CN115335447B - 成核剂、树脂组合物、树脂组合物的制造方法和成形品 - Google Patents
成核剂、树脂组合物、树脂组合物的制造方法和成形品 Download PDFInfo
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- CN115335447B CN115335447B CN202180024124.1A CN202180024124A CN115335447B CN 115335447 B CN115335447 B CN 115335447B CN 202180024124 A CN202180024124 A CN 202180024124A CN 115335447 B CN115335447 B CN 115335447B
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- metal salt
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- nucleating agent
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 107
- 239000002184 metal Substances 0.000 claims abstract description 107
- 150000003839 salts Chemical class 0.000 claims abstract description 102
- -1 aromatic phosphoric acid ester Chemical class 0.000 claims abstract description 96
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- HDVDLQFPDLTOSI-UHFFFAOYSA-L O[AlH]O Chemical compound O[AlH]O HDVDLQFPDLTOSI-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920005672 polyolefin resin Polymers 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
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- 235000014113 dietary fatty acids Nutrition 0.000 description 25
- 239000000194 fatty acid Substances 0.000 description 25
- 229930195729 fatty acid Natural products 0.000 description 25
- 150000004665 fatty acids Chemical class 0.000 description 21
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- 235000021317 phosphate Nutrition 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 239000010452 phosphate Substances 0.000 description 14
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- 150000001875 compounds Chemical class 0.000 description 8
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 8
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 5
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- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
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- 229910052744 lithium Inorganic materials 0.000 description 4
- KJSPVJJOPONRTK-UHFFFAOYSA-M lithium;tetradecanoate Chemical compound [Li+].CCCCCCCCCCCCCC([O-])=O KJSPVJJOPONRTK-UHFFFAOYSA-M 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
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- DTOSIQBPPRVQHS-PDBXOOCHSA-M linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O DTOSIQBPPRVQHS-PDBXOOCHSA-M 0.000 description 2
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
本发明提供能够对成形品赋予优异力学特性的成核剂、树脂组合物、树脂组合物的制造方法和成形品。一种成核剂,其包含(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐和(B)具有下述通式(2)所示结构的羧酸金属盐。(式(1)中,R1~R5各自独立地表示氢原子或烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝。)(式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2。Z表示具有式(3)或(4)所示结构的基团。)
Description
技术领域
本发明涉及成核剂、树脂组合物、树脂组合物的制造方法(以下也简称为“制造方法”)和成形品,详细而言,涉及能够对成形品赋予优异力学特性的成核剂、树脂组合物、树脂组合物的制造方法和成形品。
背景技术
在各种热塑性通用树脂之中,从物性、成形加工性、价格等观点出发,聚烯烃系树脂作为应用领域最广的塑料材料之一而被用于广泛的用途。
有时对由聚烯烃系树脂形成的成形品要求优异的刚性。作为对由聚烯烃系树脂形成的成形品赋予优异刚性的方法之一,已知的是向聚烯烃系树脂中添加成核剂的方法。作为向聚烯烃系树脂中添加的成核剂,例如,下述专利文献1中提出了包含芳香族磷酸酯金属盐的成核剂。
现有技术文献
专利文献
专利文献1:日本特开昭58-1736号公报
发明内容
发明要解决的问题
然而,从对成形品赋予充分的力学特性的观点出发,上述专利文献1所述的成核剂尚有进一步改善的余地。
因而,本发明的目的在于,提供能够对成形品赋予优异力学特性的成核剂、树脂组合物、树脂组合物的制造方法和成形品。
用于解决问题的方案
本发明人等进行深入研究的结果发现:根据包含特定的芳香族磷酸酯金属盐和特定的羧酸金属盐的成核剂,能够解决上述课题,从而完成了本发明。
