JPH07109380A - Phenolic antioxidant composition - Google Patents
Phenolic antioxidant compositionInfo
- Publication number
- JPH07109380A JPH07109380A JP25401593A JP25401593A JPH07109380A JP H07109380 A JPH07109380 A JP H07109380A JP 25401593 A JP25401593 A JP 25401593A JP 25401593 A JP25401593 A JP 25401593A JP H07109380 A JPH07109380 A JP H07109380A
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- JP
- Japan
- Prior art keywords
- tert
- weight
- butyl
- phenolic antioxidant
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は熱可塑性樹脂の安定化に
優れ、特に変色の発生しにくいフェノール系酸化防止剤
組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenolic antioxidant composition which is excellent in the stability of a thermoplastic resin and is particularly resistant to discoloration.
【０００２】[0002]
【従来の技術】一般に熱可塑性樹脂は機械的性質に優
れ、融点以上の高温でフイルム，成形品，繊維など成形
加工して広く使用されている。成形加工時の熱可塑性樹
脂の劣化を防止し、さらに成形品の使用時における安定
性を向上させるために特に、２，６−ジ−第三ブチル−
ｐ−クレゾール（ＢＨＴ）のようなアルキル置換フェノ
ール系酸化防止剤が熱可塑性樹脂の酸化防止剤として広
く用いられている。2. Description of the Related Art Generally, a thermoplastic resin is excellent in mechanical properties and is widely used by forming a film, a molded product, a fiber and the like at a temperature higher than its melting point. In order to prevent deterioration of the thermoplastic resin during molding and further improve the stability of the molded product during use, 2,6-di-tert-butyl-
Alkyl-substituted phenolic antioxidants such as p-cresol (BHT) are widely used as antioxidants for thermoplastic resins.
【０００３】しかし、アルキル置換フェノール系酸化防
止剤を熱可塑性樹脂に配合した場合に、その成形品が常
温で次第に黄色あるいは褐色に着色することが知られて
おり、この現象は黄変と呼ばれている。これはアルキル
置換フェノール系酸化防止剤が酸化され、その結果生成
したキノン構造またはスチルベンキノン構造のような共
役二重結合を持つカルボニル化合物に起因するものであ
ることが良く知られている。例えば、２，６−ジ−第三
ブチル−ｐ−クレゾールは酸化されて３, ５, ３',５'
−テトラ−第三ブチル−４, ４' −スチルベンキノン
（以後ＳＢＱと略す）を生成する。このものは可視領域
の吸光係数が非常に大きいために、熱可塑性樹脂中に微
量生成しても黄色に着色する。とりわけ、ラジカル発生
剤（パーオキサイド）やヒンダードアミン系光安定剤，
アミン系帯電防止剤と共存した場合、またＮＯχ等の酸
化性の強いガスと接触した場合、黄変が著しく促進され
る。着色した成形品は商品価値が著しく失われるため、
黄変を防ぐことは非常に重要なことである。However, it is known that when an alkyl-substituted phenolic antioxidant is mixed with a thermoplastic resin, the molded product gradually becomes yellow or brown at room temperature, and this phenomenon is called yellowing. ing. It is well known that this is due to a carbonyl compound having a conjugated double bond such as a quinone structure or a stilbenequinone structure, which is generated as a result of oxidation of an alkyl-substituted phenolic antioxidant. For example, 2,6-di-tert-butyl-p-cresol is oxidized to 3,5,3 ', 5'.
-Tetra-tert-butyl-4,4'-stilbenequinone (hereinafter abbreviated as SBQ) is produced. Since this substance has a very large absorption coefficient in the visible region, it is colored yellow even if it is formed in a small amount in the thermoplastic resin. In particular, radical generators (peroxides) and hindered amine light stabilizers,
When it coexists with an amine-based antistatic agent, or when it comes into contact with a highly oxidizing gas such as NOx, yellowing is significantly promoted. Colored molded articles lose their commercial value significantly, so
Preventing yellowing is very important.
