JP5615425B2 - Flame retardant compositions of phosphinates and nitroxyl derivatives - Google Patents

Description

  The present invention relates to a flame retardant polymer composition comprising a phosphinate in combination with a so-called sterically hindered nitroxyl derivative. The composition is particularly useful in the production of flame retardant compositions based on thermoplastic polymers, especially polyolefin homopolymers and copolymers and copolymers with vinyl monomers.

  A flame retardant is added to the polymer material (synthetic or natural) to enhance the flame retardant properties of the polymer. Depending on their composition, the flame retardants are either in the solid phase, liquid phase or gas phase, chemically, for example as a foam by liberation of nitrogen, and / or physically, for example by the generation of a foam coating. Can work. Flame retardants interfere during certain stages of the combustion process, for example during heating, decomposition, ignition or flame diffusion.

  There remains a need for flame retardant compositions with improved properties that can be used with different polymer substrates. Regulations have become more stringent as a result of increased standards regarding safety and environmental requirements. In particular, known halogen-containing flame retardants no longer meet all requirements. Accordingly, halogen-free flame retardancy is preferred from the perspective of their better performance, particularly with respect to smoke concentrations associated with fire. Improved thermal stability and low corrosive behavior are further advantages of halogen-free flame retardant compositions.

  It has been surprisingly found that when phosphinates are added to the polymer substrate in combination with so-called sterically hindered amines, polymer compositions with excellent flame retardant properties are produced.

  Further advantages of the composition of the present invention are improved electrical properties (CTI = comparative tracking index) and improved lightfastness compared to the use of halogenated FR systems. Furthermore, the flame retardant composition is resistant to so-called leaching. Contact with water does not diminish their flame retardant activity.

  It has been surprisingly found that by using the flame retardant composition according to the present invention, halogen-containing flame retardants such as decabromodiphenyl oxide, antimony compounds, and fillers can be largely reduced or replaced.

（式中、
Ｒ¹およびＲ²のうちの一方は、水素もしくはＣ₁〜Ｃ₈アルキルを表す；またはＲ¹およびＲ²はどちらもＣ₁〜Ｃ₈アルキルを表す；そして
Ｒ³は、Ｃ₁〜Ｃ₁₀アルキレン、フェニレンによって中断されたＣ₂〜Ｃ₁₀アルキレン、フェニレン、（Ｃ₁〜Ｃ₄アルキル）_1〜3フェニレン、またはフェニル−Ｃ₁〜Ｃ₄アルキレンを表す）によって表されるホスフィン酸の塩；
ｂ）２，２，６，６−テトラアルキルピペリジン−１−オキシド、１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、１−アルコキシ−２，２，６，６−テトラアルキルピペリジン、１−アシルオキシ−２，２，６，６−ピペリジン、１−ヒドロキシ−２，２，６，６−テトラアルキルピペラジン、１−アルコキシ−２，２，６，６−テトラアルキルピペラジン、および１−アシルオキシ−２，２，６，６−ピペラジンからなる群から選択されるテトラアルキルピペリジンまたはテトラアルキルピペラジン誘導体；ならびに
ｃ）ポリマー基体
を含む難燃剤組成物に関する。 The present invention provides compositions, in particular
a) Structural formula

(Where
One of R ¹ and R ² represents hydrogen or C ₁ -C ₈ alkyl; or R ¹ and R ² both represent C ₁ -C ₈ alkyl; and R ³ represents C ₁ -C ₁₀ A salt of phosphinic acid represented by alkylene, C ₂ -C ₁₀ alkylene interrupted by phenylene, phenylene, (C ₁ -C ₄ alkyl) _1-3 phenylene, or phenyl-C ₁ -C ₄ alkylene);
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6-piperidine, 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2,6,6-tetraalkylpiperazine, and 1-acyloxy -A flame retardant composition comprising a tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the group consisting of 2,2,6,6-piperazine; and c) a polymer substrate.

  The above-defined composition for use as a flame retardant is another embodiment of the present invention.

によって表されるジエチルホスフィン酸（Ｉ）のアルミニウム塩
ｂ）２，２，６，６−テトラアルキルピペリジン−１−オキシド、１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、１−アルコキシ−２，２，６，６−テトラアルキルピペリジンおよび１−アシルオキシ−２，２，６，６−ピペリジンからなる群から選択されるテトラアルキルピペリジン誘導体；および
ｃ）熱可塑性ポリマー基体
を含む。 A preferred embodiment of the present invention relates to a composition, in particular a flame retardant composition, which composition comprises a) formula

An aluminum salt of diethylphosphinic acid (I) represented by b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy -A tetraalkylpiperidine derivative selected from the group consisting of 2,2,6,6-tetraalkylpiperidine and 1-acyloxy-2,2,6,6-piperidine; and c) a thermoplastic polymer substrate.

  The composition according to the invention exhibits excellent flame retardant properties with low concentrations of components a) and b). Depending on the concentration of components a) and b) in the polymer substrate, V-2 evaluation by UL-94 (Underwriter's Laboratories Subject 94) and other excellent evaluations in related test methods are obtained.

As defined above, the composition comprises the following components:
Ingredient a)
The term phosphinic acid also includes within its scope the derivative of phosphinic acid, H ₂ P (═O) OH, wherein one or two hydrogen atoms bonded directly to the phosphorus atom are C ₁ -C _8. Substituted by an organic substituent such as alkyl.

The term phosphinic acid also includes within its scope the tautomeric form HP (OH) ₂ , wherein the hydrogen atom directly bonded to the phosphorus atom is replaced by an organic substituent such as C ₁ -C ₈ alkyl. ing.

  The term phosphinic acid salt preferably includes within its scope metal salts such as alkali metal or alkaline earth metal salts such as sodium, potassium, magnesium or calcium salts or iron (II), iron (III), zinc Or a boron salt is included.

R ¹ and R ² defined as C ₁ -C ₈ alkyl are linear or, where possible, branched C ₁ -C ₈ alkyl, for example methyl, ethyl, n-propyl, n-butyl , Sec-butyl, tert-butyl, n-hexyl, n-octyl or 2-ethylhexyl.

R ³ defined as C ₁ -C ₁₀ alkylene is linear or, where possible, branched C ₁ -C ₁₀ alkylene, such as methylene, ethylene, 1,2- or 1,3-propylene or 1 , 2-, 1,3- or 1,4-butylene.

の二価基であり、式中、点線は炭素原子の結合を指す。 R ³ defined as C ₂ -C ₁₀ alkylene interrupted by phenylene is, for example, a partial formula

In the formula, a dotted line indicates a bond of carbon atoms.

R ³ defined as phenylene is 1,2-, 1,3- or 1,4-phenylene.

R ³ defined as (C ₁ -C ₄ alkyl) _1-3 phenylene is, for example, 1,2-, 1,3- or 1,4-phenylene substituted with 1 to 3 methyl or ethyl groups It is.

R ³ defined as phenyl-C ₁ -C ₄ alkylene is, for example, _{one of} the aforementioned C ₁ -C ₈ alkyl groups substituted by phenyl.

  According to a preferred embodiment, the composition comprises an aluminum salt of diethylphosphinic acid.

According to another embodiment, the term salt is non-metallic salts, e.g., phosphinic acid, ammonia, amines or amides, such as (C ₁ -C _{4 ^{alkyl) 4 N +, (C 1}} ~C 4 alkyl) ₃ NH ⁺ , (C ₂ -C ₄ alkyl OH) ₄ N ⁺ , (C ₂ -C ₄ alkyl OH) ₃ NH ⁺ , (C ₂ -C ₄ alkyl OH) ₂ N (CH ₃ ) ₂ ⁺ , (C ₂ -C ₄ alkyl ^{_{OH) 2 NHCH 3 +, (}} C 6 H 5) 4 N +, (C 6 H 5) 3 NH +, (C 6 H 5 CH 3) 4 N +, (C 6 H 5 CH ₃ ) Including acid addition salts obtained by reaction with ₃ NH ⁺ , NH ₄ ⁺ , melamine or guanidine salts.

Among the acid addition salts, ammonium, (C ₁ -C ₄ alkyl) _1-4 ammonium or (2-hydroxyethyl) _1-4 ammonium, such as tetramethylammonium, tetraethylammonium, 2-hydroxyethyltrimethylammonium, melamine or guanidine A salt is particularly preferred.