即,本发明的成核剂的特征在于,其包含(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐和(B)具有下述通式(2)所示结构的羧酸金属盐。
(上述通式(1)中,R1~R5各自独立地表示氢原子或碳原子数1~6的烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝。)
(上述通式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2。Z表示具有下述通式(3)或(4)所示结构的基团。)
(上述通式(3)和(4)中,Y表示单键或碳原子数1~4的亚烷基;R6~R15各自独立地表示氢原子、卤素原子或碳原子数1~6的烷基;*表示与羰基碳键合的位置。)
前述通式(2)中的M2优选为钠。
另外,前述(A)芳香族磷酸酯金属盐的含量与前述(B)羧酸金属盐的含量的质量比(A)/(B)优选为1/99~50/50。
进而,前述(A)芳香族磷酸酯金属盐的含量与前述(B)羧酸金属盐的含量的质量比(A)/(B)还优选为50/50~99/1,更优选为50/50~80/20。
本发明的树脂组合物的特征在于,其包含聚烯烃系树脂、(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐、以及(B)具有下述通式(2)所示结构的羧酸金属盐,
前述(A)芳香族磷酸酯金属盐与前述(B)羧酸金属盐的总含量相对于前述聚烯烃系树脂100质量份为0.001~10质量份。
(上述通式(1)中,R1~R5各自独立地表示氢原子或碳原子数1~6的烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝。)
(上述通式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2。Z表示具有下述通式(3)或(4)所示结构的基团。)
(上述通式(3)和(4)中,Y表示单键或碳原子数1~4的亚烷基;R6~R15各自独立地表示氢原子、卤素原子或碳原子数1~6的烷基;*表示与羰基碳键合的位置。)
前述聚烯烃系树脂优选为聚丙烯系树脂。
另外,本发明的树脂组合物的制造方法的特征在于,其具备将上述成核剂配混至聚烯烃系树脂中的配混工序。
进而,本发明的成形品的特征在于,其是将上述树脂组合物进行成形而得到的。
发明的效果
根据本发明,可提供能够对成形品赋予优异力学特性的成核剂、树脂组合物、树脂组合物的制造方法和成形品。
具体实施方式
以下,针对本发明的实施方式进行详细说明。首先,针对本发明的成核剂的实施方式进行说明。
<成核剂>
本实施方式的成核剂包含(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐和(B)具有下述通式(2)所示结构的羧酸金属盐。
此处,通式(1)中,R1~R5各自独立地表示氢原子或碳原子数1~6的烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝。另外,通式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2。Z表示具有下述通式(3)或(4)所示结构的基团。
此处,通式(3)和(4)中,Y表示单键或碳原子数1~4的亚烷基;R6~R15各自独立地表示氢原子、卤素原子或碳原子数1~6的烷基;*表示与羰基碳键合的位置。
根据本实施方式的成核剂,能够对成形品赋予优异的力学特性。
(A)芳香族磷酸酯金属盐具有上述通式(1)所示的结构。在通式(1)中,作为M1的具体例,可列举出锂、钠、钾、镁、钙、钡、羟基铝、二羟基铝、锌等。从对成形品赋予更优异的力学特性的观点出发,M1优选为锂、钠、羟基铝或二羟基铝,特别优选为钠。另外,通式(1)中的n优选为1。
通式(1)中,作为R1~R5所示的碳原子数1~6的烷基,可列举出例如甲基、乙基、正丙基、异丙基、环丙基、正丁基、仲丁基、叔丁基、异丁基、环丁基、正戊基、叔戊基、环戊基、正己基、环己基等。从对成形品赋予更优异的力学特性的观点出发,R1~R4特别优选为叔丁基。另外,从对成形品赋予更优异的力学特性的观点出发,R5优选为氢原子或甲基,特别优选为氢原子。
作为(A)芳香族磷酸酯金属盐的具体例,可列举出以下的物质。它们可以单独包含一种,也可以组合包含两种以上。其中,(A)芳香族磷酸酯金属盐不限定于它们。
(B)羧酸金属盐具有上述通式(2)所示的结构。在通式(2)中,作为M2的具体例,可列举出锂、钠、钾、镁、钙、钡、羟基铝、二羟基铝等。从对成形品赋予更优异的力学特性的观点出发,M2优选为钠、钙、羟基铝或二羟基铝,优选为钠或羟基铝,特别优选为钠。另外,在通式(2)中,优选的是:x为1、a为2。
通式(2)中的Z优选为具有通式(4)所示结构的基团。该情况下,能够对成形品赋予更优异的力学特性。
作为通式(3)和(4)中的Y所示的碳原子数1~4的亚烷基,可列举出例如亚甲基、亚乙基、亚丙基、亚丁基、亚异丁基等。从对成形品赋予更优异的力学特性的观点出发,Y优选为单键或亚甲基,进一步优选为单键。
作为通式(3)和(4)中的R6~R15所示的卤素原子,可列举出氟、氯、溴、碘。这些之中,从对成形品赋予更优异的力学特性的观点出发,特别优选为氯。
作为通式(3)和(4)中的R6~R15所示的碳原子数1~6的烷基,可列举出例如直链状或支链状的烷基、或者、碳原子数3~6的环烷基等。作为碳原子数1~6的烷基的具体例,可列举出例如甲基、乙基、正丙基、异丙基、环丙基、正丁基、仲丁基、叔丁基、异丁基、环丁基、正戊基、叔戊基、环戊基、正己基、环己基等。
作为通式(3)和(4)中的R6~R15,从对成形品赋予更优异的力学特性的观点出发,优选为氢原子或卤素原子,特别优选为氢原子。
作为(B)羧酸金属盐的具体例,可列举出以下的物质。它们可以单独包含一种,也可以组合包含两种以上。其中,(B)羧酸金属盐不限定于它们。
(B)羧酸金属盐可通过在氢氧化钠等碱的存在下例如使天冬氨酸与苯甲酰氯、环己甲酰氯等羧酰氯发生反应的方法等来制造。
本实施方式的成核剂中,只要(A)芳香族磷酸酯金属盐的含量与(B)羧酸金属盐的含量的质量比(A)/(B)例如为1/99~99/1即可。另外,质量比(A)/(B)优选为1/99~50/50。该情况下,能够对成形品赋予优异的耐冲击性。从获得具备优异的耐冲击性且具备充分的刚性的成形品的观点出发,(A)/(B)更优选为1/99~20/80、进一步优选为4/96~20/80、更进一步优选为4/96~16/84。
进而,本实施方式的成核剂中,质量比(A)/(B)还优选为50/50~99/1。该情况下,能够对成形品赋予更优异的刚性。从对成形品赋予更优异的刚性的观点出发,(A)/(B)更优选为50/50~96/4、进一步优选为50/50~84/16、更进一步优选为50/50~80/20、其中特别优选为60/40~80/20。
本实施方式的成核剂可以进一步包含(C)脂肪酸金属盐。该情况下,(A)芳香族磷酸酯金属盐和(B)羧酸金属盐的分散性提高,能够对成形品赋予更优异的力学特性。
作为(C)脂肪酸金属盐,可列举出例如包含直链状或支链状的脂肪酸残基的碳原子数12~20的脂肪酸的金属盐等。作为构成脂肪酸金属盐的金属离子,可列举出例如钠离子、钾离子、锂离子、二羟基铝离子、钙离子、锌离子、钡离子、镁离子、羟基铝离子等,这些之中,特别优选为钠离子、钾离子、锂离子、钙离子。
