Application as a variety of products. Although the polymer substrate has the above advantages, the above polymer substrate is easily oxidatively degraded by thermal energy, causing yellowing and a decrease in mechanical properties.

Therefore, in order to prevent oxidative degradation of the above polymer substrate, an antioxidant may be added in the processing to reduce the oxidative degradation of the polymer substrate to enhance the mechanical properties and heat resistance of the polymer substrate; however, the antioxidant It may itself cause a decrease in color and processing stability of the polymer substrate. In addition, an antacid is usually added to the processing process to suppress the degradation of the polymer substrate caused by the acidic substance. However, when the type or amount of the antacid is large, the polymer substrate is also caused. Color and processing stability are reduced.

Accordingly, it is a first object of the present invention to provide a modified polymeric material which maintains better color stability and processing stability during the forming process.

Thus, the modified polymeric material of the present invention comprises: a polymeric substrate selected from the group consisting of olefin based polymers, ethylene/vinyl acetate copolymers or combinations thereof; and a composite stabilizer composition, including : a phosphorus-containing organic antioxidant selected from at least one of Chemical Formula 1 to Chemical Formula 8, and a sulfur-containing carboxylate selected from at least one of Chemical Formula 9 to Chemical Formula 12, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] In Chemical Formula 1 to Chemical Formula 7, R ¹¹ to R ¹³ , R ²¹ to R ²⁶ , R ³¹ to R ³⁵ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁶ , R ⁶¹ to R ⁶⁴ , and R ⁷¹ to R ⁷⁸ Each independently represents hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; T represents a C ₁ to C ₁₈ hydrocarbon group or R ⁶⁵ to R ⁶⁷ each independently represent hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; and Z ⁴¹ , Z ⁴² , Z ⁵¹ and Z ⁶¹ each independently represent O, S. Or C ₁ to C ₄ alkyl group, in Chemical Formula 9, M ^{q +} represents Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Zn ²⁺ or Al ³⁺ , q represents 2 or 3, and t represents 0 to 6 An integer of R ⁹¹ represents hydrogen or C ₁ to C ₁₈ alkyl, and R ⁹² represents a C ₁ to C ₃₀ alkyl group, a C ₆ to C ₁₈ arene group or Wherein R ⁹³ 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, and in Chemical Formula 10, X ¹¹ and X ¹² each independently represent Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , Y ¹¹ and Y ¹² each independently represent a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ arene group, and a and b each independently represent 1 to 6, in the formula 11, p An integer representing from 1 to 9, X ²¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , and G ¹ and G ² are each independently represented Wherein c and d each independently represent 1 to 6, and when p ≥ 2, a plurality of G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different, and in Chemical Formula 12, X ³¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , 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 ⁹³ 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, a second object of the present invention is to provide a composite stabilizer composition for modifying the above polymeric substrate.

The composite stabilizer composition of the present invention comprises: a phosphorus-containing organic antioxidant selected from at least one of Chemical Formula 1 to Chemical Formula 8, and a sulfur-containing compound selected from at least one of Chemical Formula 9 to Chemical Formula 12 Carboxylate. Among them, the chemical formulas 1 to 12 are as described above, and therefore will not be described again.

The effect of the present invention is to make the modified polymer material in a processing process by adding the composite stabilizer composition containing a specific phosphorus-containing organic antioxidant and a sulfur-containing carboxylate to the polymer substrate. It maintains good color stability and processing stability, and then produces high quality molded products.

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

[Polymer substrate]

The polymer substrate is selected from the group consisting of an olefin polymer, an ethylene/vinyl acetate copolymer, or a combination thereof. Preferably, the olefin-based polymer is selected from the group consisting of polyethylene, polypropylene, or a combination thereof.

[Composite stabilizer composition]

The phosphorus-containing organic antioxidant represented by the chemical formula 1 is, for example but not limited to, tris(2,4-ditert-butylphenyl) phosphite (abbreviated as antioxidant 168) , triphenyl phosphite, tris (4-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite [tris (tris) Nonylphenyl) phosphite], or tris(p-cumylphenyl) phosphite [tris(p-cumylphenyl) phosphite].