によって表され、
（式中、
Ｒ¹およびＲ²のうちの一方は水素もしくはＣ₁〜Ｃ₈アルキルを表す；またはＲ¹およびＲ²はどちらもＣ₁〜Ｃ₈アルキルを表す；
Ｍは、（Ｃ₁〜Ｃ₄アルキル）₄Ｎ、（Ｃ₁〜Ｃ₄アルキル）₃ＮＨ、（Ｃ₂〜Ｃ₄アルキルＯＨ）₄Ｎ、（Ｃ₂〜Ｃ₄アルキルＯＨ）₃ＮＨ、（Ｃ₂〜Ｃ₄アルキルＯＨ）₂Ｎ（ＣＨ₃）₂、（Ｃ₂〜Ｃ₄アルキルＯＨ）₂ＮＨＣＨ₃、（Ｃ₆Ｈ₅）₄Ｎ、（Ｃ₆Ｈ₅）₃ＮＨ、（Ｃ₆Ｈ₅ＣＨ₃）₄Ｎ、（Ｃ₆Ｈ₅ＣＨ₃）₃ＮＨ、ＮＨ₄、メラミン、グアニジン、アルカリ金属もしくはアルカリ土類金属イオン、またはアルミニウム、亜鉛、鉄もしくはホウ素イオンを表す；
ｍは１〜３の数であり、Ｍ上の正電荷の数を示す；そして
ｎは１〜３の数であり、Ｍ^m+に対応するホスフィン酸アニオンの数を示す。 According to a particularly preferred embodiment, the salt of phosphinic acid (I) has the formula

Represented by
(Where
One of R ¹ and R ² represents hydrogen or C ₁ -C ₈ alkyl; or R ¹ and R ² both represent C ₁ -C ₈ alkyl;
M is (C ₁ -C ₄ alkyl) ₄ N, (C ₁ -C ₄ alkyl) ₃ NH, (C ₂ -C ₄ alkyl OH) ₄ N, (C ₂ -C ₄ alkyl OH) ₃ NH, ( C ₂ -C ₄ alkyl OH) ₂ N (CH ₃ ) ₂ , (C ₂ -C ₄ alkyl OH) ₂ NHCH ₃ , (C ₆ H ₅ ) ₄ N, (C ₆ H ₅ ) ₃ NH, (C ₆ H ₅ CH ₃ ) ₄ N, (C ₆ H ₅ CH ₃ ) ₃ NH, NH ₄ , melamine, guanidine, alkali metal or alkaline earth metal ion, or aluminum, zinc, iron or boron ion;
m is a number from 1 to 3, indicating the number of positive charges on M; and n is a number from 1 to 3, indicating the number of phosphinic acid anions corresponding to M ^{m +} .

によって表される。 According to a particularly preferred embodiment, the salt of phosphinic acid (I) of component a) has the formula

Represented by

  Component a) is preferably in the flame retardant composition according to the invention in an amount of 0.1 to 45.0% by weight, preferably 1 to 30.0% by weight, based on the weight basis of the polymer substrate component c). And component b) is preferably included in an amount of 0.05 to 5.0% by weight, preferably 0.1 to 2.0% by weight. The preferred ratio of components a): b) is 50: 1 to 1: 5, preferably 20: 1 to 1: 2.

Further embodiments of the invention include:
a) where
One of R ¹ and R ² represents hydrogen or C ₁ -C ₈ alkyl; or R ¹ and R ² both represent C ₁ -C ₈ alkyl; and R ³ represents C ₁ -C ₁₀ alkylene , C ₂ -C ₁₀ alkylene interrupted by phenylene, phenylene, (C ₁ -C ₄ alkyl) _1-3 phenylene, or phenyl-C ₁ -C ₄ alkylene, according to structural formula (I) or (II) Phosphinic acid salts represented; and b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2 , 6,6-tetraalkylpiperidine and a mixture comprising a tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6-piperidine.

  The mixture is useful for imparting flame retardancy to the polymer substrate.

  A further embodiment of the invention relates to a method of imparting flame retardancy to a polymer substrate, comprising adding to the polymer substrate of component c) a mixture of components a) and b) as defined above.

Component b)
Suitable tetraalkylpiperidine or tetraalkylpiperazine derivatives are 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2, 2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6-piperidine, 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2,6, It is selected from the group consisting of 6-tetraalkylpiperazine and 1-acyloxy-2,2,6,6-piperazine.

によって表すことができ、
式中、Ｒ₁〜Ｒ₄は、Ｃ₁〜Ｃ₄アルキル、好ましくはメチルまたはエチルを表す。好ましい実施形態によれば、Ｒ₁およびＲ₂の一方ならびにＲ₃およびＲ₄の一方はエチルを表し、もう一方はメチルを表すか、あるいはＲ₁〜Ｒ₄はすべてメチルを表す；そして
Ｅは、水素、Ｃ₁〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキルもしくはＣ₂〜Ｃ₂₀アルキル、更なる置換基を有するＣ₅〜Ｃ₆シクロアルキルもしくはＣ₂〜Ｃ₂₀アルケニルを表す；またはＣ₁〜Ｃ₂₀モノカルボン酸またはＣ₂〜Ｃ₂₀ジカルボン酸のアシル基を表す。 Such compounds have the partial formula

Can be represented by
In the formula, R _{1 to} R ₄ represent C _{1 to} C ₄ alkyl, preferably methyl or ethyl. According to a preferred embodiment, _one of R ₁ and R ₂ and one of R ₃ and R ₄ represents ethyl and the other represents methyl, or R _{1 to} R ₄ all represent methyl; , hydrogen, C ₁ -C ₂₀ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkyl represents C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl having further substituents; or C ₁ -C represents a ₂₀ monocarboxylic acids or C ₂ -C ₂₀ acyl group of a dicarboxylic acid.

  In the compound corresponding to the partial formula a, one of the dotted lines at the 4-position of piperidine represents a bond to hydrogen or an N substituent, and the other represents a bond to an O substituent or a C substituent.

  Alternatively, the dotted line at the 4-position of piperidine both represents a bond to hydrogen, an O or C substituent, or represents a double bond to oxygen.

  In the compound corresponding to partial formula b, the nitrogen at the 4-position of piperazine is bonded to hydrogen or a carbon substituent.

A typical structural formula is described below:

In these compounds (A) to (R), E represents hydrogen, C _{1 to} C ₂₀ alkyl, C _{5 to} C ₆ cycloalkyl or C _{2 to} C ₂₀ alkyl, and C _{5 to} C ₆ cycloalkyl having a further substituent. Or represents a C ₂ -C ₂₀ alkenyl; or represents an acyl group of a C ₁ -C ₂₀ monocarboxylic acid or C ₂ -C ₂₀ dicarboxylic acid; or alternatively, a> N-O-E group is> N Substituted with -O group.

  Alkyl is linear or branched, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

  Cycloalkyl groups include cyclopentyl and cyclohexyl; typical cycloalkenyl groups include cyclohexenyl; while typical aralkyl groups include benzyl, alpha-methyl-benzyl, alpha, alpha-dimethyl. Examples include benzyl or phenethyl.

E is defined as the acyl group of C ₁ -C ₂₀ monocarboxylic acids, preferably, -C (= O) -H, -C (= O) -C 1 ~C 19 alkyl, -C (= O) -C ₂ -C _{19 alkenyl, -C (= O) -C 2} ~C 4 alkenyl -C ₆ -C _{10 aryl, -C (= O) -C 6} ~C 10 aryl, -C (= O) - O-C ₁ ~C ₆ alkyl, -C (= O) -O- C 6 ~C 10 aryl, -C (= O) -NH- C 1 ~C 6 alkyl, -C (= O) -NH- An acyl group selected from the group consisting of C ₆ -C ₁₀ aryl and —C (═O) —N (C ₁ -C ₆ alkyl) ₂ .

C E, defined as the ₂ -C ₂₀ acyl group of a dicarboxylic acid, for example, diacyl groups such as aliphatic derived from monobasic organic acid having C radicals and two acid functions, aromatic or alicyclic A diacyl group derived from the formula dicarboxylic acid.

  Suitable aliphatic dicarboxylic acids have 2 to 40 C atoms, such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid and dimers Acids (unsaturated aliphatic carboxylic acids such as dimerization products of oleic acid), alkylated malonic acids and succinic acids such as octadecyl succinic acid.

  Suitable alicyclic dicarboxylic acids are, for example, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4- (Dicarboxymethyl) cyclohexane or 4,4′-dicyclohexyldicarboxylic acid.

  Preferred members of this group include oxalic acid, adipic acid, succinic acid, suberic acid, sebacic acid, dibutylmalonic acid phthalate, dibenzyl-malonic acid or butyl- (3,5-di-tert-butyl-4-hydroxy Benzyl) -malonic acid or an acyl group of bicycloheptene dicarboxylic acid, and specific examples include succinate, sebacate, phthalate and isophthalate.

When E is a divalent acyl group of dicarbamic acid, this is, for example, an acyl group of hexamethylene dicarbamic acid or an acyl group of 2,4-toluylene dicarbamic acid;
Is T substituted by linear or branched alkylene having 1 to 18 C atoms, cycloalkylene having 5 to 18 C atoms, cycloalkenylene having 5 to 18 C atoms, phenyl? Or a linear or branched alkylene having 1 to 4 C atoms, substituted by phenyl substituted by 1 or 2 alkyl groups having 1 to 4 C atoms;
b is 1, 2 or 3, provided that b does not exceed the number of C atoms in T, and when b is 2 or 3, each hydroxyl group is bonded to a different C atom of T And
R is hydrogen or methyl; and m is 1-4.