作为(C)脂肪酸金属盐的具体例,可列举出月桂酸钠、肉豆蔻酸钠、棕榈酸钠、硬脂酸钠、油酸钠、亚油酸钠、亚麻酸钠、花生酸钠、12-羟基硬脂酸钠、月桂酸钾、肉豆蔻酸钾、棕榈酸钾、硬脂酸钾、油酸钾、亚油酸钾、亚麻酸钾、花生酸钾、12-羟基硬脂酸钾、月桂酸锂、肉豆蔻酸锂、棕榈酸锂、硬脂酸锂、油酸锂、亚油酸锂、亚麻酸锂、花生酸锂、12-羟基硬脂酸锂、月桂酸钙、肉豆蔻酸钙、棕榈酸钙、硬脂酸钙、油酸钙、亚油酸钙、亚麻酸钙、花生酸钙、12-羟基硬脂酸钙等,这些之中,优选为肉豆蔻酸钠、硬脂酸钠、12-羟基硬脂酸钠、肉豆蔻酸锂、硬脂酸锂、12-羟基硬脂酸锂、肉豆蔻酸钙、硬脂酸钙、12-羟基硬脂酸钙,更优选为肉豆蔻酸锂、硬脂酸锂、12-羟基硬脂酸锂、肉豆蔻酸钙、硬脂酸钙、12-羟基硬脂酸钙,进一步优选为肉豆蔻酸锂、硬脂酸锂、12-羟基硬脂酸锂。
本实施方式的成核剂包含(C)脂肪酸金属盐时,只要(C)脂肪酸金属盐的含量例如相对于(A)芳香族磷酸酯金属盐的含量与(B)羧酸金属盐的含量的总计100质量份为10~150质量份即可,优选为30~120质量份,更优选为50~100质量份。
本实施方式的成核剂中,根据需要可以进一步包含与(A)芳香族磷酸酯金属盐和(B)羧酸金属盐不同且具备促进聚烯烃系树脂的结晶化这一功能的化合物、酚系抗氧化剂、磷系抗氧化剂、硫系抗氧化剂、其它的抗氧化剂、受阻胺化合物、紫外线吸收剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、抗静电剂、荧光增白剂、颜料和染料等各种添加剂。
作为与(A)芳香族磷酸酯金属盐和(B)羧酸金属盐不同且具备促进聚烯烃系树脂的结晶化这一功能的化合物,可列举出例如苯甲酸钠、4-叔丁基苯甲酸铝盐、己二酸钠、双环[2.2.1]庚烷-2,3-二羧酸二钠、环己烷-1,2-二羧酸钙等羧酸金属盐;二亚苄基山梨糖醇、双(甲基亚苄基)山梨糖醇、双(3,4-二甲基亚苄基)山梨糖醇、双(对乙基亚苄基)山梨糖醇、双(二甲基亚苄基)山梨糖醇、1,2,3-三脱氧-4,6:5,7-邻双(4-丙基亚苄基)壬醇等多元醇衍生物;N,N’,N”-三[2-甲基环己基]-1,2,3-丙烷三甲酰胺、N,N’,N”-三环己基-1,3,5-苯三甲酰胺、N,N’-二环己基萘二甲酰胺、1,3,5-三(二甲基异丙基氨基)苯等酰胺化合物等。
作为酚系抗氧化剂,可列举出例如2,6-二叔丁基-4-乙基苯酚、2-叔丁基-4,6-二甲基苯酚、苯乙烯化苯酚、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、2,2’-硫代双(6-叔丁基-4-甲基苯酚)、2,2’-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-甲基-4,6-双(辛基硫烷基甲基)苯酚、2,2’-异丁叉基双(4,6-二甲基苯酚)、异辛基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、N,N’-己烷-1,6-二基双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]、2,2’-草酰胺-双[乙基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯、2,2’-亚乙基双(4,6-二叔丁基苯酚)、3,5-二叔丁基-4-羟基苯丙酸与C13-15烷基的酯、2,5-二叔戊基氢醌、受阻酚的聚合物(ADEKA POLYMERADDITIVES EUROPE SAS公司制、商品名“AO.OH.98”)、2,2’-亚甲基双[6-(1-甲基环己基)对甲酚]、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二叔戊基苯基丙烯酸酯、6-[3-(3-叔丁基-4-羟基-5-甲基)丙氧基]-2,4,8,10-四叔丁基苯并[d,f][1,3,2]-二氧杂磷、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸酯]钙盐、5,7-双(1,1-二甲基乙基)-3-羟基-2(3H)-苯并呋喃酮与邻二甲苯的反应产物、2,6-二叔丁基-4-(4,6-双(辛基硫代)-1,3,5-三嗪-2-基氨基)苯酚、DL-a-生育酚(维生素E)、2,6-双(α-甲基苄基)-4-甲基苯酚、双[3,3-双-(4’-羟基-3’-叔丁基-苯基)丁酸]二醇酯、2,6-二叔丁基-对甲酚、2,6-二苯基-4-十八烷氧基苯酚、硬脂基(3,5-二叔丁基-4-羟基苯基)丙酸酯、二硬脂基(3,5-二叔丁基-4-羟基苄基)膦酸酯、十三烷基-3,5-叔丁基-4-羟基苄基硫代乙酸酯、硫代二亚乙基双[(3,5-二叔丁基-4-羟基苯基)丙酸酯]、4,4’-硫代双(6-叔丁基-间甲酚)、2-辛基硫代-4,6-二(3,5-二叔丁基-4-羟基苯氧基)均三嗪、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、双[3,3-双(4-羟基-3-叔丁基苯基)丁酸]二醇酯、4,4’-丁叉基双(2,6-二叔丁基苯酚)、4,4’-丁叉基双(6-叔丁基-3-甲基苯酚)、2,2’-乙叉基双(4,6-二叔丁基苯酚)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、双[2-叔丁基-4-甲基-6-(2-羟基-3-叔丁基-5-甲基苄基)苯基]对苯二甲酸酯、1,3,5-三(2,6-二甲基-3-羟基-4-叔丁基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,3,5-三[(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基]异氰脲酸酯、四[亚甲基-3-(3’,5’-叔丁基-4’-羟基苯基)丙酸酯]甲烷、2-叔丁基-4-甲基-6-(2-丙烯酰氧基-3-叔丁基-5-甲基苄基)苯酚、3,9-双[2-(3-叔丁基-4-羟基-5-甲基氢化肉桂酰氧基)-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷、三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酰胺、棕榈基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酰胺、肉豆蔻基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酰胺、月桂基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酰胺等3-(3,5-二烷基-4-羟基苯基)丙酸衍生物等。
