TW201805355A - Stabilized polyolefin resin material - Google Patents
Stabilized polyolefin resin material Download PDFInfo
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- TW201805355A TW201805355A TW106119296A TW106119296A TW201805355A TW 201805355 A TW201805355 A TW 201805355A TW 106119296 A TW106119296 A TW 106119296A TW 106119296 A TW106119296 A TW 106119296A TW 201805355 A TW201805355 A TW 201805355A
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/13—Phenols; Phenolates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
Description
本發明係關於經穩定化的樹脂材料，進一步詳細而言，本發明係關於藉由特定之主要抗氧化劑(primary antioxidant)與第二抗氧化劑之組合而經穩定化的尤其是變色得到抑制之樹脂材料。 The present invention relates to a stabilized resin material, and more specifically, the present invention relates to a resin that is stabilized, and in particular, that discoloration is suppressed by a combination of a specific primary antioxidant and a second antioxidant. material.
樹脂材料例如聚烯烴(RH)在受到熱或光、物理性刺激引起的攻擊時，生成自由基(R*)且該自由基與氧反應而生成過氧自由基(ROO*)。該過氧自由基從其他的分子(RH)奪取氫而成為氫過氧化物(ROOH)，同時進一步生成新的自由基(R*)。新產生的自由基成為接下來的反應的誘因，即產生鏈式反應從而樹脂材料的劣化進一步發展。 When a resin material such as polyolefin (RH) is attacked by heat, light, or physical stimulus, a radical (R *) is generated, and the radical reacts with oxygen to generate a peroxy radical (ROO *). This peroxy radical extracts hydrogen from other molecules (RH) to become a hydroperoxide (ROOH), and further generates a new radical (R *). The newly generated free radicals become the incentive for the next reaction, that is, a chain reaction is generated and the deterioration of the resin material is further developed.
另外，氫過氧化物(ROOH)不穩定，其自身進一步分解而生成新自由基(例如RO*)，該新自由基從其他分子奪取氫從而使自由基增加，此也導致樹脂材料劣化。這般的經過氫過氧化物的分子的分解稱作自動氧化。 In addition, hydroperoxide (ROOH) is unstable, and further decomposes itself to generate new radicals (eg, RO *). The new radicals take away hydrogen from other molecules to increase free radicals, which also causes degradation of resin materials. The decomposition of such molecules through hydroperoxide is called auto-oxidation.
為了防止這般的樹脂分子的分解即劣化，可使用抗氧化劑。已知在抗氧化劑中有：具有主要捕捉自由 基從而在自動氧化的初始階段防止氧化的作用的抗氧化劑(稱作「主要抗氧化劑」)、與經由將不穩定的氫過氧化物分解為穩定的產物從而抑制進一步生成自由基的抗氧化劑(稱作「第二抗氧化劑」)。作為主要抗氧化劑，已知例如有酚系抗氧化劑等，作為第二抗氧化劑，已知例如有磷酸系抗氧化劑、硫系抗氧化劑等。也已知合併使用主要抗氧化劑與第二抗氧化劑，也已知兩者對於抗氧化顯示出協同效果。 In order to prevent decomposition or deterioration of such resin molecules, an antioxidant may be used. Known among antioxidants: with major capture freedom Antioxidants (called "primary antioxidants") that prevent oxidation in the initial stages of auto-oxidation, and antioxidants that inhibit the further generation of free radicals by decomposing unstable hydroperoxides into stable products ( Called "secondary antioxidant"). As the main antioxidant, for example, a phenol-based antioxidant and the like are known, and as the second antioxidant, for example, a phosphoric acid-based antioxidant and a sulfur-based antioxidant are known. It is also known to use a primary antioxidant in combination with a second antioxidant, and it is also known that the two exhibit a synergistic effect on antioxidant.
另外，已知作為主要抗氧化劑而應用的酚系抗氧化劑經過醌系化合物而成為芪醌，從而使所添加的樹脂著色‧變色。由於為了防止樹脂材料的劣化而添加的抗氧化劑損害其外觀，在這點上並不理想，故而在利用酚系抗氧化劑時抑制其變色成為課題。 In addition, it is known that a phenolic antioxidant applied as a main antioxidant becomes a stilbenequinone through a quinone compound, thereby coloring and discoloring the added resin. The antioxidant added to prevent deterioration of the resin material is not desirable in this respect. Therefore, it is a problem to suppress discoloration when a phenol-based antioxidant is used.