The phosphorus-containing organic antioxidant represented by the chemical formula 2 is, for example but not limited to, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (abbreviated as antioxidant 626), 3,9-bis (2, 4-diisopropylphenylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (referred to as antioxidant 9228), diphenyl pentaerythritol II Diphenyl pentaerythritol diphosphite, or 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane {2,4,8,10-tetraoxa-3,9 -diphosphaspiro[5.5]undecane}.

The phosphorus-containing organic antioxidant represented by Chemical Formula 3 is, for example but not limited to: (CAS number 161717-32-4), 2-[2,4-bis(1,1-dimethylethyl)phenoxy]-5,5-dimethyl-1,3,2-di {2-[2,4-bis(1,1-dimethylethyl)phenoxy]-5,5-dimethyl-1,3,2-dioxaphosphorinane}, 2,4-diisopropylphenylbenzene 2,4-dicumylphenyl 2-butyl-2-ethyl-1,3-propanediol phosphite, 2-[2,4-double (1,1-dimethylethyl)phenoxy]-5-butyl-5-ethyl-1,3,2-dioxaphosphine {2-[2,4-bis(1) , 1-dimethylethyl)phenoxy]-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane}.

The phosphorus-containing organic antioxidant represented by Chemical Formula 4 is, for example but not limited to: (CAS number is 1601458-04-1).

The phosphorus-containing organic antioxidant represented by the chemical formula 5 is, for example but not limited to: (CAS number is 205518-79-2).

The phosphorus-containing organic antioxidant represented by Chemical Formula 6 is, for example but not limited to, 2,4,8,10-tetrabutylbutyl-6-[(2-ethylhexyl)oxy]-12H-diphenyl [d, g][1,3,2]dioxaphosphorane (abbreviated as HP-10), 2,2'-thiobis[t-butyl-p-cresol] cyclic monophenylphosphite {2 , 2'-thiobis [6-tert-butyl-p-cresol] cyclic monophenyl phosphite}, 2,2'-extended methyl bis(4,6-di-t-butylphenyl) (2,4-di 2,2'-methylene bis (2,4-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite].

The phosphorus-containing organic antioxidant represented by Chemical Formula 7 is, for example but not limited to, an antioxidant P-EPQ, a phosphonic acid [1,1'-biphenyl]-4,4'-diylbis-tetra[2-(1,1) - dimethylethyl) phenyl] ester {phosphonous acid, [1,1'-biphenyl]-4,4'-diylbis-,tetrakis[2-(1,1-dimethylethyl)phenyl] ester}, phosphonic acid [1,1'-biphenyl]-4,4'-diylbis-triphenyl ester {phosphonous acid, [1,1'-biphenyl]-4,4'-diylbis-, tetraphenyl ester}.

Preferably, R ⁹¹ in the chemical formula 9 represents hydrogen, and R ⁹² represents a C ₁ to C ₁₈ alkyl group, a C ₆ to C ₁₈ aromatic hydrocarbon group or Wherein R ⁹³ represents a C ₁ to C ₁₈ alkyl group, and k represents 1 or 2. The above aromatic hydrocarbon group means an aryl group, a hydrocarbon group-substituted aryl group or an aryl group-substituted hydrocarbon group. More preferably, R ⁹² in the chemical formula 9 represents a dodecyl group or . The sulfur-containing carboxylate represented by Chemical Formula 9 is, for example but not limited to, zinc 2-dodecylthioacetate, calcium 2-dodecylthioacetate, zinc 3-dodecylthiopropionate, Calcium 3-dodecylthiopropionate or aluminum trioctadecylthiopropionate.

Preferably, in the chemical formula 10, X ¹¹ and X ¹² each independently represent Ca or Zn, and Y ¹¹ and Y ¹² each independently represent -C ₇ H ₁₅ or -C ₁₇ H ₃₅ . The sulfur-containing carboxylate represented by the chemical formula 10 is, for example but not limited to: , or .

Preferably, in the chemical formula 11, X ²¹ represents Ca or Zn, and G ¹ and G ² are each independently represented. Wherein c and d each independently represent 1 or 2. The sulfur-containing carboxylate represented by the chemical formula 11 is, for example but not limited to: or Wherein p represents an integer from 1 to 9.