【０００４】アルキル置換フェノール系酸化防止剤の黄
変防止に有機ホスファイト化合物を添加する方法（特開
昭５０−５２１５２号公報，特開昭５０−１３９８３６
号公報）やポリオールやポリオールの脂肪酸エステルを
添加する方法（特開昭５８−２１３０３６号公報，特開
昭６２−２５２４４３号公報）が提案されている。しか
し、着色に対する防止効果は十分とは言えない。A method of adding an organic phosphite compound to prevent yellowing of an alkyl-substituted phenolic antioxidant (Japanese Patent Laid-Open Nos. 52521/1975 and 139836/1993).
JP-A-58-213036 and JP-A-62-252443, a method of adding a polyol or a fatty acid ester of a polyol has been proposed. However, the effect of preventing coloring is not sufficient.
【０００５】[0005]
【課題を解決するための手段】本発明者等は上記課題を
解決すべく鋭意検討の結果、アルキル置換フェノール系
酸化防止剤に特定のアミド化合物を配合した組成物はス
チルベンキノン構造を生成しにくいことを見い出し、本
発明に到達したものである。Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, the composition in which a specific amide compound is mixed with an alkyl-substituted phenolic antioxidant does not easily form a stilbenequinone structure. The present invention has been discovered and has reached the present invention.
【０００６】すなわち、本発明は、（Ａ）アルキル置換
フェノール系酸化防止剤１００重量部に対して（Ｂ）下
記一般式（１）で示されるアミド化合物２〜４０重量部
よりなること （但し、Ｒ1 は炭素数７〜２１のアルキル基，アルケニ
ル基を示し、ｍおよびｎはｍ＋ｎ＝２〜１０の関係にあ
る整数である。）を特徴とするフェノール系酸化防止剤
組成物である。That is, the present invention comprises (A) 2 to 40 parts by weight of an amide compound represented by the following general formula (1) with respect to 100 parts by weight of an alkyl-substituted phenolic antioxidant. (However, R 1 represents an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and m and n are integers in the relationship of m + n = 2 to 10.) A phenolic antioxidant composition characterized by the above-mentioned. is there.
【０００７】以下、本発明をさらに詳しく説明する。ア
ルキル置換フェノール系酸化防止剤としては例えば、
２，６−ジ第三ブチル−ｐ−クレゾール、２，６−ジフ
ェニル−４−オクタデシルオキシフェノール、ジステア
リル（３，５−ジ第三ブチル−４−ヒドロキシベンジ
ル）ホスホネート、４，４’−チオビス（６−第三ブチ
ル−ｍ−クレゾール）、２−オクチルチオ−４，６，−
ジ（３’，５’−ジヒドロキシフェノキシ）−ｓ−トリ
アジン、２，２’−メチレンビス（４−メチル−６−第
二ブチルフェノール）、２，２’−メチレンビス（４−
メチル−６−第三ブチルフェノール）、ビス［３，３−
ビス（４’−ヒドロキシ−３’−第三ブチルフェニル）
ブチリックアシッド］グリコールエステル、４，４’−
ブチリデンビス（６−第三ブチル−ｍ−クレゾール）、
２，２’−エチリデンビス（４，６−ジ第三ブチルフェ
ノール）、２，２’−エチリデンビス（４−第二ブチル
−６−第三ブチルフェノール）、２−第三ブチル−４−
メチル−６−（２’アクリロイルオキシ−３’−第三ブ
チル−５’−メチルベンジル）フェノール、ビス［２−
第三ブチル−４−メチル−６−（２’−ヒドロキシ−
３’−第三ブチル−５’−メチルベンジル）フェニル］
テレフタレート、１，１，３−トリス（２’−メチル−
４’−ヒドロキシ−５’−第三ブチルフェニル）ブタ
ン、１，３，５−トリス−２’，６’−ジメチル−３’
−ヒドロキシ−４’−第三ブチルベンジル）イソシアヌ
レート、１，３，５−トリス（３’，５’−ジ第三ブチ
ル−４’−ヒドロキシベンジル）イソシアヌレート、
１，３，５−トリス（３’，５’−ジ第三ブチル−４’
−ヒドロキシベンジル）−２，４，６−トリメチルベン
ゼン、オクタデシル−３−（３，５−ジ第三ブチル−４
−ヒドロキシフェニル）プロピオネート、テトラキス
［メチレン−３−（３，５−ジ第三ブチル−４−ヒドロ
キシフェニル）プロピオネート］メタン、２，２−チオ
ジエチレンビス［３−（３，５−ジ第三ブチル−４−ヒ
ドロキシフェニル）プロピオネート］、３，９−ビス
［１，１−ジメチル−２−［β−（３−第三ブチル−４
−ヒドロキシ−５−メチルフェニル）プロピオニルオキ
シ］エチル］−２，４，８，１０−テトラオキサスピロ
［５，５］ウンデカン等が挙げられる。特に、２，６−
ジ第三ブチル−ｐ−クレゾール、オクタデシル−３−
（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プ