（式中、ｘは０または１である）

（式中、ｙは２〜４である）
の基を表す；
ｍが２である場合、
Ｒ₂は、Ｃ₁〜Ｃ₁₂アルキレン、Ｃ₄〜Ｃ₁₂アルケニレン、キシリレン、脂肪族、脂環式、芳香脂肪族もしくは芳香族ジカルボン酸の二価アシル基またはジカルバミン酸の二価アシル基、例えば、２〜１８個のＣ原子を有する脂肪族ジカルボン酸のアシル基、８〜１４個のＣ原子を有する脂環式もしくは芳香族ジカルボン酸のアシル基、または８〜１４個のＣ原子を有する脂肪族、脂環式もしくは芳香族ジカルバミン酸のアシル基である；
または部分式

の基を表し、
式中、
Ｄ₁およびＤ₂は、独立して、水素、Ｃ₁〜Ｃ₈アルキル、アリールもしくはアラルキル、例えば３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル基である；
Ｄ₃は、水素、Ｃ₁〜Ｃ₁₈アルキルまたはＣ₁〜Ｃ₂₀アルケニルである；そして
ｄは０〜２０である；
ｍが３である場合、
Ｒ₂は、脂肪族、不飽和脂肪族、脂環式、または芳香族トリカルボン酸の三価アシル基である；
ｍが４である場合、
Ｒ₂は、飽和もしくは不飽和脂肪族または芳香族テトラ−カルボン酸、例えば、１，２，３，４−ブタンテトラカルボン酸、１，２，３，４−ブト−２−エンテトラカルボン酸、ならびに１，２，３，５−および１，２，４，５−ペンタンテトラカルボン酸の四価アシル基である；
前述の化合物において、変数ｐが１、２または３である場合、
Ｒ₃は、水素、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₇〜Ｃ₉アラルキル、Ｃ₂〜Ｃ₁₈アルカノイル、Ｃ₃〜Ｃ₅アルケノイルまたはベンゾイルである；
ｐが１である場合、
Ｒ₄は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₅〜Ｃ₇シクロアルキル、非置換またはシアノ、カルボニルもしくはカルバミドによって置換されたＣ₂〜Ｃ₈アルケニルであるか、あるいはアリール、アラルキル、もしくはグリシジル、部分式−ＣＨ₂−ＣＨ（ＯＨ）−Ｚまたは部分式−ＣＯ−Ｚもしくは−ＣＯＮＨ−Ｚ（式中、Ｚは、水素、メチルまたはフェニルである）の基であるか、または、部分式

（式中、ｈは０または１である）
の基を表す；
Ｒ₃およびＲ₄は一緒になって、ｐが１である場合、４〜６個のＣ原子を有するアルキレンまたは２−オキソ−ポリアルキレン、あるいは脂肪族または芳香族１，２−または１，３−ジカルボン酸の環状アシル基を表す；
ｐが２である場合、
Ｒ₄は、直接結合であるか、またはＣ₁〜Ｃ₁₂アルキレン、Ｃ₆〜Ｃ₁₂アリーレン、キシリレン、−ＣＨ₂ＣＨ（ＯＨ）−ＣＨ₂基または部分式−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｘ−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−（式中、Ｘは、Ｃ₂〜Ｃ₁₀アルキレン、Ｃ₆〜Ｃ₁₅アリーレンもしくはＣ₆〜Ｃ₁₂シクロアルキレンである）の基である；または、 Ｒ₃がアルカノイル、アルケノイルまたはベンゾイル以外であるとすると、Ｒ₄は、さらに脂肪族、脂環式もしくは芳香族ジカルボン酸またはジカルバミン酸の二価アシル基を表すか、あるいは基−ＣＯ−を表す；あるいは
Ｒ₄は、部分式

（式中、Ｔ₈およびＴ₉は独立して、水素、Ｃ₁〜Ｃ₁₈アルキルであるか、またはＴ₈およびＴ₉は一緒になって、Ｃ₄〜Ｃ₈アルキレンもしくは３−オキサペンタメチレンを表し、例えばＴ₈およびＴ₉は一緒になって３−オキサペンタメチレンである）
の基を表す；
ｐが３である場合、
Ｒ₄は２，４，６−トリアジニルである；
ｎは１または２である；
ｎが１である場合、
Ｒ₅およびＲ’₅は、独立して、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₂〜Ｃ₁₂アルケニル、Ｃ₇〜Ｃ₁₂アラルキルであるか、またはＲ₅はさらに水素を表すか、あるいはＲ₅およびＲ’₅は一緒になって、Ｃ₂〜Ｃ₈アルキレンもしくはヒドロキシアルキレンまたはＣ₄〜Ｃ₂₄アシルオキシアルキレンである；
ｎが２である場合、
Ｒ₅およびＲ’₅は一緒になって、部分式（−ＣＨ₂）₂Ｃ（ＣＨ₂−）₂の基である；
Ｒ₆は、水素、Ｃ₁〜Ｃ₁₂アルキル、アリル、ベンジル、グリシジルもしくはＣ₂〜Ｃ₆アルコキシアルキルである；または
ｎが１である場合、
Ｒ₇は、水素、Ｃ₁〜Ｃ₁₂アルキル、Ｃ₃〜Ｃ₅アルケニル、Ｃ₇〜Ｃ₉アラルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₂〜Ｃ₄ヒドロキシアルキル、Ｃ₂〜Ｃ₆アルコキシアルキル、Ｃ₆〜Ｃ₁₀アリール、グリシジル、部分式−（ＣＨ₂）_ｔ−ＣＯＯ−Ｑの基または部分式−（ＣＨ₂）_ｔ−Ｏ−ＣＯ−Ｑ（式中、ｔは１もしくは２であり、ＱはＣ₁〜Ｃ₄アルキルもしくはフェニルである）の基である；または
ｎが２である場合、
Ｒ₇は、Ｃ₂〜Ｃ₁₂アルキレン、Ｃ₆〜Ｃ₁₂アリーレン、部分式
−ＣＨ₂ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−Ｘ−Ｏ−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−の基であり、
式中、Ｘは、Ｃ₂〜Ｃ₁₀アルキレン、Ｃ₆〜Ｃ₁₅アリーレンもしくはＣ₆〜Ｃ₁₂シクロアルキレン、または部分式
−ＣＨ₂ＣＨ（ＯＺ’）ＣＨ₂−（ＯＣＨ₂−ＣＨ（ＯＺ’）ＣＨ₂）₂−
の基であり、
式中、Ｚ’は、水素、Ｃ₁〜Ｃ₁₈アルキル、アリル、ベンジル、Ｃ₂〜Ｃ₁₂アルカノイルまたはベンゾイルである；
Ｑ₁は、−Ｎ（Ｒ₈）−または−Ｏ−である；Ｅ₇は、Ｃ₁〜Ｃ₃アルキレン、−ＣＨ₂−ＣＨ（Ｒ₉）−Ｏ−基（式中、Ｒ₉は、水素、メチルもしくはフェニルである）、−（ＣＨ₂）₃−ＮＨ−基または直接結合である；
Ｒ₁₀は、水素またはＣ₁〜Ｃ₁₈アルキルであり、Ｒ₈は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₅〜Ｃ₇シクロアルキル、Ｃ₇〜Ｃ₁₂アラルキル、シアノエチル、Ｃ₆〜Ｃ₁₀アリール、−ＣＨ₂−ＣＨ（Ｒ₉）−ＯＨ基（式中、Ｒ₉は前記定義の意味を有する）である；または部分式

の基を表し、
式中、Ｇ₄は、Ｃ₂〜Ｃ₆アルキレンもしくはＣ₆〜Ｃ₁₂アリーレンである；またはＲ₈は、部分式−Ｅ₇−ＣＯ−ＮＨ−ＣＨ₂−ＯＲ₁₀の基である；
式Ｆは、Ｔ₃がエチレンまたは１，２−プロピレンであるポリマーの反復構造単位を示し、アルキルアクリレートまたはメタクリレートとのアルファ−オレフィンコポリマー；例えば、エチレンおよびエチルアクリレートのコポリマーから誘導される反復構造単位であり、ここで、ｋは２〜１００である；
Ｔ₄は、ｐが１または２である場合のＲ₄と同じ意味を有する；
Ｔ₅はメチルである；
Ｔ₆はメチルもしくはエチルであるか、またはＴ₅およびＴ₆は一緒になって、テトラメチレンまたはペンタメチレンであり、例えばＴ₅およびＴ₆はそれぞれメチルである；
ＭおよびＹは、独立して、メチレンまたはカルボニルであり、そしてＴ₄はエチレンであり、ここで、ｎは２である；
Ｔ₇はＲ₇として定義されたとおりであり、そしてＴ₇は例えばオクタメチレンであり、ここで、ｎは２である；
Ｔ₁₀およびＴ₁₁は、独立して２〜１２個のＣ原子を有するアルキレンである；または Ｔ₁₁は、部分式