有關變色抑制，例如日本特表2002-527595號公報(專利文獻1)公開了作為主要抗氧化劑及第二抗氧化劑的組合，將與本發明的結構類似但不同的化合物群作為抗氧化劑，並經由其組合來使聚合物的穩定度與白色度增加。然而，在該專利文獻1中，將消除由作為防止主要抗氧化劑變色的第二抗氧化劑的亞磷酸酯的添加引起的不利作為課題，且以水的存在作為前提。另外，日本特開2005-82642號公報(專利文獻2)公開了將本發明中使用化合物群作為抗氧化劑，但並未公開將它們具體組合使用的情況，當然其效果也並未確認。 Regarding inhibition of discoloration, for example, Japanese Patent Publication No. 2002-527595 (Patent Document 1) discloses a combination of a main antioxidant and a second antioxidant, and uses a compound group similar to but different in structure from the present invention as an antioxidant, It is combined to increase the stability and whiteness of the polymer. However, in this patent document 1, it is a subject to eliminate the disadvantage caused by the addition of a phosphite which is a second antioxidant that prevents discoloration of the main antioxidant, and the premise is the presence of water. In addition, Japanese Patent Application Laid-Open No. 2005-82642 (Patent Document 2) discloses that the compound group used in the present invention is used as an antioxidant, but does not disclose a case where these compounds are used in combination, and of course, its effect has not been confirmed.
[專利文獻1]日本特表2002-527595號公報 [Patent Document 1] Japanese Patent Publication No. 2002-527595
[專利文獻2]日本特開2005-82642號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2005-82642
本發明者此次得到了如下見解：經由組合使用特定的兩種第二抗氧化劑，可長時間有效防止認為起因於酚系抗氧化劑的變色(紅~粉)，得到見解。本發明基於相關見解。 The present inventors have obtained the insight that the use of specific two kinds of second antioxidants in combination can effectively prevent discoloration (red to pink) thought to be caused by phenolic antioxidants for a long period of time. The present invention is based on relevant insights.
因此，本發明在於提供如下樹脂材料：其為包含聚烯烴的樹脂材料，可有效作用於使用酚系抗氧化劑時產生的樹脂的變色作為其目的。 Accordingly, the present invention is to provide a resin material which is a resin material containing a polyolefin, and its object is to effectively act on discoloration of a resin generated when a phenol-based antioxidant is used.
另外，本發明在於提供在以聚烯烴作為主要高分子成分的樹脂材料中可與酚系抗氧化劑組合使用的抗氧化劑的組合作為目的。 The present invention also aims to provide a combination of antioxidants that can be used in combination with a phenolic antioxidant in a resin material containing polyolefin as a main polymer component.
另外，本發明在於提供聚烯烴用抗氧化劑及成形體作為目的。 Another object of the present invention is to provide an antioxidant for polyolefin and a molded article.
因此，根據本發明的樹脂材料的特徵在於，包含如下物質而成：(1)聚烯烴；(2)以下述(I)表示的化合物：
式中，R1及R2各自獨立地表示直鏈及支鏈狀的碳數1~20的烴基；(3)以下述式(II)表示的化合物：
式中，R3、R4、R5、R6、R7及R8獨立表示直鏈或支鏈烷基的碳數1~20的烴基；(4)酚系抗氧化劑。 In the formula, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently represent a hydrocarbon group having 1 to 20 carbon atoms in a straight or branched alkyl group; (4) a phenolic antioxidant.
另外，根據本發明的聚烯烴用抗氧化劑的特徵在於以包含上述式(I)表示的化合物、以式(II)表示的化合物及酚系抗氧化劑而成。 In addition, the antioxidant for polyolefin according to the present invention is characterized by comprising a compound represented by the formula (I), a compound represented by the formula (II), and a phenol-based antioxidant.