ロピオネート、２，２’−メチレンビス（４−メチル−
６−第三ブチルフェノール）、４，４’−チオビス（６
−第三ブチル−ｍ−クレゾール）、テトラキス［メチレ
ン−３−（３，５−ジ第三ブチル−４−ヒドロキシフェ
ニル）プロピオネート］メタンが好ましい。The present invention will be described in more detail below. Examples of alkyl-substituted phenol-based antioxidants include:
2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6,-
Di (3 ', 5'-dihydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-
Methyl-6-tert-butylphenol), bis [3,3-
Bis (4'-hydroxy-3'-tert-butylphenyl)
Butyric acid] glycol ester, 4,4′-
Butylidene bis (6-tert-butyl-m-cresol),
2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-tert-butylphenol), 2-tert-butyl-4-
Methyl-6- (2'acryloyloxy-3'-tert-butyl-5'-methylbenzyl) phenol, bis [2-
Tert-Butyl-4-methyl-6- (2'-hydroxy-
3'-tert-butyl-5'-methylbenzyl) phenyl]
Terephthalate, 1,1,3-tris (2'-methyl-
4'-hydroxy-5'-tert-butylphenyl) butane, 1,3,5-tris-2 ', 6'-dimethyl-3'
-Hydroxy-4'-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanurate,
1,3,5-Tris (3 ', 5'-di-tert-butyl-4'
-Hydroxybenzyl) -2,4,6-trimethylbenzene, octadecyl-3- (3,5-ditert-butyl-4)
-Hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,2-thiodiethylenebis [3- (3,5-di-tert-butyl) -4-Hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4]
-Hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Especially 2,6-
Di-tert-butyl-p-cresol, octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-)
6-tert-butylphenol), 4,4′-thiobis (6
-Tert-butyl-m-cresol), tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane are preferred.
【０００８】本発明の組成物における下記一般式（１） （但し、Ｒ1 は炭素は炭素数７〜２１のアルキル基，ア
ルケニル基を示し、ｍおよびｎはｍ＋ｎ＝２〜１０の関
係にある整数である。）で表されるアミド化合物として
は、特にＲ1 がアルキル基、特にＲ1 がアルキル基、ｍ
＝ｎ＝１，ｍ＝ｎ＝２のものが好ましい。In the composition of the present invention, the following general formula (1) (Wherein R1 is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and m and n are integers having a relation of m + n = 2 to 10). 1 is an alkyl group, especially R1 is an alkyl group, m
= N = 1, m = n = 2 are preferable.
【０００９】アミド化合物の具体例としては、下記の化
合物が挙げられる。 Specific examples of the amide compound include the following compounds.
【００１０】アルキル置換フェノール系酸化防止剤１０
０重量部に対し、アミド化合物は２〜４０重量部、好ま
しくは５〜２０重量部である。アミド化合物の配合量が
４０重量部以上ではアルキル置換フェノール系酸化防止
剤の酸化防止効果に悪影響を及ぼすことがある。１重量
部以下の配合では本発明の効果を十分に達成できない。Alkyl-substituted phenolic antioxidant 10
The amide compound is 2 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 0 parts by weight. If the amount of the amide compound is 40 parts by weight or more, the antioxidant effect of the alkyl-substituted phenol-based antioxidant may be adversely affected. If the amount is 1 part by weight or less, the effect of the present invention cannot be sufficiently achieved.