The sulfur-containing carboxylate represented by Chemical Formula 12 is, for example but not limited to: or .

The ratio of the phosphorus-containing organic antioxidant to the sulfur-containing carboxylate ranges from 1..99 to 99..1.

[modified polymer material]

Preferably, the content of the composite stabilizer composition is from 0.01 to 2.2 parts by weight based on 100 parts by weight of the polymer substrate.

The method for preparing the modified polymer material is not particularly limited, and is, for example, but not limited to, mixing the polymer substrate with the composite stabilizer composition.

The processing method of the modified polymer material is not particularly limited, and may be processed by a general processing method of an olefin polymer or an ethylene/vinyl acetate copolymer depending on the subsequent product requirements. The method of forming is, for example, but not limited to, extrusion molding, injection molding, and the like.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

[Experimental Drugs] 1. Polypropylene: purchased from Taihua Company, the product name is B8001, and Table 1 and Table 2 are referred to as PP. 2. Polyethylene: purchased from Formosa Plastics Co., Ltd., the product name is LL120, and referred to as PE in Table 1 and Table 2. 3. Tris(2,4-di-t-butyl) phosphite: the phosphorus-containing organic antioxidant represented by Chemical Formula 1, referred to as antioxidant 168, referred to as A1 in Table 1 and Table 2. 4. Bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite: the phosphorus-containing organic antioxidant represented by Chemical Formula 2, referred to as antioxidant 626, and A2 in Table 1 and Table 2. 5. 3,9-Bis(2,4-diisopropylphenylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane: The phosphorus-containing organic antioxidant represented by Chemical Formula 2, abbreviated as Antioxidant 9228, is referred to as A3 in Table 1 and Table 2. 6. 2,4,8,10-tetratributyl-6-[(2-ethylhexyl)oxy]-12H-diphenyl[d,g][1,3,2]dioxaphosphorus Ring: is a phosphorus-containing organic antioxidant represented by Chemical Formula 6, referred to as HP-10, and referred to as A4 in Table 1 and Table 2. 7. : a phosphorus-containing organic antioxidant represented by Chemical Formula 7, abbreviated as P-EPQ, and referred to as A5 in Table 1 and Table 2. 8. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: a phosphorus-containing organic antioxidant represented by Chemical Formula 8, abbreviated as DOPO, and abbreviated as A6 in Table 1 and Table 2. 9. : the phosphorus-containing organic antioxidant represented by Chemical Formula 3, the CAS number is 161717-32-4, and the abbreviation A7 in Table 1 and Table 2. 10. : the phosphorus-containing organic antioxidant represented by Chemical Formula 5, the CAS number is 205518-79-2, and the abbreviation A8 in Table 1 and Table 2. 11. : the phosphorus-containing organic antioxidant represented by Chemical Formula 4, the CAS number is 1601458-04-1, and the abbreviation A9 in Table 1 and Table 2. 12. [C ₁₂ H ₂₅ ─S—CH ₂ CH ₂ COO] ₂ Ca: a sulfur-containing carboxylate represented by Chemical Formula 9, and referred to as B1 in Table 1 and Table 2. 13. [C ₁₂ H ₂₅ ─ S-CH ₂ CH ₂ COO] ₃ Al: a sulfur-containing carboxylate represented by Chemical Formula 9, and abbreviated as B2 in Table 1 and Table 2. 14. : a sulfur-containing carboxylate represented by Chemical Formula 10, referred to as B3 in Table 1 and Table 2; : the sulfur-containing carboxylate represented by Chemical Formula 11, and referred to as B4 in Table 1 and Table 2. 16. : a sulfur-containing carboxylate represented by Chemical Formula 12, and abbreviated as B5 in Table 1 and Table 2. 17. Dioctadecyl thiodipropionate: English name is disteaxyl thiodipropionate, hereinafter referred to as DSTDP.

<Examples 1 to 18> Modified polymer materials

According to the composition and ratio (parts by weight) shown in Table 1, 100 parts by weight of polypropylene or 100 parts by weight of polyethylene and the composite stabilizer composition were uniformly mixed at 25 ° C to obtain the solutions of Examples 1 to 18, respectively. Modified polymeric materials E1' to E18'.