進而，根據本發明的成形體包含上述的根據本發明的樹脂材料而成。 Furthermore, the molded body according to the present invention includes the resin material according to the present invention described above.
根據本發明，在包含聚烯烴的樹脂材料中可長時間有效防止認為起因於酚系抗氧化劑的變色(紅~粉)。本發明者實驗性確認了該根據本發明的效果可經由至少組合兩種特定的第二抗氧化劑來得到，與其他結構類似的第二抗氧化劑相比非常顯著。 According to the present invention, in a resin material containing a polyolefin, discoloration (red to pink) that is thought to be caused by a phenol-based antioxidant can be effectively prevented for a long period of time. The present inventors have experimentally confirmed that the effect according to the present invention can be obtained by combining at least two specific second antioxidants, which is very significant compared to other second antioxidants having similar structures.
[用以實施本發明之最佳形態] [Best Mode for Carrying Out the Invention]
樹脂材料 Resin material
根據本發明的樹脂材料至少包含(1)聚烯烴、(2)式(I)的化合物、(3)式(II)的化合物、(4)酚系抗氧化劑而成。根據本發明，藉由組合(2)、(3)及(4)的抗氧化劑，可長時間有效防止認為起因於樹脂材料的酚系抗氧化劑的變色(紅~粉)。其理由並不明確，認為如下。認為酚系抗氧化劑經過醌系化合物而成為芪醌的理由多種多樣，但認為是自由基捕捉的結果從而使其結構變化，最終成為芪醌，認為在本發明中式(I)的化合物與式(II)的化合物協同作用，從而有效防止來自不穩定的氫過氧化物的自由基的產生，並高效率抑制酚系抗氧化劑向發色結構的變化。尤其是，從後述的實施例與對比例的對比認為，亞磷酸的酯結構之一較佳為在2,4,6位上被烷基取代的苯結構。以上終歸是假說，本發明的解釋並不限定於此。 The resin material according to the present invention includes at least (1) a polyolefin, (2) a compound of formula (I), (3) a compound of formula (II), and (4) a phenolic antioxidant. According to the present invention, by combining the antioxidants (2), (3), and (4), it is possible to effectively prevent discoloration (red to pink) of the phenolic antioxidant which is thought to be caused by the resin material for a long time. The reason is not clear, and it is considered as follows. There are various reasons why phenolic antioxidants can be converted into stilbenequinones through quinone compounds. However, it is thought that the structure of the phenolic antioxidants is changed as a result of radical capture and finally become stilbenequinones. In the present invention, the compound of formula (I) and the formula ( The compounds of II) act synergistically, thereby effectively preventing the generation of free radicals from unstable hydroperoxides, and efficiently suppressing the change of the phenolic antioxidant to the chromonic structure. In particular, from the comparison of the examples and comparative examples described later, it is considered that one of the ester structures of phosphorous acid is preferably a benzene structure substituted with an alkyl group at the 2, 4, and 6 positions. The above is a hypothesis, and the explanation of the present invention is not limited to this.
根據本發明的樹脂材料將多個抗氧化劑組合來包含，在該點上也有利。 The resin material according to the present invention is also advantageous in that a plurality of antioxidants are contained in combination.
尚，根據本發明的樹脂材料允許不可避免的水分的存在，而且不需要添加水，由於通常水的存在會在樹脂材料的成形過程中產生不良影響從而發生外觀不良，故而較佳避開水。 However, the resin material according to the present invention allows the presence of unavoidable moisture and does not require the addition of water. Since the presence of water usually has an adverse effect on the molding process of the resin material, resulting in poor appearance, it is better to avoid water.