【００１１】また本発明のアルキル置換フェノール系酸
化防止剤組成物の熱可塑性樹脂に対する添加量は熱可塑
性樹脂１００重量部に対し０．０１〜１．０重量部であ
る。The addition amount of the alkyl-substituted phenolic antioxidant composition of the present invention to the thermoplastic resin is 0.01 to 1.0 part by weight based on 100 parts by weight of the thermoplastic resin.
【００１２】本発明組成物の製造方法は、アルキル置換
フェノール系酸化防止剤とアミド化合物を溶融混合ある
いはアルコール等の有機溶媒中で溶解混合の後、溶媒を
除去して得られる。また熱可塑性樹脂へ配合の際に両者
を同時添加（アミド化合物を先に添加する方がより好ま
しい）でも良い。The method for producing the composition of the present invention can be obtained by melt-mixing an alkyl-substituted phenolic antioxidant and an amide compound or by dissolving and mixing in an organic solvent such as alcohol, and then removing the solvent. Further, both may be simultaneously added (more preferably added first with the amide compound) at the time of blending with the thermoplastic resin.
【００１３】本発明のアルキル置換フェノール系酸化防
止剤組成物が適用できる熱可塑性樹脂は、ポリオレフィ
ン、スチレン系樹脂、合成ゴム、ポリ塩化ビニル、ポリ
アミド、ポリカーボネート、ポリフェニレンオキサイ
ド、ポリエステル，エラストマー等が挙げられる。The thermoplastic resin to which the alkyl-substituted phenol antioxidant composition of the present invention can be applied includes polyolefin, styrene resin, synthetic rubber, polyvinyl chloride, polyamide, polycarbonate, polyphenylene oxide, polyester, elastomer and the like. .
【００１４】また本発明組成物には、その特性を害さな
い限り、他の添加剤、例えば中和剤、チオエーテル系酸
化防止剤、ホスファイト系酸化防止剤、重金属不活性化
剤、光安定剤、滑剤、造核剤、帯電防止剤、離型剤、可
塑剤、プロセス油、潤滑油、フィラー、顔料、防かび剤
等を添加することができる。とりわけホスファイト系酸
化防止剤と併用使用すると変色抑制に効果的である。In the composition of the present invention, other additives such as a neutralizing agent, a thioether antioxidant, a phosphite antioxidant, a heavy metal deactivator, and a light stabilizer may be added to the composition of the present invention as long as the characteristics thereof are not impaired. Further, a lubricant, a nucleating agent, an antistatic agent, a release agent, a plasticizer, a process oil, a lubricating oil, a filler, a pigment, an antifungal agent and the like can be added. In particular, when used in combination with a phosphite type antioxidant, it is effective in suppressing discoloration.
【００１５】本発明組成物の熱可塑性樹脂への配合は、
一軸押出機、二軸押出機、バンバリーミキサー、ロー
ル、ニーダー等の通常の混練機を用いて加熱溶融状態で
混練することによって得られる。以上本発明のフェノー
ル系酸化防止剤組成物を配合した熱可塑性樹脂は極めて
変色が少なく、優れた酸化防止効果を有している。The blending of the composition of the present invention with a thermoplastic resin is
It can be obtained by kneading in a heat-melted state using an ordinary kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll and a kneader. As described above, the thermoplastic resin containing the phenolic antioxidant composition of the present invention has very little discoloration and has an excellent antioxidant effect.