の基を表す
Ｔ₁₂はピペラジニルであるか、または部分式

の基を表し、
式中、Ｒ₁₁は、Ｒ₃として定義されたとおりであるか、またはさらに部分式

の基を表す
ａ、ｂおよびｃは、独立して、２または３であり、ｆは０または１であり、例えば、ａおよびｃはそれぞれ３であり、ｂは２であり、ｆは１である；そして
ｅは、２、３または４であり、例えば４である；
Ｔ₁₃は、Ｒ₂と同じである。ただし、Ｔ₁₃は、ｎが１である場合は水素以外であるとする；
Ｅ₁およびＥ₂は、異なり、それぞれ、−ＣＯ−または−Ｎ（Ｅ₅）−（式中、Ｅ₅は水素、Ｃ₁〜Ｃ₁₂アルキルもしくはＣ₄〜Ｃ₂₄アルコキシカルボニルアルキルである）であり、例えばＥ₁は−ＣＯ−であり、Ｅ₂は−Ｎ（Ｅ₅）−である；
Ｅ₃は、水素、Ｃ₁〜Ｃ₃₀アルキル、フェニル、ナフチル、塩素もしくはＣ₁〜Ｃ₄アルキルによって置換された前記フェニルまたは前記ナフチル、またはＣ₇〜Ｃ₁₂フェニルアルキル、あるいは１〜４個のＣ原子を有するＣ₁〜Ｃ₄アルキルによって置換された前記フェニルアルキルである；
Ｅ₄は、水素、１〜３０個のＣ原子を有するアルキル、フェニル、ナフチルもしくは７〜１２個のＣ原子を有するフェニルアルキルであるか、または
Ｅ₃およびＥ₄は、一緒になって、４〜１７個のＣ原子を有するポリメチレン、または４個までのＣ₁〜Ｃ₄アルキル基、例えばメチルによって置換された前記ポリメチレンである；
Ｅ₆は、脂肪族または芳香族四価基である；
式（Ｎ）のＲ₂は、ｍが１である場合に、前記定義のとおりである；
Ｇ₁は、直接結合、Ｃ₁〜Ｃ₁₂アルキレン、フェニレンまたは−ＮＨ−Ｇ’−ＮＨであり、式中、Ｇ’はＣ₁〜Ｃ₁₂アルキレンである。 In the compound, when the variable m is 1,
R ₂ is hydrogen, C ₁ -C ₁₈ alkyl or optionally said alkyl interrupted by one or more oxygen atoms, C ₂ -C ₁₂ alkenyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₈ aralkyl, glycidyl, A monovalent acyl group of an aliphatic, alicyclic or aromatic carboxylic acid, or a carbamic acid, for example an acyl group of an aliphatic carboxylic acid having 2 to 18 C atoms, an alicyclic ring having 5 to 12 C atoms An acyl group of the formula carboxylic acid or an acyl group of an aromatic carboxylic acid having 7 to 15 C atoms, or a partial formula

(Wherein x is 0 or 1)

(Wherein y is 2-4)
Represents a group of
If m is 2,
R ₂ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid divalent acyl group or dicarbamic acid divalent acyl group, for example An acyl group of an aliphatic dicarboxylic acid having 2 to 18 C atoms, an acyl group of an alicyclic or aromatic dicarboxylic acid having 8 to 14 C atoms, or a fat having 8 to 14 C atoms An acyl group of an aromatic, alicyclic or aromatic dicarbamic acid;
Or subexpression

Represents the group of
Where
D ₁ and D ₂ are independently hydrogen, C ₁ -C ₈ alkyl, aryl or aralkyl, such as a 3,5-di-tert-butyl-4-hydroxybenzyl group;
D ₃ is hydrogen, C ₁ -C ₁₈ alkyl or C ₁ -C ₂₀ alkenyl; and d is 0-20;
If m is 3,
R ₂ is a trivalent acyl group of an aliphatic, unsaturated aliphatic, alicyclic, or aromatic tricarboxylic acid;
If m is 4,
R ₂ is a saturated or unsaturated aliphatic or aromatic tetra-carboxylic acid, such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic acid, And 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic acid tetravalent acyl groups;
In the aforementioned compound, when the variable p is 1, 2 or 3,
R ₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₉ aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl or benzoyl;
If p is 1,
R ₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, unsubstituted or C ₂ -C ₈ alkenyl substituted by cyano, carbonyl or carbamide, or aryl, aralkyl, or glycidyl A group of the partial formula —CH ₂ —CH (OH) —Z or a partial formula —CO—Z or —CONH—Z, wherein Z is hydrogen, methyl or phenyl, or a partial formula

(Where h is 0 or 1)
Represents a group of
R ₃ and R _{4 taken} together when p is 1, alkylene or 2-oxo-polyalkylene having 4 to 6 C atoms, or aliphatic or aromatic 1,2- or 1,3 -Represents a cyclic acyl group of a dicarboxylic acid;
If p is 2,
R ₄ is a direct bond, or C ₁ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylylene, —CH ₂ CH (OH) —CH ₂ group or partial formula —CH ₂ —CH (OH) —. CH ₂ —O—X—O—CH ₂ —CH (OH) —CH ₂ —, wherein X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene. Or if R ₃ is other than alkanoyl, alkenoyl or benzoyl, R ₄ further represents a divalent acyl group of an aliphatic, alicyclic or aromatic dicarboxylic acid or dicarbamic acid, Or represents the group —CO—; or R ₄ represents a partial formula

Wherein T ₈ and T ₉ are independently hydrogen, C ₁ -C ₁₈ alkyl, or T ₈ and T ₉ together are C ₄ -C ₈ alkylene or 3-oxapentamethylene. For example, T ₈ and T ₉ together are 3-oxapentamethylene)
Represents a group of
If p is 3,
R ₄ is 2,4,6-triazinyl;
n is 1 or 2;
When n is 1,
R ₅ and R ′ ₅ are independently C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₇ -C ₁₂ aralkyl, or R ₅ further represents hydrogen, or R ₅ and R ′ _{5 taken} together is C ₂ -C ₈ alkylene or hydroxyalkylene or C ₄ -C ₂₄ acyloxyalkylene;
If n is 2,
R ₅ and R ′ ₅ together are a group of the partial formula (—CH ₂ ) ₂ C (CH ₂ —) ₂ ;
R ₆ is hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl; or, when n is 1,
R ₇ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₆ alkoxyalkyl , C ₆ -C ₁₀ aryl, glycidyl, a group of the partial formula — (CH ₂ ) _t —COO—Q or a partial formula — (CH ₂ ) _t —O—CO—Q wherein t is 1 or 2 , Q is C ₁ -C ₄ alkyl or phenyl); or when n is 2,
R ₇ is a C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, group of the partial formula —CH ₂ CH (OH) —CH ₂ —O—X—O—CH ₂ —CH (OH) —CH ₂ —. And
Where X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene, or the partial formula —CH ₂ CH (OZ ′) CH ₂ — (OCH ₂ —CH (OZ ′) ) CH ₂ ) ₂ −
The basis of
Where Z ′ is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl;
Q ₁ is —N (R ₈ ) — or —O—; E ₇ is a C ₁ -C ₃ alkylene, —CH ₂ —CH (R ₉ ) —O— group wherein R ₉ is Hydrogen, methyl or phenyl), a — (CH ₂ ) ₃ —NH— group or a direct bond;
R ₁₀ is hydrogen or C ₁ -C ₁₈ alkyl, R ₈ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₁₂ aralkyl, cyanoethyl, C ₆ -C ₁₀ An aryl, —CH ₂ —CH (R ₉ ) —OH group, wherein R ₉ has the meaning as defined above; or a partial formula

Represents the group of
Where G ₄ is C ₂ -C ₆ alkylene or C ₆ -C ₁₂ arylene; or R ₈ is a group of the sub-formula -E ₇ -CO-NH-CH ₂ -OR ₁₀ ;
Formula F represents a repeating structural unit of a polymer where T ₃ is ethylene or 1,2-propylene and is an alpha-olefin copolymer with an alkyl acrylate or methacrylate; for example, a repeating structural unit derived from a copolymer of ethylene and ethyl acrylate Where k is 2 to 100;
T ₄ has the same meaning as R ₄ when p is 1 or 2;
T ₅ is methyl;
T ₆ is methyl or ethyl, or T ₅ and T _{6 taken} together are tetramethylene or pentamethylene, for example, T ₅ and T ₆ are each methyl;
M and Y are independently methylene or carbonyl, and T ₄ is ethylene, where n is 2.
T ₇ is as defined as R ₇ and T ₇ is, for example, octamethylene, where n is 2;
T ₁₀ and T ₁₁ are independently alkylene having 2 to 12 C atoms; or T ₁₁ is a partial formula