(1)聚烯烴 (1) Polyolefin
根據本發明的樹脂材料包含聚烯烴。在本發明中，聚烯烴意味著烯烴化合物即作為碳間的鍵具有至少一個雙鍵的烴的聚合物，也可為均聚物及共聚物中的任一種。烯烴化合物即作為單體，例如可列舉碳數2~16的單-1-烯烴，較佳碳數為2~10個的單-1-烯烴，更佳碳數2~6個的單-1-烯烴，作為其具體例，可列舉乙烯、丙烯、1-丁烯、1-戊烯、1-己烯及1-辛烯等，但並不限定於此。作為本發明較佳應用的聚烯烴的例子，可列舉聚乙烯、聚丙烯等。 The resin material according to the present invention contains a polyolefin. In the present invention, polyolefin means an olefin compound, that is, a polymer having a hydrocarbon having at least one double bond as a bond between carbons, and may be any of a homopolymer and a copolymer. An olefin compound is a monomer, and examples thereof include a mono-1-olefin having 2 to 16 carbon atoms, a mono-1-olefin having 2 to 10 carbon atoms is preferred, and a mono-1 having 2 to 6 carbon atoms is more preferred. -Olefin includes, but is not limited to, specific examples thereof, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Examples of the polyolefin to which the present invention is preferably applied include polyethylene, polypropylene, and the like.
根據本發明的一個較佳方式，在本發明中作為聚烯烴，可使用將聚烯烴與所謂的彈性體成分組合的烯烴系彈性體。作為彈性體成分，可列舉天然橡膠、乙丙橡膠、聚丁二烯橡膠等，添加的形態還可為經由彈性體成分的微分散等進行混合的方式、伴隨著化學交聯的方式。本發明為公知的烯烴系彈性體及今後可知的物質，可在分類為烯烴系彈性體的物質中廣泛應用。 According to a preferable aspect of the present invention, as the polyolefin in the present invention, an olefin-based elastomer in which a polyolefin and a so-called elastomer component are combined can be used. Examples of the elastomer component include natural rubber, ethylene-propylene rubber, polybutadiene rubber, and the like. The form of addition may be a method of mixing via microdispersion of the elastomer component or the like, or a method accompanied by chemical crosslinking. The present invention is a known olefin-based elastomer and a substance that will be known in the future, and can be widely applied to substances classified as olefin-based elastomers.
根據本發明的樹脂材料作為聚烯烴可沒有特 別限制地使用，尤其是較佳用於變色會損害其商品價值的用途。 The resin material according to the present invention does not have special properties as a polyolefin. Do not use it in a restricted way, especially for a use where the discoloration will damage its value.
(2)式(I)的化合物
在本發明中前述式(I)的化合物為第二抗氧化劑，式中，R1及R2各自獨立地表示直鏈及支鏈狀的碳數1~20的烴基，較佳碳數為1~16，更佳表示碳數1~8的烴基，例如可列舉甲基、叔丁基、1,1-二甲基丙基。 In the present invention, the compound of the formula (I) is a second antioxidant. In the formula, R 1 and R 2 each independently represent a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and preferably 1 carbon number. ~ 16, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include methyl, t-butyl, and 1,1-dimethylpropyl.
作為式(I)的化合物較佳的具體例，可列舉三(2,4-二-叔丁基苯基)亞磷酸酯、三(2-叔丁基苯基)亞磷酸酯、三[2,4-二-(1,1-二甲基丙基)苯基]亞磷酸酯。 Preferred specific examples of the compound of formula (I) include tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butylphenyl) phosphite, and tris [2 , 4-Di- (1,1-dimethylpropyl) phenyl] phosphite.
式(I)的化合物的添加量可考慮其效果來適當確定，例如較佳相對於高分子成分為0.01~1質量%左右，較佳0.05~0.5質量%左右。 The addition amount of the compound of the formula (I) may be appropriately determined in consideration of the effect thereof. For example, it is preferably about 0.01 to 1% by mass, and more preferably about 0.05 to 0.5% by mass with respect to the polymer component.
(3)式(II)的化合物 (3) Compound of formula (II)
在本發明中前述式(II)的化合物亦為第二抗氧化劑，式中，R3、R4、R5、R6、R7及R8獨立表示直鏈或支鏈烷基的碳數1~20的烴基，較佳碳數為1~16，更佳表示碳數1~8的烴基，例如可列舉甲基、叔丁基、1,1-二甲基丙基。 In the present invention, the compound of the aforementioned formula (II) is also a second antioxidant. In the formula, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 independently represent the carbon number of a linear or branched alkyl group. The hydrocarbon group of 1 to 20 preferably has a carbon number of 1 to 16, and more preferably represents a hydrocarbon group of 1 to 8 carbon atoms. Examples thereof include methyl, tert-butyl, and 1,1-dimethylpropyl.