作为磷系抗氧化剂,可列举出例如亚磷酸三苯酯、亚磷酸二异辛酯、七(二丙二醇)三亚磷酸酯、亚磷酸三异癸酯、亚磷酸二苯基异辛酯、亚磷酸二异辛基苯酯、亚磷酸二苯基十三烷基酯、亚磷酸三异辛酯、亚磷酸三(十二烷基)酯、亚磷酸二苯酯、三(二丙二醇)亚磷酸酯、亚磷酸二(油烯基)酯、三硫代亚磷酸三(十二烷基)酯、亚磷酸双(十三烷基)酯、亚磷酸三(异癸基)酯、亚磷酸三(十三烷基)酯、亚磷酸二苯基癸酯、亚磷酸二壬基苯基双(壬基苯基)酯、聚(二丙二醇)苯基亚磷酸酯、四苯基二丙二醇二亚磷酸酯、亚磷酸三壬基苯酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三(2,4-二叔丁基-5-甲基苯基)酯、亚磷酸三〔2-叔丁基-4-(3-叔丁基-4-羟基-5-甲基苯基硫代)-5-甲基苯基〕酯、亚磷酸三癸酯、亚磷酸辛基二苯酯、亚磷酸二癸基单苯酯、二硬脂基季戊四醇与硬脂酸钙盐的混合物、烷基(C10)双酚A亚磷酸酯、四苯基-四(十三烷基)季戊四醇四亚磷酸酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙酯、四(十三烷基)异丙叉基二苯酚二亚磷酸酯、四(十三烷基)-4,4’-正丁叉基双(2-叔丁基-5-甲基苯酚)二亚磷酸酯、六(十三烷基)-1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷三亚磷酸酯、四(2,4-二叔丁基苯基)亚联苯基二亚膦酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、(1-甲基-1-丙烯基-3-叉)三(1,1-二甲基乙基)-5-甲基-4,1-亚苯基)六(十三烷基)亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-2-乙基己基亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-十八烷基亚磷酸酯、2,2’-乙叉基双(4,6-二叔丁基苯基)氟亚磷酸酯、4,4’-丁叉基双(3-甲基-6-叔丁基苯基二(十三烷基))亚磷酸酯、三(2-〔(2,4,8,10-四叔丁基二苯并〔d,f〕〔1,3,2〕二氧杂膦-6-基)氧基〕乙基)胺、3,9-双(4-壬基苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺[5,5]十一烷、2,4,6-三叔丁基苯基-2-丁基-2-乙基-1,3-丙二醇亚磷酸酯、聚4,4’-异丙叉基二苯酚C12-15醇亚磷酸酯、双(二异癸基)季戊四醇二亚磷酸酯、双(十三烷基)季戊四醇二亚磷酸酯、双(十八烷基)季戊四醇二亚磷酸酯、双(壬基苯基)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯等。
作为硫系抗氧化剂,可列举出例如四[亚甲基-3-(月桂基硫代)丙酸酯]甲烷、双(甲基-4-[3-正烷基(C12/C14)硫代丙酰氧基]5-叔丁基苯基)硫化物、二(十三烷基)-3,3’-硫代二丙酸酯、二月桂基-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯、月桂基/硬脂基硫代二丙酸酯、4,4’-硫代双(6-叔丁基-间甲酚)、2,2’-硫代双(6-叔丁基-对甲酚)、二硬脂基-二硫醚。
作为其它的抗氧化剂,可列举出N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-辛基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十七烷基硝酮等硝酮化合物;3-芳基苯并呋喃-2(3H)-酮、3-(烷氧基苯基)苯并呋喃-2-酮、3-(酰氧基苯基)苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(4-羟基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-{4-(2-羟基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二叔-2-氧代-2,3-二氢苯并呋喃-3-基)苯氧基)乙氧基)-6-氧代己基-6-((6-羟基己酰基)氧基)己酸酯、5-二叔丁基-3-(4-((15-羟基-3,6,9,13-四氧杂十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等苯并呋喃化合物等。
作为受阻胺化合物,可列举出例如2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、双(2,2,6,6-四甲基-4-哌啶基)·二(十三烷基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二叔丁基-4-羟基苄基)丙二酸酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶/琥珀酸二乙酯缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-吗啉基-均三嗪缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-叔辛基氨基-均三嗪缩聚物、1,5,8,12-四〔2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8,12-四氮杂十二烷、1,5,8,12-四〔2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8-12-四氮杂十二烷、1,6,11-三[2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基-均三嗪-6-基氨基]十一烷、1,6,11-三[2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基-均三嗪-6-基氨基]十一烷、3,9-双〔1,1-二甲基-2-{三(2,2,6,6-四甲基-4-哌啶基氧基羰基)丁基羰基氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、3,9-双〔1,1-二甲基-2-{三(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)丁基羰基氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、双(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)碳酸酯、2,2,6,6-四甲基-4-哌啶基己酸酯、2,2,6,6-四甲基-4-哌啶基十八烷酸酯等。
作为紫外线吸收剂,可列举出例如2,4-二羟基二苯甲酮、5,5’-亚甲基双(2-羟基-4-甲氧基二苯甲酮)等2-羟基二苯甲酮类;2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羟基-3,5-二枯基苯基)苯并三唑、2,2’-亚甲基双(4-叔辛基-6-苯并三唑基苯酚)、2-(2-羟基-3-叔丁基-5-羧基苯基)苯并三唑的聚乙二醇酯、2-〔2-羟基-3-(2-丙烯酰氧基乙基)-5-甲基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔辛基苯基〕苯并三唑、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕-5-氯苯并三唑、2-〔2-羟基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔丁基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔戊基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并三唑、2-〔2-羟基-3-叔丁基-5-(3-甲基丙烯酰氧基丙基)苯基〕-5-氯苯并三唑、2-〔2-羟基-4-