【００１６】[0016]
【実施例】以下実施例を挙げ、本発明をさらに具体的に
説明する。 実施例−１〜３ 結晶性エチレン−プロピレンブロック共重合体（エチレ
ン含有量：７．２重量％、メルトインデックス：３．０
ｇ／１０分）の粉末１００重量部に対し、ステアリン酸
カルシウム０．０５重量部、フェノール系酸化防止剤と
して２，６−ジ−第三ブチル−Ｐ−クレゾール（ＢＨ
Ｔ）０．５重量部とアミド化合物としてラウリルジエタ
ノールアミドを表−１に示す０．０１重量部（実施例−
１），０．０２５重量部（実施例−２）および０．０５
重量部（実施例−３）を混合した。さらに黄変を促進さ
せる目的でヒンダードアミン系光安定剤のビス（２，
２，６，６−テトラメチル−４−ピペリジル）セバケー
ト０．３重量部とラジカル発生剤の２，５−ジメチル−
２，５−ジ−第三ブチル−パーオキシヘキサン０．０２
５重量部を加えてヘンシェルミキサーで混合した。 混
合後、ブラベンダー社製ブラベンダープラスチコーダー
で温度２００℃、ローラー回転数５０ｒｐｍで８分間溶
融混練した。次に混練物から厚さ１mmのプレスートを作
成し、シート作成直後から変色（黄変）状況をスガ試験
機製カラーコンピューターＳＭ５ＣＨを使用してイエロ
ーネスインデックス（以後ＹＩと略す）で経時追跡し
た。また３０日経時シートについては、黄変の原因物質
であるＳＢＱの発生量を調べるため、同シートをソック
スレー抽出器を用いて、アセトン溶媒で7 時間還流抽出
し、抽出液を島津製作所製フォトダイオードアレイ紫外
−可視検出器（ＳＰＤ- Ｍ６Ａ型）を接続した液体クロ
マトグラフィーで分析した。結果を表−１に示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. Examples-1 to 3 Crystalline ethylene-propylene block copolymer (ethylene content: 7.2% by weight, melt index: 3.0
(g / 10 min) 100 parts by weight of powder, 0.05 parts by weight of calcium stearate, 2,6-di-tert-butyl-P-cresol (BH as a phenolic antioxidant
T) 0.5 part by weight and 0.01 part by weight of lauryl diethanolamide as an amide compound shown in Table 1 (Example-
1), 0.025 parts by weight (Example-2) and 0.05
Parts by weight (Example-3) were mixed. Further, for the purpose of promoting yellowing, the hindered amine light stabilizer bis (2,
0.3 parts by weight of 2,6,6-tetramethyl-4-piperidyl) sebacate and 2,5-dimethyl-radical generator
2,5-di-tert-butyl-peroxyhexane 0.02
5 parts by weight were added and mixed with a Henschel mixer. After mixing, the mixture was melt-kneaded for 8 minutes at a temperature of 200 ° C. and a roller rotation speed of 50 rpm with a Brabender Plasticorder made by Brabender. Next, a presto having a thickness of 1 mm was prepared from the kneaded product, and the discoloration (yellowing) state was immediately followed by a yellowness index (hereinafter abbreviated as YI) using a color computer SM5CH manufactured by Suga Test Instruments immediately after the sheet was prepared. In addition, in order to investigate the amount of SBQ, which is the causative agent of yellowing, for the 30-day-old sheet, the sheet was reflux-extracted with an acetone solvent for 7 hours using a Soxhlet extractor, and the extract was used by a Shimadzu photodiode. It was analyzed by liquid chromatography connected to an array UV-visible detector (SPD-M6A type). The results are shown in Table-1.
【００１７】実施例−４ アミド化合物をラウリルジエタノールアミドに替えてス
テアリルジエタノールアミド０．０５重量部を添加した
他は、実施例−１と同様に行った。結果を表−１に示
す。Example 4 Example 4 was repeated except that the amide compound was replaced with lauryl diethanol amide and 0.05 part by weight of stearyl diethanol amide was added. The results are shown in Table-1.
【００１８】比較例−１ アミド化合物のラウリルジエタノールアミドを添加しな
い他は、実施例−１と同様に行った。結果を表−１に示
す。 この場合は経時に伴う黄変が顕著である。Comparative Example-1 The procedure of Example-1 was repeated except that the amide compound, lauryldiethanolamide, was not added. The results are shown in Table-1. In this case, yellowing with time is remarkable.