作為式(II)的化合物較佳的具體例，可列舉雙-(2,6-二-叔丁基-4-甲基苯基)季戊四醇醇-二亞磷酸 酯。 Preferred specific examples of the compound of formula (II) include bis- (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite ester.
式(II)的化合物的添加量可考慮其效果來適當確定，例如較佳相對於高分子成分為0.01~1質量%左右，較佳0.05~0.5質量%左右。 The addition amount of the compound of the formula (II) may be appropriately determined in consideration of the effect thereof. For example, it is preferably about 0.01 to 1% by mass, and more preferably about 0.05 to 0.5% by mass with respect to the polymer component.
(4)酚系抗氧化劑 (4) Phenolic antioxidants
根據本發明的樹脂材料所包含的酚系抗氧化劑作為所謂的主要抗氧化劑，可防止聚烯烴的劣化。在本發明中，酚系抗氧化劑意味著主要具有自由基捕捉作用的抗氧化劑，較佳分類為受阻酚。可選自單酚、雙酚、硫代雙酚、聚苯酚、羥基苄基芳香族羧酸酯、β-(3,5-二-叔丁基-4-羥基苯基)丙酸的醯胺、β-(3,5-二-叔丁基-4-羥基苯基)丙酸與一元或多元醇的酯、螺化合物及此等的混合物。 The phenol-based antioxidant contained in the resin material according to the present invention can prevent deterioration of polyolefin as a so-called main antioxidant. In the present invention, the phenol-based antioxidant means an antioxidant mainly having a radical-capturing effect, and is preferably classified as a hindered phenol. May be selected from monophenols, bisphenols, thiobisphenols, polyphenols, hydroxybenzyl aromatic carboxylic acid esters, amidines of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols, spiro compounds, and mixtures thereof.
作為單酚，可列舉2,6-二-叔丁基-4-甲基苯酚、2-叔丁基-4-甲氧基苯酚及4-(羥基甲基)-2,6-二-叔丁基苯酚。 Examples of the monophenol include 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, and 4- (hydroxymethyl) -2,6-di-tert Butylphenol.
作為雙酚，可列舉2,2’-亞甲基雙(6-叔丁基-4-甲基苯酚)、2,2’-亞甲基雙(6-叔丁基-4-乙基苯酚)、2,2-亞甲基雙[4-甲基-6-(α-甲基環己基)苯酚]、1,1-雙(5-叔丁基-4-羥基-2-甲基苯基)丁烷、2,2-雙(5-叔丁基-4-羥基-2-甲基苯基)丁烷、2,2-雙(3,5-二-叔丁基-4-羥基苯基)丙烷、1,1,3-三(5-叔丁基-4-羥基-2-甲基苯基)丁烷、2,2-雙(5-叔丁基-4-羥基-2-甲基苯基)-4-正十二烷基巰基丁烷、1,1,5,5-四-(5-叔丁基-4-羥基-2-甲基苯 基)戊烷、乙二醇-雙[3,3-雙(3’-叔丁基-4’-羥基苯基)丁酸酯、1,1-雙(3,5-二甲基-2-羥基苯基)-3-(正十二烷基硫代)丁烷及4,4’-硫代雙(6-叔丁基-3-甲基苯酚)。 Examples of the bisphenol include 2,2'-methylenebis (6-tert-butyl-4-methylphenol) and 2,2'-methylenebis (6-tert-butyl-4-ethylphenol) ), 2,2-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 1,1-bis (5-tert-butyl-4-hydroxy-2-methylbenzene ) Butane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy Phenyl) propane, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (5-tert-butyl-4-hydroxy-2 -Methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylbenzene ) Pentane, ethylene glycol-bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate, 1,1-bis (3,5-dimethyl-2 -Hydroxyphenyl) -3- (n-dodecylthio) butane and 4,4'-thiobis (6-tert-butyl-3-methylphenol).