(2-甲基丙烯酰氧基甲基)苯基〕苯并三唑、2-〔2-羟基-4-(3-甲基丙烯酰氧基-2-羟基丙基)苯基〕苯并三唑、2-〔2-羟基-4-(3-甲基丙烯酰氧基丙基)苯基〕苯并三唑等2-(2-羟基苯基)苯并三唑类;水杨酸苯酯、间苯二酚单苯甲酸酯、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、(3,5-二叔丁基-4-羟基)苯甲酸辛酯、(3,5-二叔丁基-4-羟基)苯甲酸十二烷基酯、(3,5-二叔丁基-4-羟基)苯甲酸十四烷基酯、(3,5-二叔丁基-4-羟基)苯甲酸十六烷基酯、(3,5-二叔丁基-4-羟基)苯甲酸十八烷基酯、(3,5-二叔丁基-4-羟基)苯甲酸山萮酯等苯甲酸酯类;2-乙基-2’-乙氧基草酰替苯胺、2-乙氧基-4’-十二烷基草酰替苯胺等取代草酰替苯胺类;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(对甲氧基苯基)丙烯酸酯等氰基丙烯酸酯类;2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基苯酚、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、三辛基-2,2’,2”-((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4-,1-二基)三丙酸酯)、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己酰氧基)乙氧基]苯酚、2,4,6-三(2-羟基-4-己氧基-3-甲基苯基)-1,3,5-三嗪、1,12-双[2-[4-(4,6-二苯基-1,3,5-三嗪-2-基)-3-羟基苯氧基]乙基]十二烷二酸酯等三嗪类;各种金属盐或金属螯合物,尤其是镍、铬的盐或螯合物类等。
作为阻燃剂,可列举出例如磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯基)酯、磷酸甲苯基二苯酯、甲苯基-2,6-二(二甲苯基)磷酸酯、间苯二酚双(二苯基磷酸酯)、(1-甲基乙叉基)-4,1-亚苯基四苯基二磷酸酯、1,3-亚苯基四(2,6-二甲基苯基)磷酸酯、ADEKA公司制的商品名“ADEKASTAB FP-500”、“ADEKASTAB FP-600”、“ADEKASTAB FP-800”的芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸(1-丁烯基)酯等膦酸酯;二苯基次膦酸苯酯、二苯基次膦酸甲酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物等次膦酸酯;双(2-烯丙基苯氧基)磷腈、二甲苯基磷腈等磷腈化合物;磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺、多磷酸蜜白胺、多磷酸铵、磷酸哌嗪、焦磷酸哌嗪、多磷酸哌嗪、含磷的乙烯基苄基化合物和红磷等磷系阻燃剂;氢氧化镁、氢氧化铝等金属氢氧化物;溴化双酚A型环氧树脂、溴化苯酚酚醛清漆型环氧树脂、六溴苯、五溴甲苯、亚乙基双(五溴苯)、亚乙基双四溴苯二甲酰亚胺、1,2-二溴-4-(1,2-二溴乙基)环己烷、四溴环辛烷、六溴环十二烷、双(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯和2,4,6-三(三溴苯氧基)-1,3,5-三嗪、三溴苯基马来酰亚胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴双酚A型二甲基丙烯酸酯、丙烯酸五溴苄酯和溴化苯乙烯等溴系阻燃剂等。这些阻燃剂优选与氟树脂等抗滴落剂、多元醇、水滑石等阻燃助剂组合使用。
作为润滑剂,可列举出例如油酸酰胺、芥酸酰胺等不饱和脂肪酸酰胺;山萮酰胺、硬脂酰胺等饱和脂肪酸酰胺、硬脂酸丁酯、硬脂醇、硬脂酸单甘油酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇单硬脂酸酯、甘露醇、硬脂酸、氢化蓖麻油、硬脂酸酰胺、油酸酰胺、亚乙基双硬脂酸酰胺等。
作为填充剂,可列举出例如滑石、云母、碳酸钙、氧化钙、氢氧化钙、碳酸镁、氢氧化镁、氧化镁、硫酸镁、氢氧化铝、硫酸钡、玻璃粉末、玻璃纤维、粘土、白云石、二氧化硅、氧化铝、钛酸钾晶须、硅灰石、纤维状碱式硫酸镁等,可适当选择粒径(对于纤维状而言是纤维直径、纤维长度和长径比)来使用。这些填充剂之中,从赋予刚性的效果优异且容易获取的方面出发,特别优选使用滑石。另外,填充剂可根据需要而使用表面处理物。
水滑石类是作为天然物、合成物而已知的由镁、铝、羟基、碳酸基和任意结晶水形成的复盐化合物,可列举出:将镁或铝的一部分用碱金属、锌等其它金属取代而成的化合物;将羟基、碳酸基用其它阴离子基团取代而成的化合物。水滑石类可以为将结晶水脱水而成的化合物,也可以利用硬脂酸等高级脂肪酸、油酸碱金属盐等高级脂肪酸金属盐、十二烷基苯磺酸碱金属盐等有机磺酸金属盐、高级脂肪酸酰胺、高级脂肪酸酯或蜡等进行被覆而成者。水滑石类可以为天然物,另外,也可以为合成品。作为水滑石类的合成方法,可列举出日本特公昭46-2280号公报、日本特公昭50-30039号公报、日本特公昭51-29129号公报、日本特公平3-36839号公报、日本特开昭61-174270号公报、日本特开平5-179052号公报等中记载的公知方法。另外,水滑石类可以不限定其晶体结构、结晶颗粒等地加以使用。
作为抗静电剂,可列举出例如基于非离子性、阴离子性、阳离子性或两性的表面活性剂等的低分子型抗静电剂;基于高分子化合物的高分子型抗静电剂。作为非离子性表面活性剂,可列举出高级醇环氧乙烷加成物、脂肪酸环氧乙烷加成物、高级烷基胺环氧乙烷加成物、聚烯烃二醇环氧乙烷加成物等聚乙二醇型非离子表面活性剂;聚环氧乙烷、甘油的脂肪酸酯、季戊四醇的脂肪酸酯、山梨醇或脱水山梨糖醇的脂肪酸酯、多元醇的烷基醚、烷醇胺的脂肪族酰胺等多元醇型非离子表面活性剂等,作为阴离子性表面活性剂,可列举出例如高级脂肪酸的碱金属盐等羧酸盐;高级醇硫酸酯盐、高级烷基醚硫酸酯盐等硫酸酯盐;烷基苯磺酸盐、烷基磺酸盐、链烷烃磺酸盐等磺酸盐;高级醇磷酸酯盐等磷酸酯盐等,作为阳离子性表面活性剂,可列举出烷基三甲基铵盐等季铵盐等。作为两性表面活性剂,可列举出高级烷基氨基丙酸盐等氨基酸型两性表面活性剂;高级烷基二甲基甜菜碱、高级烷基二羟基乙基甜菜碱等甜菜碱型两性表面活性剂等。这些之中,优选为阴离子性表面活性剂,特别优选为烷基苯磺酸盐、烷基磺酸盐、链烷烃磺酸盐等磺酸盐。
作为高分子型抗静电剂,可列举出离聚物、以聚乙二醇为亲水部的嵌段聚合物等。作为离聚物,可列举出日本特开2010-132927号公报中记载的离聚物。作为以聚乙二醇为亲水部的聚合物,可列举出例如日本特开平7-10989号公报中记载的聚醚酯酰胺、美国专利第6552131号公报中记载的由聚烯烃和聚乙二醇形成的聚合物、日本特开2016-023254号公报中记载的由聚酯和聚乙二醇形成的聚合物等。
荧光增白剂是指:吸收太阳光、人工光的紫外线,通过将其变更为紫色~蓝色的可见光线并进行辐射的荧光作用,从而助长成形体的白色度、蓝色度的化合物。作为荧光增白剂,可列举出苯并噁唑系化合物C.I.Fluorescent Brightener184;香豆素系化合物C.I.Fluorescent Brightener52;二氨基茋二磺酸系化合物C.I.FluorescentBrightener24、85、71等。