<Comparative Examples 1 to 21> Modified Polymer Materials

According to the composition and ratio (parts by weight) shown in Table 2, 100 parts by weight of polypropylene or 100 parts by weight of polyethylene and the stabilizer composition were uniformly mixed at 25 ° C to obtain modified versions of Comparative Examples 1 to 21, respectively. Polymer materials CE1' to CE21'.

[evaluation test]

The above-mentioned modified polymer materials E1' to E18' and CE1' to CE21' were respectively mixed and extruded by a twin-screw extruder (Taiwan Hongsheng Machinery Co., Ltd. PSM20A) (temperature setting was 190 to 230 ° C, and the screw rotation speed was Samples E1 to E18 and CE1 to CE21 were prepared by cooling, air drying, pelletizing, and drying at 200 rpm and feeding speed of 6 rpm. Samples E1 to E18 and CE1 to CE21 were respectively subjected to the above-described steps of extrusion, cooling, air drying, pelletizing, and drying to evaluate the change in yellowness and melt index of the sample after a plurality of processing steps, and the change in yellowness was observed. Smaller represents the better color stability of the modified polymer material in the processing process, and the smaller the change of the melt index, the better the processing stability of the modified polymer material in the processing process.

1. Yellow color difference (Δb* value)

The color difference (Δb* value) of the samples E1 to E18 and CE1 to CE21 after the 3rd and 5th extrusions was compared with the first extrusion using the colorimeter (ColorQuest XE of HunterLab). Tables 3 and 4 show.

2. Melting index (MI) change (ΔMI)

The melt index change ΔMI of the samples E1 to E18 and CE1 to CE21 after the third and fifth extrusions compared to the first extrusion was measured using a laboratory melt indexer (Dynisco's Laboratory Melt Indexer LMI D4004). = The results are shown in Tables 3 and 4.

Table 1

Table 2 Note: In Table 1 and Table 2, “–” means no addition.

table 3

Table 4

It can be seen from Tables 3 and 4 that the samples E1 to E18 prepared in Examples 1 to 18 have a Δb* value of 2.66 or less after the third extrusion, and a Δb* value of 5.04 or less after the fifth extrusion. However, in the samples CE1 to CE21 prepared in Comparative Examples 1 to 21, the Δb* value after the third extrusion was 3.12 or more, and the Δb* value after the fifth extrusion was 6.12 or more, which was shown to be compared with Comparative Example 1 to 21 using a stabilizer composition, the modified polymer materials of Examples 1 to 18 pass through the use of the composite stabilizer composition, so that the modified polymer material has better color stability, thereby making the obtained The sample has a lower yellow color difference (Δb* value) and the yellowing is less pronounced.

According to the change of the melt index (ΔMI), the samples E1 to E18 prepared in Examples 1 to 18 had a ΔMI of 161.58% or less after the third extrusion, and a ΔMI of 55.88% below the fifth extrusion; From the samples CE1 to CE21 prepared in Comparative Examples 1 to 21, the ΔMI after the third extrusion was 175.79% or more, and the ΔMI after the fifth extrusion was 314.11% or more, indicating that the stabilizer was used as compared with Comparative Examples 1 to 21. The composition, the modified polymer materials of Examples 1 to 18 are used to pass the composite stabilizer composition, so that the modified polymer material has better processing stability (physical properties), thereby making the obtained The sample has a lower melt index change ([Delta]MI).

In summary, the present invention allows the modified polymeric material to be added by adding a specific stabilizer composition containing a specific phosphorus-containing organic antioxidant and the sulfur-containing carboxylate to the polymer substrate. The color stability and processing stability can be maintained during the 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 (6)