作為硫代雙酚，可列舉4,4’-硫代雙(6-叔丁基-間甲酚)、1,1’-硫代雙(2-萘酚)及2,2’-硫代雙(4-甲基-6-叔丁基苯酚)。 Examples of thiobisphenols include 4,4'-thiobis (6-tert-butyl-m-cresol), 1,1'-thiobis (2-naphthol), and 2,2'-thio Bis (4-methyl-6-tert-butylphenol).
作為聚苯酚，可列舉四(亞甲基-3-(3,5-二-叔丁基-4-羥基苯基)丙酸酯)甲烷、1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羥基苄基)苯、1,3,5-三(3,5-二-叔丁基-4-羥基苄基)異氰脲酸酯及四[亞甲基-(3,5-二-叔丁基-4-羥基苯丙酸酯)]甲烷。 Examples of the polyphenol include tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane and 1,3,5-trimethyl-2,4. 1,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Acid esters and tetrakis [methylene- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)] methane.
作為羥基苄基芳香族羧酸酯，可列舉1,3,5-三(3,5-二-叔丁基-4-羥基苄基)-2,4,6-三甲基苯、2,2-雙(3,5-二-叔丁基-4-羥基苄基)丙二酸二十八烷基酯、1,3,5-三(3,5-二-叔丁基-4-羥基苄基)異氰脲酸酯及3,5-二-叔丁基-4-羥基苄基膦酸二乙酯。 Examples of the hydroxybenzyl aromatic carboxylic acid ester include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2, 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) octadecyl malonate, 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate and diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
作為β-(3,5-二-叔丁基-4-羥基苯基)丙酸的醯胺，可列舉1,3,5-三(3,5-二-叔丁基-4-羥基苯基-丙醯基-六氫-均三嗪及N,N’-二(3,5-二-叔丁基-4-羥基苯基-丙醯基)六亞甲基二胺。 Examples of the amidine of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid include 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzene -Propanyl-hexahydro-mesytriazine and N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propanyl) hexamethylenediamine.
酚類系抗氧化劑的添加量可考慮其效果來適當確定，例如較佳相對於高分子成分為0.01~1質量%左右，較佳0.05~0.5質量%左右。 The amount of the phenolic antioxidant to be added may be appropriately determined in consideration of its effect. For example, it is preferably about 0.01 to 1% by mass, and more preferably about 0.05 to 0.5% by mass relative to the polymer component.
其他成分 Other ingredients
在根據本發明的樹脂材料中可添加在聚烯烴中通常或一般任意添加的各種成分。 In the resin material according to the present invention, various components which are generally or generally arbitrarily added to polyolefin can be added.
抗氧化劑及成形體 Antioxidants and shaped bodies
由以上可知，根據本發明的一個方式可提供聚烯烴用抗氧化劑，該聚烯烴用抗氧化劑包含以上述式(I)表示的化合物、以式(II)表示的化合物及酚系抗氧化劑而成。另外，根據本發明的其他方式可提供上述的包含根據上述之本發明的樹脂材料而成的成形體，該成形體即使因抗氧化劑的添加也不會使其各種物性變化，從而可用於所期望的用途，另一方面可有效防止變色。 From the above, according to one aspect of the present invention, it is possible to provide an antioxidant for polyolefin. The antioxidant for polyolefin includes a compound represented by the formula (I), a compound represented by the formula (II), and a phenolic antioxidant. . In addition, according to another aspect of the present invention, it is possible to provide the above-mentioned formed body including the resin material according to the present invention described above, and the formed body can be used for desired properties without changing various physical properties even with the addition of an antioxidant. Use, on the other hand can effectively prevent discoloration.
[實施例] [Example]
本發明經由以下的實施例進一步進行了詳細說明，但本發明並不限定於此等實施例。尚，只要沒有特別聲明，以下%意味著質量%。 The present invention is further described in detail through the following examples, but the present invention is not limited to these examples. As long as there is no special statement, the following% means mass%.
1.樣品之製作 1. Production of samples
準備具有下述組成的樹脂材料。 A resin material having the following composition was prepared.
表中具體材料係如下所示。 The specific materials in the table are shown below.