作为颜料,没有特别限定,也可以使用市售的颜料。作为颜料的具体例,可列举出例如颜料红1、2、3、9、10、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;颜料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;颜料黄1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;颜料绿7、10、36;颜料蓝15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、29、56、60、61、62、64;颜料紫1、15、19、23、27、29、30、32、37、40、50等。
作为染料,可列举出偶氮染料、蒽醌染料、靛蓝染料、三芳基甲烷染料、呫吨染料、茜素染料、吖啶染料、茋染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲达胺染料、噁嗪染料、酞菁染料、花菁染料等。
本实施方式的成核剂也可以是进一步配混粘结剂、蜡、溶剂、二氧化硅等造粒助剂并进行造粒而得到的一体型(one pack)复合添加剂。另外,本实施方式的成核剂可以是还包含聚烯烃系树脂的母料。
作为母料中包含的聚烯烃系树脂,可列举出例如低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、交联聚乙烯、超高分子量聚乙烯等聚乙烯系树脂;均聚聚丙烯、无规共聚物聚丙烯、嵌段共聚物聚丙烯、抗冲共聚物聚丙烯、高抗冲共聚物聚丙烯、马来酸酐改性聚丙烯等聚丙烯系树脂;聚丁烯-1、环烯烃聚合物、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等α-烯烃聚合物;乙烯-甲基丙烯酸甲酯共聚物、乙烯-乙酸乙烯酯共聚物等α-烯烃共聚物等。这些聚烯烃系树脂可以单独使用1种,也可以组合使用2种以上。另外,聚烯烃系树脂可以进行合金化。聚烯烃系树脂的分子量、聚合度、密度、软化点、溶剂中的不溶成分的比例、立构规整性的程度、催化剂残渣的有无、成为原料的单体的种类、配混比率、聚合中使用的催化剂的种类(例如齐格勒催化剂、茂金属催化剂等)等没有特别限定,可适当选择。
作为母料中包含的聚烯烃系树脂,特别优选为聚丙烯系树脂。
成核剂为包含聚烯烃系树脂的母料时,只要母料中的聚烯烃系树脂的含量例如为90质量%以下即可,优选为80质量%以下、更优选为60质量%以下。另外,只要母料中的聚烯烃系树脂的含量例如为20质量%以上即可。
接着,针对本发明的树脂组合物的实施方式进行说明。
<树脂组合物>
本实施方式的树脂组合物包含聚烯烃系树脂、(A)具有上述通式(1)所示结构的芳香族磷酸酯金属盐、以及(B)具有上述通式(2)所示结构的羧酸金属盐。并且,本实施方式的树脂组合物中,上述(A)芳香族磷酸酯金属盐与上述(B)羧酸金属盐的总含量相对于聚烯烃系树脂100质量份为0.001~10质量份。
另外,本实施方式的树脂组合物可以包含聚烯烃系树脂和上述成核剂。该情况下,成核剂的含量相对于聚烯烃系树脂100质量份为0.001~10质量份。
将本实施方式的树脂组合物成形而得到的成形品具备优异的力学特性。
只要本实施方式的树脂组合物中包含的聚烯烃系树脂与上述母料中包含的聚烯烃系树脂相同即可。作为树脂组合物中包含的聚烯烃系树脂,在这些之中,优选为聚丙烯系树脂。该情况下,将树脂组合物成形而得到的成形品具备优异的力学特性,且具备优异的耐热性。
如上所述,相对于聚烯烃系树脂100质量份而言的(A)芳香族磷酸酯金属盐与(B)羧酸金属盐的总含量、或者成核剂的含量为0.001~10质量份。相对于聚烯烃系树脂100质量份而言的(A)芳香族磷酸酯金属盐与(B)羧酸金属盐的总含量、或者成核剂的含量小于0.001质量份时,将树脂组合物成形而得到的成形品的力学特性不充分。另外,相对于聚烯烃系树脂100质量份而言的(A)芳香族磷酸酯金属盐与(B)羧酸金属盐的总含量、或者成核剂的含量超过10质量份时,有时从成形品的表面发生起霜,或者,(A)芳香族磷酸酯金属盐、(B)羧酸金属盐或成核剂从成形品向外部转移。
从使得将树脂组合物成形而得到的成形品的力学特性更优异、且充分抑制自成形品发生起霜、(A)芳香族磷酸酯金属盐、(B)羧酸金属盐或成核剂的转移的观点出发,相对于聚烯烃系树脂100质量份而言的(A)芳香族磷酸酯金属盐与(B)羧酸金属盐的总含量、或者成核剂的含量更优选为0.01~1质量份、进一步优选为0.02~0.2质量份。
相对于聚烯烃系树脂100质量份而言的(A)芳香族磷酸酯金属盐的含量没有特别限定,只要为例如0.0005~9.9995质量份即可,优选为0.001~5质量份、更优选为0.01~1质量份、进一步优选为0.02~0.2质量份。另外,相对于聚烯烃系树脂100质量份而言的(B)羧酸金属盐的含量没有特别限定,只要为例如0.0005~9.9995质量份即可,优选为0.001~5质量份、更优选为0.01~1质量份、进一步优选为0.02~0.2质量份。
本实施方式的树脂组合物中,只要(A)芳香族磷酸酯金属盐的含量与(B)羧酸金属盐的含量的质量比(A)/(B)例如为1/99~99/1即可。另外,质量比(A)/(B)优选为1/99~50/50。该情况下,能够对成形品赋予优异的耐冲击性。从获得具备优异的耐冲击性且具备充分的刚性的成形品的观点出发,(A)/(B)更优选为1/99~20/80、进一步优选为4/96~20/80、更进一步优选为4/96~16/84。
进而,本实施方式的树脂组合物中,质量比(A)/(B)还优选为50/50~99/1。该情况下,能够对成形品赋予更优异的刚性。从对成形品赋予更优异的刚性的观点出发,(A)/(B)更优选为50/50~96/4、进一步优选为50/50~84/16、更进一步优选为50/50~80/20、其中特别优选为60/40~80/20。
本实施方式的树脂组合物中,可以进一步包含(C)脂肪酸金属盐。该情况下,(A)芳香族磷酸酯金属盐和(B)羧酸金属盐的分散性提高,能够对成形品赋予更优异的力学特性。
作为(C)脂肪酸金属盐,可以使用与针对成核剂而列举的物质相同的物质。
本实施方式的树脂组合物包含(C)脂肪酸金属盐时,只要(C)脂肪酸金属盐的含量相对于例如(A)芳香族磷酸酯金属盐的含量与(B)羧酸金属盐的含量的总计100质量份为10~150质量份即可,优选为30~120质量份、更优选为50~100质量份。
另外,本实施方式的树脂组合物包含(C)脂肪酸金属盐时,相对于聚烯烃系树脂100质量份而言的(C)脂肪酸金属盐的含量没有特别限定,只要例如为0.001~10质量份即可,更优选为0.01~1质量份、进一步优选为0.02~0.2质量份。
本实施方式的树脂组合物优选还包含填充剂。该情况下,将树脂组合物成形而得到的成形品的刚性变得更优异。作为填充剂,可列举出与作为成核剂中任选包含的填充剂而列举的物质相同的物质。这些填充剂之中,从获得具备更优异的刚性的成形品的观点出发,特别优选为滑石。只要树脂组合物中包含的填充剂的含量相对于聚烯烃系树脂100质量份例如为0.01~80质量份即可,优选为1~50质量份。
本实施方式的树脂组合物中,根据需要可以进一步包含与(A)芳香族磷酸酯金属盐和(B)羧酸金属盐不同且具备促进聚烯烃系树脂的结晶化这一功能的化合物、酚系抗氧化剂、磷系抗氧化剂、硫系抗氧化剂、其它的抗氧化剂、受阻胺化合物、紫外线吸收剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、抗静电剂、荧光增白剂、颜料和染料等各种添加剂。作为这些各种添加剂,可列举出与作为成核剂中任选包含的各种添加剂而列举的物质相同的物质。