T ₁₂ representing the group of is piperazinyl or a partial formula

Represents the group of
In which R ₁₁ is as defined as R ₃ or is

A, b and c each independently represent 2 or 3, f is 0 or 1, for example, a and c are each 3, b is 2, and f is 1. And e is 2, 3 or 4, for example 4;
T ₁₃ is the same as R ₂ . Provided that T ₁₃ is other than hydrogen when n is 1;
E ₁ and E ₂ are different and are each —CO— or —N (E ₅ ) —, where E ₅ is hydrogen, C ₁ -C ₁₂ alkyl or C ₄ -C ₂₄ alkoxycarbonylalkyl. For example, E ₁ is —CO— and E ₂ is —N (E ₅ ) —;
E ₃ is hydrogen, C ₁ -C ₃₀ alkyl, phenyl, naphthyl, chlorine or the phenyl or naphthyl substituted by C ₁ -C ₄ alkyl, or C ₇ -C ₁₂ phenylalkyl, or 1-4 substituted by C ₁ -C ₄ alkyl having C atoms were located in the phenylalkyl;
E ₄ is hydrogen, alkyl having 1 to 30 C atoms, phenyl, naphthyl or phenylalkyl having 7 to 12 C atoms, or E ₃ and E ₄ together are 4 A polymethylene having ˜17 C atoms, or said polymethylene substituted by up to ₄ C ₁ -C ₄ alkyl groups such as methyl;
E ₆ is an aliphatic or aromatic tetravalent group;
R _{2 in} formula (N) is as defined above when m is 1.
G ₁ is a direct bond, C ₁ -C ₁₂ alkylene, phenylene or —NH—G′—NH, where G ′ is C ₁ -C ₁₂ alkylene.

Suitable tetraalkylpiperidine or tetraalkylpiperazine derivatives are, for example, compounds of the formulas 1-12:

の基を表す。 Where
E ₁ , E ₂ , E ₃ and E ₄ are independently C ₁ -C ₄ alkyl, or E ₁ and E ₂ are independently C ₁ -C ₄ alkyl, E ₃ and E ₄ Are pentamethylene together, or E ₁ and E ₂ ; and E ₃ and E ₄ are together pentamethylene;
R ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, a bicyclic or tricyclic hydrocarbon group having 7 to 12 carbon atoms, C ₇ -C ₁₅ phenylalkyl, C _6- C ₁₀ aryl or said aryl substituted by _{1 to} 3 C ₁ -C ₈ alkyl;
R ₂ is hydrogen or linear or branched C ₁ -C ₁₂ alkyl;
R ₃ is alkylene having 1 to 8 carbon atoms, or R ₃ is —CO—, —CO—R ₄ —, —CONR ₂ —, or —CO—NR ₂ —R ₄ . ;
R ₄ is C ₁ -C ₈ alkylene;
R ₅ is hydrogen, linear or branched C ₁ -C ₁₂ alkyl, or a partial formula

Represents a group of

の基を表す
ただし、Ｒ₆が前記構造である場合、Ｙは−ＯＨ以外であるとする；
Ａは、−Ｏ−または−ＮＲ₇−であり、ここで、Ｒ₇は、水素、直線状もしくは分枝鎖Ｃ₁〜Ｃ₁₂アルキルである；またはＲ₇は、部分式

の基である
Ｔは、フェノキシ、１もしくは２個のＣ₁〜Ｃ₈アルキルまたはＣ₁〜Ｃ₈アルコキシによって置換されたフェノキシ、あるいは−Ｎ（Ｒ₂）₂であり、ただし、Ｒ₂は水素以外であるとする；あるいはＴは部分式

の基である
Ｘは、−ＮＨ₂、−ＮＣＯ、−ＯＨ、−Ｏ−グリシジル、または−ＮＨＮＨ₂であり、そして
Ｙは、−ＯＨ、−ＮＨ₂、−ＮＨＲ₂であり、ここで、Ｒ₂は水素以外である；またはＹは、−ＮＣＯ、−ＣＯＯＨ、オキシラニル、−Ｏ−グリシジル、もしくは−Ｓｉ（ＯＲ₂）₃である；
あるいは組み合わせＲ₃−Ｙ−は、−ＣＨ₂ＣＨ（ＯＨ）Ｒ₂であり、ここで、Ｒ₂はアルキルまたは１〜４個の酸素原子によって中断された前記アルキルであるか、あるいはＲ₃−Ｙ−は−ＣＨ₂ＯＲ₂である；あるいは
ここで、ヒンダードアミン化合物は、Ｎ，Ｎ’，Ｎ’’’−トリス｛２，４−ビス［（１−ヒドロカルビルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）アルキルアミノ］−ｓ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン；Ｎ，Ｎ’，Ｎ’’−トリス｛２，４−ビス［（１−ヒドロカルビルオキシ−２，２，６，６−テトラメチルピペリジン−４−イル）アルキルアミノ］−ｓ−トリアジン−６−イル｝−３，３’−エチレンジイミノジプロピルアミン、および式
Ｒ₁ＮＨ−ＣＨ₂ＣＨ₂ＣＨ₂ＮＲ₂ＣＨ₂ＣＨ₂ＮＲ₃ＣＨ₂ＣＨ₂ＣＨ₂ＮＨＲ₄（１３）
Ｔ−Ｅ₁−Ｔ₁ （１４）
Ｔ−Ｅ₁ （１５）
Ｇ−Ｅ₁−Ｇ₁−Ｅ₁−Ｇ₂ （１６）
により記載されるような架橋誘導体の混合物である
ここで、テトラアミン（１３）において、
Ｒ₁およびＲ₂はｓ−トリアジン部分Ｅである；Ｒ₃およびＲ₄の一方はｓ−トリアジン部分Ｅであり、Ｒ₃またはＲ₄のもう一方は水素である；
Ｅは

である
Ｒは、メチル、プロピル、シクロヘキシルまたはオクチル、例えばシクロヘキシルである；
Ｒ₅はＣ₁〜Ｃ₁₂アルキル、例えばｎ−ブチルである；
ここで、式（１４）および（１５）の化合物において、Ｒがプロピル、シクロヘキシルまたはオクチルである場合、ＴおよびΤ₁は、式１３で定義されるように、それぞれＲ₁〜Ｒ₄によって置換されたテトラアミンであり、ここで
（１）各テトラアミン中のｓ−トリアジン部分Ｅのうちの１つは、基Ｅ₁によって置換され、これは２つのテトラアミンＴとＴ₁の間にブリッジを形成する；
Ｅ₁は、部分式

の基である、または
（２）基Ｅ₁は、式１５と同じテトラアミンＴにおいて両末端を有し得、ここで、テトラアミンの２つのＥ部分は、１つのＥ₁基により置換される；または
（３）テトラアミンＴの３つのｓ−トリアジン置換基は全てＥ₁であり得、したがって１つのＥ₁がＴおよびＴ₁と結合し、第２のＥ₁はテトラアミンＴで両端を有する；
Ｌは、プロパンジイル、シクロヘキサンジイルまたはオクタンジイルである；
ここで、化合物（１６）において、
Ｇ、Ｇ₁およびＧ₂はそれぞれ、ＧおよびＧ₂がそれぞれＥ₁によって置換されたｓ−トリアジン部分Ｅの１つを有し、Ｇ₁がＥ₁によって置換された２つのトリアジン部分Ｅを有し、したがって、ＧとＧ₁の間にブリッジがあり、Ｇ₁とＧ₂の間に第２のブリッジがある以外、式Ｉで定義されるようなＲ₁〜Ｒ₄によって置換されたテトラアミンである；
この混合物は、２〜４当量の２，４−ビス［（１−ヒドロカルビル−オキシ−２，２，６，６−テトラメチルピペリジン−４−イル）ブチルアミノ］−６−クロロ−ｓ−トリアジンを１当量のＮ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミンと反応させることによって製造される；
あるいは、ヒンダードアミンは、式（１７）

の化合物である
式中、添字ｎは１〜１５であり；
Ｒ₁₂は、Ｃ₂〜Ｃ₁₂アルキレン、Ｃ₄〜Ｃ₁₂アルケニレン、Ｃ₅〜Ｃ₇シクロアルキレン、Ｃ₅〜Ｃ₇シクロアルキレン−ジ（Ｃ₁〜Ｃ₄アルキレン）、Ｃ₁〜Ｃ₄アルキレン−ジ（Ｃ₅〜Ｃ₇シクロアルキレン）、フェニレン−ジ（Ｃ₁〜Ｃ₄アルキレン）または１，４−ピペラジンジイル、−Ｏ−もしくは＞Ｎ−Ｘ₁によって中断されたＣ₄〜Ｃ₁₂アルキレンであり、Ｘ₁はＣ₁〜Ｃ₁₂アシルもしくは（Ｃ₁〜Ｃ₁₂アルコキシ）カルボニルであるか、または水素以外の下記のＲ₁₄の定義の１つを有するか；またはＲ₁₂は部分式：