【００１９】比較例−２ ラウリルジエタノールアミドに替えてグリセリンモノス
テアレート０．０５重量部を添加した他は、実施例−１
と同様に行った。結果を表−１に示す。この場合は殆ど
黄変抑制効果が認められない。Comparative Example-2 Example 1 except that 0.05 part by weight of glycerin monostearate was added instead of lauryl diethanolamide.
I went the same way. The results are shown in Table-1. In this case, almost no effect of suppressing yellowing is observed.
【００２０】比較例−３ ラウリルジエタノールアミドに替えてラウリルモノエタ
ノールアミド０．０５重量部を添加した他は、実施例−
１と同様に行った。結果を表−１に示す。この場合は経
時初期で若干黄変抑制効果認められるが、経時に伴い黄
変抑制効果が認められなくなる。Comparative Example-3 Example 2 was repeated except that 0.05 part by weight of lauryl monoethanolamide was added instead of lauryl diethanolamide.
The same procedure as 1 was performed. The results are shown in Table-1. In this case, the yellowing-suppressing effect is slightly observed in the early stage of aging, but the yellowing-suppressing effect is not observed over time.
【００２１】比較例−４ ラウリルジエタノールアミドをＮ，Ｎ−ビスヒドロキシ
エチルステアリルアミン０．０５重量部に変更した他
は、実施例−１と同様に行った。結果を表−１に示す。
この場合は黄変促進作用が認められる。Comparative Example-4 The procedure of Example-1 was repeated, except that lauryldiethanolamide was changed to 0.05 parts by weight of N, N-bishydroxyethylstearylamine. The results are shown in Table-1.
In this case, a yellowing promoting action is recognized.
【００２２】比較例−５ ラウリルジエタノールアミドに替えてトリス（２，４−
ジ−第三ブチルフェニル）ホスファイト０．０５重量部
を添加した他は、実施例−１と同様に行った。結果を表
−１に示す。この場合は経時初期で黄変抑制効果認めら
れるが、経時が長くなると抑制効果が著しく低下してい
る。Comparative Example 5 Instead of lauryl diethanolamide, tris (2,4-
Example 1 was repeated except that 0.05 part by weight of di-tert-butylphenyl) phosphite was added. The results are shown in Table-1. In this case, the yellowing-suppressing effect is recognized at the beginning of the aging, but the suppressing effect remarkably decreases with the lapse of time.
【００２３】実施例−５ フェノール系酸化防止剤を２，６−ジ−第三ブチル−ｐ
−クレゾールに替えて２，２’−メチレンビス（４−メ
チル−６−第三ブチルフェノール）０．５重量部を添加
し、ラウリルジエタノールアミドを０．１重量部添加し
た他は、実施例−１と同様に行った。この場合はＹＩの
み経時追跡した。結果を表−１に示す。Example 5 A phenolic antioxidant was added to 2,6-di-tert-butyl-p.
-In place of cresol, 0.5 parts by weight of 2,2'-methylenebis (4-methyl-6-tert-butylphenol) was added, and 0.1 part by weight of lauryl diethanolamide was added. I went the same way. In this case, only YI was followed over time. The results are shown in Table-1.
【００２４】比較例−６ アミド化合物のラウリルジエタノールアミドを添加しな
い他は、実施例−５と同様に行った。結果を表−１に示
す。この場合は直後から着色（黒褐色）が顕著である。Comparative Example 6 The procedure of Example 5 was repeated, except that the amide compound, lauryl diethanolamide, was not added. The results are shown in Table-1. In this case, coloring (blackish brown) is remarkable immediately after.