接着,针对本发明的树脂组合物的制造方法的实施方式进行说明。
<树脂组合物的制造方法>
本实施方式的树脂组合物的制造方法具备将上述成核剂配混至聚烯烃系树脂中的配混工序。
将利用本实施方式的制造方法而制造的树脂组合物成形而得到的成形品具备优异的力学特性。
(准备工序)
本实施方式的制造方法中,首先,准备上述聚烯烃系树脂和上述成核剂。
(配混工序)
接着,将成核剂配混至聚烯烃系树脂中。作为配混方法,没有特别限定,可列举出例如:在添加聚烯烃系树脂、成核剂和根据需要的上述各种添加剂后,使用亨舍尔混合器、磨辊、班伯里密炼机、超级搅拌器等混合装置进行混合的方法等。此处,可以在聚烯烃系树脂单体或低聚物的聚合前或聚合中添加成核剂和上述各种添加剂之中的至少一种成分,并向所得聚合物中添加剩余的成分。
另外,本实施方式的树脂组合物的制造方法中,可以按照适当的顺序对聚烯烃系树脂配混(A)芳香族磷酸酯金属盐、(B)羧酸金属盐和根据需要的各种添加剂。此时的准备工序和配混工序可按照上述(准备工序)和(配混工序)的记载同样地进行。
如上那样操作来制造树脂组合物。树脂组合物的制造方法可以为具备熔融混炼工序的方法,所述熔融混炼工序中,进一步使用单螺杆挤出机、双螺杆挤出机等熔融混炼装置,对利用上述方法而得到的混合物进行熔融混炼。此处,熔融混炼的温度只要例如为160~260℃即可。另外,树脂组合物的制造方法可以为具备对通过熔融混炼而得到的混炼物进行造粒的造粒工序的方法。此处,作为造粒方法,没有特别限定,可列举出例如使用造粒机等造粒装置的方法等。进行造粒而得到的树脂组合物的形状没有特别限定,只要为例如粒料状即可。
接着,针对本发明的成形品的实施方式进行说明。
<成形品>
本实施方式的成形品是将上述树脂组合物进行成形而得到的。该成形品具备优异的力学特性。
作为本实施方式的成形品,可列举出例如注射成形品、纤维、扁平长丝纱、双轴拉伸薄膜、单轴拉伸薄膜、无拉伸薄膜、片、热压成形品、挤出吹塑成形品、注射吹塑成形品、注射拉伸吹塑成形品、不规则形状挤出成形品、旋转成形品等,更具体而言,可列举出汽车外饰部件、汽车内饰部件、壳体、容器、配管等。作为汽车外饰部件,可列举出例如保险杠、散热器格栅(radiator grilles)、前格栅(front grilles)、前面板、挡泥板、立柱、立柱罩、车门后视镜固定座外罩(door mirror stay covers)、窗玻璃滑槽、车门后视镜外壳、灯罩、轮罩、扰流板、空气阻流板、挡风雨条、车窗口压条、车身装饰条(belt moldings)、车顶天窗、前端模块(front-end modules)、车门控制模块(door modules)、后门控制模块、外板等,作为汽车内饰部件,可列举出例如仪表板、车门内饰板(door trim panels)、立柱饰板、门贴脸、柱装饰件(pillar garnishes)、行李箱托盘(package trays)、后托盘(rear trays)、座间储物箱、空调导管等,作为壳体,可列举出例如家电用壳体、电子游戏机用壳体、家庭用游戏机用壳体、便携型游戏机用壳体、照相机用壳体、手机用壳体、智能手机用壳体、电子设备用壳体、二次电池用壳体、安全断路器用壳体等,作为容器,可列举出例如餐具、配菜容器、冷冻食品容器、微波炉耐热容器、冷冻保存容器、蒸煮容器、杯、冰点杯等食品用容器、饮料瓶、输液瓶、医疗用中空瓶等瓶容器、烧杯、量筒等理化试验用容器、药品容器、医疗用容器、洗剂容器、化妆品容器、香水容器、调色剂容器等,作为配管,可列举出例如自来水管、气体管、基础设施结构用管、工场设施用管、车辆用燃料运输管、车辆用进气管等各种管、化妆品/香水喷雾用管、医疗用管、输液管等各种管、自来水软管、车辆用导气软管等各种软管等。
作为本实施方式的成形品的成形方法,没有特别限定,可列举出例如注射成形法、挤出成形法、吹塑成形法、旋转成形、真空成形法、吹胀成形法、压延成形法、凝塑成形法、浸渍成形法、热压成形法等。
实施例
以下,列举出实施例,更具体地说明本发明,但本发明不受以下的实施例等的任何限定。
本实施例中使用的聚烯烃系树脂、(A)芳香族磷酸酯金属盐、(B)羧酸金属盐和(C)脂肪酸金属盐如下所示。
<聚烯烃系树脂>
(PO-1)均聚聚丙烯(料筒温度:230℃、2.16kg载荷下的熔体流动速率:8g/10min)
<(A)芳香族磷酸酯金属盐>
(A-1)2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸钠
(A-2)双[2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝
(A-3)2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸锂
<(B)羧酸金属盐>
(B-1)N-苯甲酰基-L-天冬氨酸二钠
(B-2)N-环己基羰基-L-天冬氨酸二钠
(B-3)N-(4-甲基苯甲酰基)-L-天冬氨酸二钠
(B-4)N-(2,4,6-三甲基苯甲酰基)-L-天冬氨酸铝氢氧化物
<(C)脂肪酸金属盐>
(C-1)硬脂酸钙
(C-2)肉豆蔻酸锂
<树脂组合物的制备>
对于聚烯烃系树脂100质量份,按照下述表1~5中记载的配混量,配混(A)芳香族磷酸酯金属盐、(B)羧酸金属盐和(C)脂肪酸金属盐,进而配混酚系抗氧化剂(四[亚甲基-3-(3’,5’-叔丁基-4’-羟基苯基)丙酸酯]甲烷)0.05质量份、磷系抗氧化剂(三(2,4-二叔丁基苯基)亚磷酸酯)0.1质量份后,使用亨舍尔混合器(三井矿山公司制、FM200),以1000rpm的旋转速度混合1分钟。使用双螺杆挤出机(日本制钢所公司制、TEX-28V),在树脂温度为220℃、螺杆速度为150rpm的加工条件下,对所得混合物进行熔融混炼后,进行造粒,从而得到实施例1~20和比较例1~2的粒料。所得粒料在以80℃干燥8小时后,用于特性评价。需要说明的是,在下述表1~5中,配混量的单位为质量份。
<特性评价>
按照以下记载,通过测定弯曲弹性模量和冲击强度来评价将实施例1~20和比较例1~2的粒料成形而得到的成形品的力学特性。
(弯曲弹性模量)
将实施例1~20和比较例1~2的粒料以80℃干燥8小时后,使用注射成形机(东芝机械公司制、EC-220),在树脂温度为230℃、模具温度为40℃的条件下进行注射成形,制作80mm×10mm×4mm的弯曲试验片。将该试验片在温度23℃、湿度50%的恒温恒湿槽内静置48小时后,从恒温恒湿槽中取出试验片,使用弯曲试验机(岛津制作所制、AG-IS),按照ISO178来测定试验片的弯曲弹性模量(MPa)。将其结果示于下述表1~5。
(冲击强度)
将实施例1~20和比较例1~2的粒料以80℃干燥8小时后,利用注射成形机(装置;日精树脂工业公司制、卧式注射成形机NEX80),在树脂温度为230℃、模具温度为40℃的加工条件下进行成形,制作在中央部具有V字型缺口的80mm×10mm×4mm的夏比冲击强度测定用试验片。将该试验片在温度23℃、湿度60%的恒温恒湿槽内静置7天后,从恒温恒湿槽中取出试验片,按照ISO179-1来测定试验片的夏比冲击强度(kJ/m2)。将其结果作为“冲击强度(kJ/m2)”而示于下述表1~5。
[表1]
[表2]
[表3]
[表4]
[表5]