の基である
Ｘ₂は、Ｃ₁〜Ｃ₁₈アルキル、置換されていないか、または１、２もしくは３個のＣ₁〜Ｃ₄アルキルで置換されたＣ₅〜Ｃ₁₂シクロアルキル；置換されていないか、または１、２もしくは３個のＣ₁〜Ｃ₄アルキルもしくはＣ₁〜Ｃ₄アルコキシにより置換されたフェニル；置換されていないか、またはフェニル上で１、２もしくは３個のＣ₁〜Ｃ₄アルキルにより置換されたＣ₇〜Ｃ₉フェニルアルキルである；そして
Ｘ₃基は、互いに独立して、Ｃ₂〜Ｃ₁₂アルキレンである；
Ｒ₁₃、Ｒ₁₄およびＲ₁₅は、同一または異なり、水素、Ｃ₁〜Ｃ₁₈アルキル、置換されていないか、または１、２もしくは３個のＣ₁〜Ｃ₄アルキルにより置換されたＣ₅〜Ｃ₁₂シクロアルキル；Ｃ₃〜Ｃ₁₈アルケニル、置換されていないか、または１、２もしくは３個のＣ₁〜Ｃ₄アルキルもしくはＣ₁〜Ｃ₄アルコキシにより置換されたフェニル；置換されていないか、またはフェニル上で１、２もしくは３個のＣ₁〜Ｃ₄アルキルによって置換されたＣ₇〜Ｃ₉フェニルアルキル；テトラヒドロフルフリルまたは
２、３もしくは４位で−ＯＨ、Ｃ₁〜Ｃ₈アルコキシ、ジ（Ｃ₁〜Ｃ₄アルキル）アミノまたは部分式：

の基により置換されたＣ₂〜Ｃ₄アルキルであり、
Ｙは、−Ｏ−、−ＣＨ₂−、−ＣＨ₂ＣＨ₂−もしくは＞Ｎ−ＣＨ₃であるか、または−Ｎ（Ｒ₁₄）（Ｒ₁₅）はさらに基

である；
Ａ基は、互いに独立して、−ＯＲ₁₃、−Ｎ（Ｒ₁₄）（Ｒ₁₅）または部分式：

の基である
ここで、
Ｘは−Ｏ−または＞Ｎ−Ｒ₁₆である；
Ｒ₁₆は、水素、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₃〜Ｃ₁₈アルケニル、置換されていないか、または１、２もしくは３個のＣ₁〜Ｃ₄アルキルにより置換されたＣ₅〜Ｃ₁₂シクロアルキル；置換されていないか、またはフェニル上で１、２もしくは３個のＣ₁〜Ｃ₄アルキルにより置換されたＣ₇〜Ｃ₉フェニルアルキル；テトラヒドロフルフリル、部分式：

の基、または２、３もしくは４位で、−ＯＨ、Ｃ₁〜Ｃ₈アルコキシ、ジ（Ｃ₁〜Ｃ₄アルキル）アミノまたは部分式

の基により置換されたＣ₂〜Ｃ₄アルキルである、
Ｒ₁₁は、Ｒ₁₆についての定義のうちの１つを有する；そして
Ｂ基は、互いに独立して、Ａについて記載した定義のうちの１つを有する。 Alternatively, when R ₄ is ethylene, the two R ₅ methyl substituents can be linked by a direct bond with the triazine bridging group —N (R ₅ ) —R ₄ —N (R ₅ ) — and piperazine Forming a -1,4-diyl group;
R ₆ is C ₂ -C ₈ alkylene or a partial formula

Provided that when R ₆ is the above structure, Y is other than —OH;
A is —O— or —NR ₇ —, wherein R ₇ is hydrogen, linear or branched C ₁ -C ₁₂ alkyl; or R ₇ is a sub-formula

T is phenoxy, phenoxy substituted by 1 or 2 C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or -N (R ₂ ) ₂ , where R ₂ is hydrogen Or T is a subexpression

X is —NH ₂ , —NCO, —OH, —O-glycidyl, or —NHNH ₂ , and Y is —OH, —NH ₂ , —NHR ₂ , where R ₂ is other than hydrogen; or Y is —NCO, —COOH, oxiranyl, —O-glycidyl, or —Si (OR ₂ ) ₃ ;
Alternatively, the combination R ₃ —Y— is —CH ₂ CH (OH) R ₂ , where R ₂ is alkyl or said alkyl interrupted by 1 to 4 oxygen atoms, or R ₃ — Y— is —CH ₂ OR ₂ ; or wherein the hindered amine compound is N, N ′, N ′ ″-tris {2,4-bis [(1-hydrocarbyloxy-2,2,6,6 -Tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3′-ethylenediiminodipropylamine; N, N ′, N ″ -tris {2,4-bis [(1-Hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3′-ethylenediiminodipropylamine and the formula R ₁ NH-CH ₂ CH ₂ CH ₂ NR ₂ CH ₂ CH ₂ NR ₃ CH ₂ CH ₂ CH ₂ NHR ₄ (13)
T-E ₁ -T ₁ (14)
T-E ₁ (15)
GE ₁ -G ₁ -E ₁ -G ₂ (16)
Is a mixture of cross-linked derivatives as described by: wherein in tetraamine (13):
R ₁ and R ₂ are the s-triazine moiety E; one of R ₃ and R ₄ is the s-triazine moiety E and the other of R ₃ or R ₄ is hydrogen;
E is

R is methyl, propyl, cyclohexyl or octyl, such as cyclohexyl;
R ₅ is C ₁ -C ₁₂ alkyl, such as n-butyl;
Here, in the compounds of formulas (14) and (15), when R is propyl, cyclohexyl or octyl, T and Τ ₁ are each substituted by R _{1 to} R ₄ as defined in formula 13 (1) one of the s-triazine moieties E in each tetraamine is replaced by a group E ₁ , which forms a bridge between the two tetraamines T and T ₁ ;
E ₁ is a partial expression

Or (2) the group E ₁ can have both ends in the same tetraamine T as in formula 15, wherein the two E moieties of the tetraamine are replaced by one E ₁ group; or (3) All three s-triazine substituents of tetraamine T can be E ₁ , so one E ₁ is bound to T and T ₁ and the second E ₁ is tetraamine T and has both ends;
L is propanediyl, cyclohexanediyl or octanediyl;
Here, in the compound (16),
G, respectively, G ₁ and G ₂ has one of the s- triazine moiety E which is substituted by E ₁ G and G ₂ each, have a two-triazine moieties E in which G ₁ is substituted by E ₁ and, therefore, there is a bridge between G and G _1, except for the second bridge between in G ₁ and G _2, in tetraamine substituted by R ₁ to R ₄ as defined in formula I is there;
This mixture contains 2-4 equivalents of 2,4-bis [(1-hydrocarbyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine. Prepared by reacting with 1 equivalent of N, N′-bis (3-aminopropyl) ethylenediamine;
Alternatively, the hindered amine has the formula (17)

Wherein the subscript n is 1-15;
R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylene. C ₄ -C ₁₂ alkylene interrupted by -di (C ₅ -C ₇ cycloalkylene), phenylene-di (C ₁ -C ₄ alkylene) or 1,4-piperazinediyl, -O- or> N-X ₁ And X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl, or has one of the following definitions of R ₁₄ other than hydrogen; or R ₁₂ is a sub-formula:

X ₂ is a C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; either unsubstituted or 1, 2 or 3 C ₁ -on the phenyl C ₇ -C ₉ phenylalkyl substituted by C ₄ alkyl; and the X ₃ groups, independently of one another, are C ₂ -C ₁₂ alkylene;
R _13, R ₁₄ and R ₁₅ are identical or different and are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ ~ which is unsubstituted or substituted, or 2 or by 3 C ₁ -C ₄ alkyl C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl, phenyl that is unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Or C ₇ -C ₉ phenylalkyl substituted on the phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; tetrahydrofurfuryl or —OH, C ₁ -C ₈ alkoxy in the 2, 3 or 4 position Di (C ₁ -C ₄ alkyl) amino or partial formula:

A of C ₂ -C ₄ alkyl substituted by a group,
Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ , or —N (R ₁₄ ) (R ₁₅ ) is a further group.

Is
A groups, independently of one another, are —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or a partial formula:

Where
X is —O— or> N—R ₁₆ ;
R ₁₆ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cyclo, unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl. Alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl with 1, 2 or 3 C ₁ -C ₄ alkyl; tetrahydrofurfuryl, sub-formula:

Or —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or partial formula at the 2, 3 or 4 position

Is a C ₂ -C ₄ alkyl substituted by a group,
R ₁₁ has one of the definitions for R ₁₆ ; and the B group, independently of one another, has one of the definitions described for A.