【００２５】 [0025]
【００２６】尚、表中で使用したフェノール系酸化防止
剤、アミド化合物等は以下のとおりである。 Ａ−１ ： 2,6-ジ- 第三ブチル- ｐ−クレゾール(BH
T) Ａ−２ ： 2,2'- メチレンビス(4- メチル-6- 第三ブ
チルフェノール) Ｂ−１ ： ラウリルジエタノールアミド Ｂ−２ ： ステアリルジエタノールアミド Ｃ−１ ： グリセリンモノステアレート Ｃ−２ ： ラウリルモノエタノールアミド Ｃ−３ ： N,N-ビスヒドロキシエチルステアリルアミ
ン Ｃ−４ ： トリス(2,4- ジ- 第三ブチルフェニル) ホ
スファイトThe phenolic antioxidants and amide compounds used in the table are as follows. A-1: 2,6-di-tert-butyl-p-cresol (BH
T) A-2: 2,2′-methylenebis (4-methyl-6-tert-butylphenol) B-1: lauryldiethanolamide B-2: stearyldiethanolamide C-1: glycerin monostearate C-2: lauryl Monoethanolamide C-3: N, N-bishydroxyethylstearylamine C-4: Tris (2,4-di-tert-butylphenyl) phosphite
【００２７】実施例−６ 結晶性エチレン−プロピレンブロック共重合体（エチレ
ン含有量：７．２重量％、メルトインデックス：３．０
ｇ／１０分）の粉末１００重量部に対し、ステアリン酸
カルシウム０．０５重量部、フェノール系酸化防止剤と
して２，６−ジ−第三ブチル−Ｐ−クレゾール（ＢＨ
Ｔ）０．５重量部とアミド化合物としてラウリルジエタ
ノールアミドを０．１重量部添加した。さらに黄変を促
進させる目的でヒンダードアミン系光安定剤のビス
（２，２，６，６−テトラメチル−４−ピペリジル）セ
バケート０．３重量部を加えてヘンシェルミキサーで混
合した。 混合後、ブラベンダー社製ブラベンダープラ
スチコーダーで温度２００℃、ローラー回転数５０ｒｐ
ｍで８分間溶融混練した。次に混練物から厚さ１mmのプ
レスートを作成し、このシート（４cm×３cm）をＪＩＳ
−Ｌ−０８５５−１９６７（酸化窒素ガスに対する染色
堅ろう度試験方法）に準拠して発生させた酸化窒素ガス
（雰囲気温度：５０℃）に１時間暴露させる。 酸化窒
素ガス暴露を終えたシートは水洗の後、変色（黄変）状
況をスガ試験機製カラーコンピューターＳＭ５ＣＨを使
用してＹＩで経時（室温で）追跡した。 結果を表−２
に示す。Example 6 Crystalline ethylene-propylene block copolymer (ethylene content: 7.2% by weight, melt index: 3.0)
(g / 10 min) 100 parts by weight of powder, 0.05 parts by weight of calcium stearate, 2,6-di-tert-butyl-P-cresol (BH as a phenolic antioxidant
T) 0.5 part by weight and 0.1 part by weight of lauryl diethanolamide as an amide compound were added. Further, for the purpose of promoting yellowing, 0.3 part by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate as a hindered amine light stabilizer was added and mixed with a Henschel mixer. After mixing, the temperature is 200 ° C and the number of rotations of the roller is 50 rp with a Brabender Plasticorder made by Brabender.
melt kneading for 8 minutes. Next, make a 1 mm thick presto from the kneaded material, and use this sheet (4 cm x 3 cm) according to JIS.
It is exposed to a nitric oxide gas (atmosphere temperature: 50 ° C.) generated according to L-0855-1967 (testing method for dye fastness to nitric oxide gas) for 1 hour. After the sheet that had been exposed to the nitric oxide gas was washed with water, the discoloration (yellowing) state was tracked over time (at room temperature) by YI using a color computer SM5CH manufactured by Suga Test Instruments. The results are shown in Table-2.
Shown in.
【００２８】比較例−７ アミド化合物のラウリルジエタノールアミドを添加しな
い他は、実施例−６と同様に行った。結果を表−２に示
す。この場合は経時に伴う黄変が顕著である。Comparative Example-7 The procedure of Example-6 was repeated except that the amide compound, lauryldiethanolamide, was not added. The results are shown in Table-2. In this case, yellowing with time is remarkable.