A modified polymeric material comprising: a polymeric substrate selected from the group consisting of an olefinic polymer, an ethylene/vinyl acetate copolymer, or a combination thereof; and a composite stabilizer composition comprising: a phosphorus-containing organic antioxidant selected from at least one of Chemical Formula 1 to Chemical Formula 8, and a sulfur-containing carboxylate selected from at least one of Chemical Formula 9 to Chemical Formula 12, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] In Chemical Formula 1 to Chemical Formula 7, R ¹¹ to R ¹³ , R ²¹ to R ²⁶ , R ³¹ to R ³⁵ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁶ , R ⁶¹ to R ⁶⁴ , and R ⁷¹ to R ⁷⁸ Each independently represents hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; T represents a C ₁ to C ₁₈ hydrocarbon group or R ⁶⁵ to R ⁶⁷ each independently represent hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; and Z ⁴¹ , Z ⁴² , Z ⁵¹ and Z ⁶¹ each independently represent O, S. Or C ₁ to C ₄ alkyl group, in Chemical Formula 9, M ^{q +} represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ or Al ³⁺ , q represents 2 or 3, and t represents 0 to 6 An integer of R ⁹¹ represents hydrogen or C ₁ to C ₁₈ alkyl, and R ⁹² represents a C ₁ to C ₃₀ alkyl group, a C ₆ to C ₁₈ arene group or Wherein R ⁹³ 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, and in Chemical Formula 10, X ¹¹ and X ¹² each independently represent Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , Y ¹¹ and Y ¹² 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, in Chemical Formula 11 , p represents an integer from 1 to 9, and X ²¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , and G ¹ and G ² are each independently represented Wherein c and d each independently represent an integer from 1 to 6, and when p ≥ 2, a plurality of G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different, and in Chemical Formula 12, X ³¹ Representing Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , 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 ⁹³ 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 polymer material according to claim 1, wherein the content of the composite stabilizer composition is from 0.01 to 2.2 parts by weight based on 100 parts by weight of the polymer substrate. The modified polymeric material of claim 1, wherein the olefinic polymer is selected from the group consisting of polyethylene, polypropylene, or a combination thereof. A composite stabilizer composition comprising: a phosphorus-containing organic antioxidant selected from at least one of Chemical Formula 1 to Chemical Formula 8; and a sulfur-containing carboxylate selected from at least one of Chemical Formula 9 to Chemical Formula 12 [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] In Chemical Formula 1 to Chemical Formula 7, R ¹¹ to R ¹³ , R ²¹ to R ²⁶ , R ³¹ to R ³⁵ , R ⁴¹ to R ⁴⁸ , R ⁵¹ to R ⁵⁶ , R ⁶¹ to R ⁶⁴ , and R ⁷¹ to R ⁷⁸ Each independently represents hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; T represents a C ₁ to C ₁₈ hydrocarbon group or R ⁶⁵ to R ⁶⁷ each independently represent hydrogen, a third butyl group, a cumyl group or a C ₁ to C ₈ linear alkyl group; and Z ⁴¹ , Z ⁴² , Z ⁵¹ and Z ⁶¹ each independently represent O, S. Or C ₁ to C ₄ alkyl; In Chemical Formula 9, M ^{q +} represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ or Al ³⁺ , q represents 2 or 3, and t represents 0 to 6 An integer of R ⁹¹ represents hydrogen or C ₁ to C ₁₈ alkyl, and R ⁹² represents a C ₁ to C ₃₀ alkyl group, a C ₆ to C ₁₈ arene group or Wherein R ⁹³ 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; in Chemical Formula 10, X ¹¹ and X ¹² each independently represent Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , Y ¹¹ and Y ¹² each independently represent a C ₁ to C ₃₀ alkyl group or a C ₆ to C ₁₈ arene group, and a and b each independently represent an integer of 1 to 6; , p represents an integer from 1 to 9, and X ²¹ represents Ca ²⁺ , Ba ²⁺ , Mg ²⁺ or Zn ²⁺ , and G ¹ and G ² are each independently represented Wherein c and d each independently represent an integer from 1 to 6, and when p ≥ 2, a plurality of G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different; in Chemical Formula 12, X ³¹ Representing Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , 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 ⁹³ 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 composite stabilizer composition according to claim 4, wherein R ⁹¹ in the chemical formula 9 represents hydrogen, and R ⁹² represents a C ₁ to C ₁₈ alkyl group, a C ₆ to C ₁₈ aromatic hydrocarbon group or Wherein R ⁹³ represents a C ₁ to C ₁₈ alkyl group, and k represents 1 or 2. The composite stabilizer composition according to claim 5, wherein R ⁹² in the chemical formula 9 represents a dodecyl group or .