  Tetraalkylpiperidine and tetraalkylpiperazine compounds are known in the art and are also known as N-alkoxyhindered amines and NOR-hindered amines or NOR-hindered amine light stabilizers or NOR-HALS, for example, US Pat. No. 004,770, No. 5,204,473, No. 5,096,950, No. 5,300,544, No. 5,112,890, No. 5,124,378, Disclosed in US Pat. No. 5,145,893, US Pat. No. 5,216,156, US Pat. No. 5,844,026, US Pat. No. 6,117,995, or US Pat. No. 6,271,377 It is.

  U.S. Pat. No. 6,271,377 and published U.S. patent application Ser. No. 09 / 505,529, filed Feb. 17, 2000, and filed Feb. 27, 2001. 09 / 794,710 discloses hindered hydroxyalkoxyamine stabilizers. Hindered hydroxyalkoxyamine stabilizers are known as N-hydroxyalkoxyhindered amines, or NORol-HALS.

A typical structure is as follows:

  Here, the definitions of R and R 'include N-, O- or C substituents.

When group E is —O—C (O) —C ₁ -C ₁₈ alkyl, the compound is a hydroxylamine ester.

  Hydroxylamine is reacted with an acid derivative to form the final hydroxylamine ester. Such esterification methods are well known and are described in the literature.

  The production of particularly suitable compounds is described in international patent application WO 01/90113.

の２，２，６，６−テトラアルキルピペリジン−１−オキシド、
式

の１−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン、
式

の１−アルコキシ−２，２，６，６−テトラアルキルピペリジン、
式

の１−アシルオキシ−２，２，６，６−ピペリジン
の群から選択され、
式中、
Ｒ_aおよびＲ_bの一方は
水素もしくはＮ置換基を表し、もう一方はＯ置換基もしくはＣ置換基を表す；または
Ｒ_aおよびＲ_bはどちらも水素、Ｏ置換基またはＣ置換基を表す；
Ｒは、Ｃ₁〜Ｃ₂₀アルキル、Ｃ₅〜Ｃ₆シクロアルキルもしくはＣ₂〜Ｃ₂₀アルキル、さらなる置換基を有するＣ₅〜Ｃ₆シクロアルキルもしくはＣ₂〜Ｃ₂₀アルケニルを表す；
Ａｃは、Ｃ₁〜Ｃ₂₀モノカルボン酸またはＣ₁〜Ｃ₂₀ジカルボン酸のアシル基を表す；そして
Ｒ₁〜Ｒ₄は、それぞれＣ₁〜Ｃ₄アルキルを表す；そして
Ｒ₅およびＲ₆は、互いに独立して、水素または、Ｃ₁〜Ｃ₄−アルキル、Ｃ₁〜Ｃ₃アルキルフェニルおよびフェニルからなる群から選択される置換基を表す；そして
Ｒ₅およびＲ₆は一緒になってオキソを表す。 According to a preferred embodiment, the tetraalkylpiperidine derivative is
formula

2,2,6,6-tetraalkylpiperidine-1-oxide of
formula

Of 1-hydroxy-2,2,6,6-tetraalkylpiperidine,
formula

1-alkoxy-2,2,6,6-tetraalkylpiperidine of
formula

Selected from the group of 1-acyloxy-2,2,6,6-piperidine of
Where
One of R _a and R _b represents hydrogen or N substituent and the other represents O substituent or C substituent; or R _a and R _b both represent hydrogen, O substituent or C substituent;
R represents a C ₁ -C ₂₀ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₂₀ alkenyl having additional substituents;
Ac represents a C ₁ -C ₂₀ monocarboxylic acid or C ₁ -C ₂₀ dicarboxylic acid acyl group; and R ₁ -R ₄ each represent C ₁ -C ₄ alkyl; and R ₅ and R ₆ are , independently of one another, hydrogen or, C ₁ -C ₄ - alkyl, represents a substituent selected from the group consisting of C ₁ -C ₃ alkylphenyl and phenyl; and R ₅ and R ₆ together oxo Represents.

According to a preferred embodiment, the composition comprises at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId as component b)
here,
One of R _a and R _b represents hydrogen or N substituent and the other represents O substituent or C substituent; or R _a and R _b both represent hydrogen, O substituent or C substituent;
R represents a C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl having additional substituents;
Ac represents an acyl group of C ₁ -C ₈ carboxylic acid; and R ₁ to R ₄ are each methyl; and each represent R ₅ and R ₆ hydrogen.

According to a particularly preferred embodiment, the composition comprises at least one tetraalkylpiperidine derivative IIIa, IIIb, IIIc or IIId as component b)
here,
One of R _a and R _b represents hydrogen or an N substituent and the other represents an O substituent or a C substituent; or R _a and R _b both represent an O substituent or a C substituent;
R represents C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkyl, or C ₅ -C ₆ cycloalkyl or C ₂ -C ₈ alkenyl substituted by hydroxy;
Ac represents an acyl group of C ₁ -C ₈ carboxylic acid; and R ₁ to R ₄ are each methyl; and each represent R ₅ and R ₆ hydrogen.

の化合物
および式

（式中、ｎは１〜１５である）（Ｆｌａｍｅｓｔａｂ ＮＯＲ１１６（登録商標））
の化合物
からなる群から選択される少なくとも１つのテトラアルキルピペリジン誘導体ＩＩＩｃまたはＩＩＩｄからなる。 According to a preferred embodiment, component b) is
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (Tinuvin NOR371®),
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
N, N′-bis (3-amino of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine Reaction product with propyl) ethylenediamine),
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,
2,4′-Hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine endcapped 2,4- An oligomeric compound which is a condensation product of dichloro-6-[(1-cyclo-hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
formula

Compounds and formulas

(In the formula, n is 1 to 15) (Frametab NOR116 (registered trademark))
And at least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of:

  The aforementioned compounds are some commercial products. Exemplary compounds are sold by Ciba under the following trade names: Flamestab NOR116®, Tinuvin NOR371® or Irgatec CR76®.

Component c)
The term polymer substrate includes within its scope thermoplastic polymers or thermosetting polymers.

A list of suitable thermoplastic polymers is given below:
1. Monoolefin and diolefin polymers such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and cycloolefin polymers such as cyclopentene or norbornene Polymers, polyethylene (which may optionally be cross-linked), such as high density polymethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be produced by different methods, in particular by the following methods:
a) Radical polymerization (usually under high pressure and at high temperature).

  b) Catalytic polymerization using a catalyst that normally contains one or more metals from groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either α or σ bond coordinated. It can be. These metal complexes can be in free form or immobilized on a substrate, typically activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalyst can be used alone in the polymerization, or further activators, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes can be used, said metal being It is an element of group Ia, IIa and / or IIIa of the periodic table. The activator can be conveniently modified with further ester, ether, and amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

  Mixtures of the polymers described in 2.1), for example, polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

  3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butene 1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cyclohexane Olefin copolymers (eg, ethylene / norbornene such as COC), ethylene / 1-olefin copolymers, where 1-olefins are produced in-situ; Lopylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers) and ethylene and propylene And terpolymers with dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with the polymers described in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / Ethylene-vinyl acetate copolymer (EVA), LDPE / Ethylene-acrylic acid copolymer (EAA) LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example mixtures of polyamide.

4). Hydrocarbon resins (eg, C ₅ -C ₉ ), such as hydrogenated modifications thereof (eg, tackifiers) and mixtures of polyalkylenes and starches;
The aforementioned homopolymers and copolymers can have a stereostructure including syndiotactic, isotactic, semi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.

  5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

  6). Including all isomers of styrene, α-methylstyrene, vinyltoluene, especially p-vinyltoluene, all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof , Aromatic homopolymers and copolymers derived from vinyl aromatic monomers. Homopolymers and copolymers can have stereostructures including syndiotactic, isotactic, semi-isotactic or atactic; where atactic polymers are preferred. Also included are stereoblock polymers;

  a) a copolymer comprising said vinyl aromatic monomer and a comonomer selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene / Butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact strength Styrene copolymers and other polymers such as polyacrylates, diene polymers or mixtures of ethylene / propylene / diene terpolymers; Down of the block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / - ethylene / propylene / styrene.

  b) Polycyclohexylethylene (PCHE) produced by hydrogenation of hydrogenated aromatic polymers derived from hydrogenation of the polymers described in 6), for example atactic polystyrene often referred to as polyvinylcyclohexane (PVCH) ).

  c) Hydrogenated aromatic polymers derived from hydrogenation of the polymers described in 6a). Homopolymers and copolymers can have stereostructures including syndiotactic, isotactic, semi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.

  7). Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer; styrene on polybutadiene and acrylonitrile (or methacrylonitrile); styrene on polybutadiene, acrylonitrile And methyl methacrylate; styrene on polybutadiene and maleic anhydride; styrene on polybutadiene, acrylonitrile and maleic anhydride or maleimide; styrene and maleimide on polybutadiene; styrene and alkyl acrylate or methacrylate on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers ; Poly-a Styrene and acrylonitrile on kill acrylates or polyalkylmethacrylates, styrene and acrylonitrile on acrylate / -butadiene copolymers, and mixtures thereof with the copolymers listed under 6), for example copolymer mixtures known as ABS, MBS, ASA or AES polymers .