根据上述表1~5所示的结果,与将包含(A)芳香族磷酸酯金属盐且不含(B)羧酸金属盐的比较例2的粒料进行成形而得到的成形品相比,将使用包含具有特定结构的(A)芳香族磷酸酯金属盐和(B)羧酸金属盐的成核剂的实施例1~20的粒料进行成形而得到的成形品具备优异的刚性或具备同等的刚性,并且具备优异的耐冲击性。
综上可确认:通过使用包含具有特定结构的(A)芳香族磷酸酯金属盐和(B)羧酸金属盐的成核剂,从而能够对成形品赋予优异的力学特性。
Claims (9)
1.一种成核剂,其特征在于,其包含(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐和(B)具有下述通式(2)所示结构的羧酸金属盐,
上述通式(1)中,R1~R5各自独立地表示氢原子或碳原子数1~6的烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝,
上述通式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2;Z表示具有下述通式(3)或(4)所示结构的基团,
上述通式(3)和(4)中,Y表示单键或碳原子数1~4的亚烷基;R6~R15各自独立地表示氢原子、卤素原子或碳原子数1~6的烷基;*表示与羰基碳键合的位置。
2.根据权利要求1所述的成核剂,其中,所述通式(2)中的M2为钠。
3.根据权利要求1所述的成核剂,其中,所述(A)芳香族磷酸酯金属盐的含量与所述(B)羧酸金属盐的含量的质量比(A)/(B)为1/99~50/50。
4.根据权利要求1所述的成核剂,其中,所述(A)芳香族磷酸酯金属盐的含量与所述(B)羧酸金属盐的含量的质量比(A)/(B)为50/50~99/1。
5.根据权利要求4所述的成核剂,其中,所述(A)芳香族磷酸酯金属盐的含量与所述(B)羧酸金属盐的含量的质量比(A)/(B)为50/50~80/20。
6.一种树脂组合物,其特征在于,其包含聚烯烃系树脂、(A)具有下述通式(1)所示结构的芳香族磷酸酯金属盐、以及(B)具有下述通式(2)所示结构的羧酸金属盐,
所述(A)芳香族磷酸酯金属盐与所述(B)羧酸金属盐的总含量相对于所述聚烯烃系树脂100质量份为0.001~10质量份,
上述通式(1)中,R1~R5各自独立地表示氢原子或碳原子数1~6的烷基;n表示1或2;n为1时,M1表示碱金属或二羟基铝;n为2时,M1表示碱土金属、锌或羟基铝,
上述通式(2)中,M2表示碱金属、碱土金属、羟基铝或二羟基铝;a表示1或2;x表示1或2;满足ax=2;Z表示具有下述通式(3)或(4)所示结构的基团,
上述通式(3)和(4)中,Y表示单键或碳原子数1~4的亚烷基;R6~R15各自独立地表示氢原子、卤素原子或碳原子数1~6的烷基;*表示与羰基碳键合的位置。
7.根据权利要求6所述的树脂组合物,其中,所述聚烯烃系树脂为聚丙烯系树脂。
8.一种树脂组合物的制造方法,其特征在于,其具备将权利要求1所述的成核剂配混至聚烯烃系树脂中的配混工序。
9.一种成形品,其特征在于,其是将权利要求6所述的树脂组合物进行成形而得到的。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2021/012754 WO2021193886A1 (ja) | 2020-03-27 | 2021-03-25 | 核剤、樹脂組成物、樹脂組成物の製造方法および成形品 |
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JP2005120237A (ja) * | 2003-10-16 | 2005-05-12 | Asahi Denka Kogyo Kk | 結晶核剤組成物及びこれを含有してなる結晶性高分子組成物 |
JP2019127518A (ja) * | 2018-01-23 | 2019-08-01 | 株式会社Adeka | 核剤組成物、これを含有するオレフィン系樹脂組成物およびその成形品 |
JP2020015862A (ja) * | 2018-07-27 | 2020-01-30 | 株式会社Adeka | ポリオレフィン用核剤、これを含有するポリオレフィン用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品 |
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JPS581736A (ja) | 1981-06-25 | 1983-01-07 | Adeka Argus Chem Co Ltd | ポリオレフイン系樹脂組成物 |
US6552131B1 (en) | 1999-02-10 | 2003-04-22 | Sanyo Chemical Industries, Ltd. | Block polymer and antistatic agent comprising the same |
JP4674839B2 (ja) * | 2001-05-17 | 2011-04-20 | 株式会社Adeka | 結晶性高分子組成物 |
WO2009072600A1 (ja) | 2007-12-07 | 2009-06-11 | Du Pont-Mitsui Polychemicals Co., Ltd. | アイオノマー、該アイオノマーを含有する樹脂組成物、該組成物から形成される未延伸フィルム、シートまたは成形体、ならびに該未延伸フィルム層を有する積層体 |
JP6377437B2 (ja) | 2014-07-22 | 2018-08-22 | 株式会社Adeka | 帯電防止剤、帯電防止剤組成物、帯電防止性樹脂組成物および成形体 |
WO2020137179A1 (ja) * | 2018-12-27 | 2020-07-02 | 株式会社Adeka | ポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂用マスターバッチ、ポリオレフィン系樹脂組成物、その成形品、そのフィルム、多孔質フィルムの製造方法および包装体 |
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JP2005120237A (ja) * | 2003-10-16 | 2005-05-12 | Asahi Denka Kogyo Kk | 結晶核剤組成物及びこれを含有してなる結晶性高分子組成物 |
JP2019127518A (ja) * | 2018-01-23 | 2019-08-01 | 株式会社Adeka | 核剤組成物、これを含有するオレフィン系樹脂組成物およびその成形品 |
JP2020015862A (ja) * | 2018-07-27 | 2020-01-30 | 株式会社Adeka | ポリオレフィン用核剤、これを含有するポリオレフィン用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品 |
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KR20220161346A (ko) | 2022-12-06 |
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JPWO2021193886A1 (zh) | 2021-09-30 |
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