【００２９】比較例−８ ラウリルジエタノールアミドに替えてグリセリンモノス
テアレート０．１重量部を添加した他は、実施例−６と
同様に行った。結果を表−２に示す。 この場合は殆ど
黄変抑制効果が認められれない。Comparative Example-8 The procedure of Example-6 was repeated, except that 0.1 part by weight of glycerin monostearate was added instead of lauryl diethanolamide. The results are shown in Table-2. In this case, almost no yellowing inhibitory effect is observed.
【００３０】 [0030]
【００３１】[0031]
【発明の効果】本発明により、熱可塑性樹脂に配合され
たフェノール系酸化防止剤による変色（黄変）を著しく
抑制することができる。EFFECTS OF THE INVENTION According to the present invention, discoloration (yellowing) due to a phenolic antioxidant incorporated in a thermoplastic resin can be significantly suppressed.
Claims (1)
剤１００重量部に対して（Ｂ）下記一般式（１）で示さ
れるアミド化合物２〜４０重量部よりなること （但し、Ｒ1 は炭素数７〜２１のアルキル基，アルケニ
ル基を示し、ｍおよびｎはｍ＋ｎ＝２〜１０の関係にあ
る整数である。）を特徴とするフェノール系酸化防止剤
組成物。1. To 100 parts by weight of an alkyl-substituted phenolic antioxidant (A), 2 to 40 parts by weight of (B) an amide compound represented by the following general formula (1). (Wherein, R 1 represents an alkyl group, an alkenyl group of 7 to 21 carbon atoms, m and n are integers having a relationship of m + n = 2 to 10.) Phenolic antioxidant composition characterized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25401593A JP3296051B2 (en) | 1993-10-12 | 1993-10-12 | Phenolic antioxidant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25401593A JP3296051B2 (en) | 1993-10-12 | 1993-10-12 | Phenolic antioxidant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109380A true JPH07109380A (en) | 1995-04-25 |
| JP3296051B2 JP3296051B2 (en) | 2002-06-24 |
Family
ID=17259073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25401593A Expired - Fee Related JP3296051B2 (en) | 1993-10-12 | 1993-10-12 | Phenolic antioxidant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3296051B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576695B1 (en) * | 1997-09-02 | 2003-06-10 | Ajinomoto Co., Inc. | Thermoplastic resin composition comprising polyglycerin fatty acid esters, and resin molded article obtained therefrom |
| JP2011246564A (en) * | 2010-05-26 | 2011-12-08 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded article obtained from the same |
| WO2014021023A1 (en) | 2012-07-31 | 2014-02-06 | 株式会社Adeka | Latent additive and composition containing latent additive |
| JP2022146578A (en) * | 2021-03-22 | 2022-10-05 | 雪ヶ谷化学工業株式会社 | Discoloration-prevented natural rubber latex sponge and method for producing the same |
-
1993
- 1993-10-12 JP JP25401593A patent/JP3296051B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6576695B1 (en) * | 1997-09-02 | 2003-06-10 | Ajinomoto Co., Inc. | Thermoplastic resin composition comprising polyglycerin fatty acid esters, and resin molded article obtained therefrom |
| JP2011246564A (en) * | 2010-05-26 | 2011-12-08 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded article obtained from the same |
| WO2014021023A1 (en) | 2012-07-31 | 2014-02-06 | 株式会社Adeka | Latent additive and composition containing latent additive |
| KR20150040797A (en) | 2012-07-31 | 2015-04-15 | 가부시키가이샤 아데카 | Latent additive and composition containing latent additive |
| US9777138B2 (en) | 2012-07-31 | 2017-10-03 | Adeka Corporation | Latent additive and composition containing latent additive |
| KR20200125749A (en) | 2012-07-31 | 2020-11-04 | 가부시키가이샤 아데카 | Latent additive and composition containing latent additive |
| EP3753997A1 (en) | 2012-07-31 | 2020-12-23 | Adeka Corporation | Latent additive and composition containing latent additive |
| JP2022146578A (en) * | 2021-03-22 | 2022-10-05 | 雪ヶ谷化学工業株式会社 | Discoloration-prevented natural rubber latex sponge and method for producing the same |
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| Publication number | Publication date |
|---|---|
| JP3296051B2 (en) | 2002-06-24 |
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