烯烴系彈性體：以PP作為硬鏈段的烯烴系熱塑性彈性體 Olefin-based elastomers: olefin-based thermoplastic elastomers with PP as a hard segment
式(I)的化合物：由股份有限公司ADEKA作為2112可獲得的在式(I)中R1及R2為叔丁基的化合物。 Compound of formula (I): A compound in which R 1 and R 2 in formula (I) are tert-butyl groups available from ADEKA Corporation as 2112.
式(II)的化合物：由股份有限公司ADEKA作為PEP-360可獲得的在式(I)中R3、R4、R6及R7為叔丁基且R5及R8為甲基的化合物。 Compound of formula (II): available from ADEKA Corporation as PEP-360. In formula (I), R 3 , R 4 , R 6 and R 7 are tert-butyl and R 5 and R 8 are methyl. Compound.
式(III)的化合物：由股份有限公司ADEKA作為HP-10可獲得的下述結構式所表示的化合物。 Compound of formula (III): A compound represented by the following structural formula available as ADE-10 from ADEKA Corporation.
將上述組成的樹脂材料射出成形而得到10cm×5cm的樣品板及啞鈴形試片。射出成形的條件為汽缸(cylinder)溫度190℃、模具溫度40℃。另外，設置於與 便座的便器連接側的便座緩衝(cushion)零件按照上述成形方法來製作。 The resin material having the above composition was injection-molded to obtain a 10 cm × 5 cm sample plate and a dumbbell-shaped test piece. The injection molding conditions were a cylinder temperature of 190 ° C and a mold temperature of 40 ° C. In addition, A toilet cushion part on the toilet connection side of the toilet seat is manufactured according to the above-mentioned forming method.
2.強制循環式熱老化試驗 2. Forced-cycle thermal aging test
將在上述1中得到的便座緩衝零件及樣品板放入強制循環式熱老化試驗機(日本ESPEC股份有限公司製)，進行由熱引起的樹脂劣化的加速試驗。設定溫度為70℃。試驗時間為最長624小時。 The toilet seat cushion part and the sample plate obtained in the above 1 were put into a forced circulation type heat aging tester (manufactured by Japan ESPEC Co., Ltd.), and an accelerated test for resin degradation by heat was performed. The set temperature is 70 ° C. The test time is up to 624 hours.
3.變色的測定及結果 3. Measurement and results of discoloration
經過下表所示的時間後從上述2的試驗機取出試片，將與初始的試片相比的變色的程度使用分光測色儀CM-5(日本柯尼卡美能達公司製)進行測定。尚，變色的程度測定a值、b值及L值，並以a值(表示紅-綠側的顏色的變化)的變化量△a及下述的△E作為指標來表示。 After the elapsed time shown in the table below, the test piece was taken out from the above 2 test machine, and the degree of discoloration compared to the initial test piece was measured using a spectrophotometer CM-5 (manufactured by Konica Minolta, Japan) . The degree of discoloration was measured by a value, b value, and L value, and the change in the value a (representing the change in color on the red-green side) Δa and the following ΔE were used as indicators.
△E^2=(△a^2+△b^2)+△L^2 △ E ^ 2 = (△ a ^ 2 + △ b ^ 2) + △ L ^ 2
结果如下表所示。 The results are shown in the following table.
可知與僅為使用式(I)的化合物的情況相比，另外與和式(III)的化合物這般的結構不同的抗氧化劑合用的情況相比，根據本發明的樹脂材料可顯著地抑制變色。 It can be seen that the resin material according to the present invention can significantly suppress discoloration compared to a case where only a compound of the formula (I) is used and a case where an antioxidant having a different structure from the compound of the formula (III) is used in combination. .
4.材料物性之評估 4. Evaluation of material properties
(a)硬度 (a) Hardness
將上述1製作的便座緩衝零件的硬度按照JIS(日本工業標準)6253-3/ISO 7619-1用硬度計進行測定。 The hardness of the toilet seat cushioning member produced in the above 1 was measured with a hardness meter in accordance with JIS (Japanese Industrial Standard) 6253-3 / ISO 7619-1.
(b)拉伸強度 (b) Tensile strength
使用上述1製作的啞鈴形試片進行拉伸強度試驗。試驗按照JIS 6251/ISO 37用自動立體測圖儀(autograph)(日本島津製作所製)以500mm/分鐘的速度進行拉伸，記錄最大應力。 A tensile strength test was performed using the dumbbell-shaped test piece prepared in 1 above. The test was performed in accordance with JIS 6251 / ISO 37 using an autograph (manufactured by Shimadzu Corporation) at a speed of 500 mm / min, and the maximum stress was recorded.
(c)撕裂強度 (c) Tear strength
從上述1製作的樣品板沖裁無刻痕的角形試片，用其進行撕裂強度試驗。試驗按照JIS 6252/ISO 34-1用自動立體測圖儀(日本島津製作所製)以500mm/分鐘的速度 進行拉伸，記錄最大應力。 An angular test piece without a notch was punched out from the sample plate prepared in 1 above, and a tear strength test was performed using it. Test in accordance with JIS 6252 / ISO 34-1 with an autostereograph (manufactured by Shimadzu Corporation) at a speed of 500 mm / min Perform stretching and record maximum stress.
(d)壓縮永久變形 (d) Compression set
使用上述1製作的樣品板按照JIS 6262/ISO 815測定25%壓縮永久變形。 A 25% compression set was measured in accordance with JIS 6262 / ISO 815 using the sample plate prepared in 1 above.
以上的結果如後述表所示。 The above results are shown in the following table.
5.耐洗滌劑性 5. Detergent resistance
將上述1製作的便座緩衝零件在下述洗滌劑中浸漬7天，將其後的變色程度按照上述3的試驗方法進行測定。 The toilet seat cushioning part produced in the above 1 was immersed in the following detergent for 7 days, and the degree of discoloration thereafter was measured according to the test method in the above 3.
酸系洗滌劑：Sunpole(日本金鳥股份有限公司) Acid detergent: Sunpole (Japan Golden Bird Co., Ltd.)
鹼系洗滌劑：Murin Forward(日本CXS股份有限公司) Alkali detergent: Murin Forward (CXS Japan)
氯系洗滌劑：Wide Haiter(日本花王股份有限公司) Chlorine detergent: Wide Haiter (Kao Corporation, Japan)
中性洗滌劑：Toilet Magiclean(日本花王股份有限公司) Neutral detergent: Toilet Magiclean (Japan Kao Corporation)
以上的結果如下表所示。 The above results are shown in the following table.
從表可知，添加根據本發明的抗氧化劑幾乎不會給樹脂的各種物性帶來影響。 As can be seen from the table, the addition of the antioxidant according to the present invention hardly affects various physical properties of the resin.
Claims (7)
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| JPS63130648A (en) * | 1986-11-21 | 1988-06-02 | Mitsubishi Petrochem Co Ltd | Polyolefin composition |
| JP3082333B2 (en) * | 1991-09-03 | 2000-08-28 | 住友化学工業株式会社 | Stabilized polyolefin composition |
| JP3377117B2 (en) * | 1993-10-21 | 2003-02-17 | 新日本石油化学株式会社 | Non-whitening polypropylene resin composition with excellent discoloration resistance |
| JPH10183423A (en) * | 1996-12-19 | 1998-07-14 | Grand Polymer:Kk | Polypropylene resin composition for fiber and its applications |
| US6613823B1 (en) * | 1998-10-21 | 2003-09-02 | Phillips Petroleum Company | Phosphite additives in polyolefins |
| JP4794724B2 (en) * | 2000-08-31 | 2011-10-19 | 三井化学株式会社 | Polyolefin resin composition for pipe and use thereof |
| US7759417B2 (en) * | 2006-05-17 | 2010-07-20 | Cytec Technology Corp. | Stabilizer compositions |
| WO2010000638A1 (en) * | 2008-07-02 | 2010-01-07 | Basf Se | Blends of stabilizers for aliphatic polyesters |
| CN103210130A (en) * | 2010-11-16 | 2013-07-17 | 株式会社Adeka | Method for stabilizing polymer for long term, method for producing nonwoven fabric, and method for producing elastomer composition |
| CN104558852A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
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| CN104558809A (en) * | 2014-12-19 | 2015-04-29 | 上海金发科技发展有限公司 | Thermo-oxidative-aging-resistant polypropylene composite and preparation method thereof |
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