  8). Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homopolymers and Copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl / vinyl acetate or vinylidene chloride /- Vinyl acetate copolymer.

  9. Impact modified with polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, butyl acrylate.

  Of the monomers described in 10.9), with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylonitrile / vinyl halide copolymers or Acrylonitrile / alkyl methacrylate / butadiene terpolymer.

  11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, vinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl Melamine; and their copolymers with the olefins as defined in 1 above.

  12 Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

  13. Polyacetals such as polyoxymethylene, and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

  14 Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene polymers or polyamides.

  15. Polyurethanes derived on the one hand from hydroxyl-terminated polyethers, polyesters or polybutadiene and on the other hand from aliphatic or aromatic polyisocyanurates, as well as their precursors.

  16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, Aromatic polyamides starting from 4/6, 12/12, polyamide 11, polyamide 12, m-xylenediamine and adipic acid; from hexamethylenediamine and isophthalic acid or / and terephthalic acid, with or without elastomer as modifier Polyamides, such as poly-2,4,4, -trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also polyolefins, olefin copolymers, ionomers or chemistry of the aforementioned polyamides Block copolymers with bonded or grafted elastomers; or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and in process Polyamide condensed with (RIM polyamide system).

  17. Polyurea, polyimide, polyamideimide, polyetherimide, polyesterimide, polyhydantoin and polyimidazole.

  18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoate As well as block co-polyether esters derived from hydroxyl-terminated polyethers; and polyesters modified with polycarbonate or MBS.

  19. Polyketone.

  20. Polysulfone, polyethersulfone and polyetherketone.

  21. Blends of the aforementioned polymers (polyblends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO , PBT / PC / ABS or PBT / PET / PC.

に対応するポリカーボネート。 22. General formula:

Polycarbonate corresponding to.

  Such polycarbonates are obtained by the interfacial method or by the melting method (catalyzed transesterification). Polycarbonates can be either branched or linear in structure and can contain optional substituents. Polycarbonate copolymers and polycarbonate blends are also included within the scope of the present invention. The term polycarbonate should be construed to include copolymers and blends with other thermoplastics. For example, US Pat. Nos. 3,030,331; 3,169,121; 4,130,458; 4,263,201; 286,083; 4,552,704; 5,210,268; and 5,606,007. A combination of two or more polycarbonates of different molecular weights can be used.

Preference is given to polycarbonates obtained by reaction of diphenols, for example bisphenol A, with a carbonate source. Examples of suitable diphenols are:

である。

It is.

  The carbonate source can be a carbonyl halide, a carbonate ester or a haloformate. The preferred carbonate halide is phosgene or carbonyl bromide. Suitable carbonate esters are dialkyl carbonates such as dimethyl carbonate or diethyl carbonate, diphenyl carbonate, phenylalkyl phenyl carbonates such as phenyl-tolyl carbonate, dialkyl carbonates such as dimethyl carbonate or diethyl carbonate, di (halophenyl) carbonates such as di (chlorophenyl). ) Carbonate, di (bromophenyl) carbonate, di (trichlorophenyl) carbonate or di (trichlorophenyl) carbonate, di (alkylphenyl) carbonate, such as di-tolyl carbonate, naphthyl carbonate, dichloronaphthyl carbonate and the like.

  The aforementioned polymer substrate comprising a polycarbonate or polycarbonate blend is a polycarbonate copolymer in which an isophthalate / terephthalate-resorcinol segment is present. Such polycarbonates are commercially available, for example Lexan® SLX (General Electrics Co. USA). Other polymer substrates of component b) are in the form of mixtures or copolymers, etc., various synthetic polymers such as polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly (meth) acrylates, thermoplastic polyurethanes, polysulfones, polyacetals and It may further contain PVC, for example a suitable compatibilizer. For example, the polymer substrate may further comprise a thermoplastic polymer selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof. Specific embodiments include polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol modified polycyclohexylene methylene terephthalate (PCTG), polysulfone (PSU). ), Polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic acid ester (ASA), acrylonitrile-ethylene-propylene-styrene (AES), styrene-anhydrous Maleic acid (SMA) or high impact polystyrene (HIPS).

の少なくとも２つのエポキシ基が存在し、これは、炭素、酸素、窒素または硫黄原子に直接結合し、ここで、ｑはゼロを表し、Ｒ₁およびＲ₃はどちらも水素を表し、Ｒ₂は水素またはメチルを表す；または、ｑは０または１を表し、Ｒ₁およびＲ₃は、一緒になって、−ＣＨ₂−ＣＨ₂−または−ＣＨ₂−ＣＨ₂−ＣＨ₂−基を形成し、Ｒ₂は水素を表す。 23. An epoxy resin composed of a difunctional or polyfunctional epoxide compound, which has a partial formula

There are at least two epoxy groups directly bonded to a carbon, oxygen, nitrogen or sulfur atom, where q represents zero, R ₁ and R ₃ both represent hydrogen, and R ₂ represents Represents hydrogen or methyl; or q represents 0 or 1, and R ₁ and R ₃ together form a —CH ₂ —CH ₂ — or —CH ₂ —CH ₂ —CH ₂ — group. , R ₂ represents hydrogen.

  Suitable hardener components include, for example, amine and anhydride hardeners such as polyamines such as ethylenediamine, diethylenetriamine, triethylenetriamine, hexamethylenediamine, methanediamine, N-aminoethylpiperazine, diaminodiphenylmethane [DDM], alkyl of DDM. Substituted derivatives, isophoronediamine [IPD], diaminodiphenylsulfone [DDS], 4,4′-methylenedianiline [MDA] or m-phenylenediamine [MPDA]), polyamide, alkyl / alkenylimidazole, dicyandiamide [DICY], 1,6-hexamethylene-bis-cyanoguanidine, or acid anhydrides such as dodecenyl succinic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride , Pyromellitic anhydride, and derivatives thereof.

  A preferred embodiment of the invention relates to a composition comprising a thermoplastic polymer as component c). Preferred thermoplastic polymers include polyolefin homopolymers and copolymers, copolymers of olefin vinyl monomers, styrenic homopolymers and copolymers thereof.

  Advantageously, the melamine and guanidine salts (I) and (II) are ground to a fine powder with an average particle size of less than 100 μm and then applied to the polymer substrate. This is because it is observed that the flame retardant properties of the composition of the present invention are improved by a small particle size.

Further components The present invention further comprises, in addition to components a), b) and c) as defined above, further optional additions selected from the group consisting of further flame retardants and so-called anti-dripping agents and polymer stabilizers. The present invention relates to a composition containing an agent.

Typical phosphorus-containing flame retardants are, for example:
Tetraphenyl resorcinol diphosphate (Fyrolflex® RDP, Akzo Nobel), resorcinol diphosphate oligomer (RDP), triphenyl phosphate, tris (2,4-di-tert-butylphenyl) phosphate, ethylenediamine diphosphate (EDAP) , Ammonium polyphosphate, diethyl-N, N-bis (2-hydroxyethyl) -aminomethylphosphonate, hydroxyalkyl esters of phosphoric acid, salts of [RX1] hypophosphoric acid (H ₃ PO ₂ ), in particular Ca ²⁺ , Zn ^2+, or Al ³⁺ salt, tetrakis (hydroxymethyl) phosphonium sulphide, triphenyl phosphine, 9,10-dihydro-9-oxa-10-phosphoryl naphthoylmethyl Nan vat 10-oxide (DOPO Derivatives, and phosphazene flame retardants.

  Nitrogen-containing flame retardants are, for example, isocyanurate flame retardants such as polyisocyanurate, esters of isocyanuric acid or isocyanurates. Representative examples include hydroxyalkyl isocyanurates such as tris- (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxy-n-proyl) isocyanurate or triglycidyl isocyanurate.

  Nitrogen-containing flame retardants include additional melamine flame retardants. Representative examples include: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate.

  As further examples: benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, urea cyanurate, ammonium polyphosphate, melem, melam, the condensation product of melamine from the melon series and And / or reaction products of higher condensation compounds or melamine with phosphoric acid or mixtures thereof.

Typical organic halogen flame retardants are, for example:
Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; Saytex® 102E), tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate (PB370) (Registered trademark), FMC Corp.), tris (2,3-dibromopropyl) phosphate, tris (2,3-dichloropropyl) phosphate, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly-α-chloro -Ethyl triphosphonate mixture, tetrabromobisphenol A bis (2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis (tetrabromophthalimide) (Saytex® BT-93), bis ( Xachlorocyclopentadieno) cyclooctane (Dechlorene Plus®), chlorinated paraffin, octabromodiphenyl ether, hexachlorocyclopentadiene derivative, 1,2-bis (tribromo-phenoxy) ethane (FF680), tetrabromo-bisphenol A (Saytex® RB100), ethylene bis- (dibromo-norbornane dicarboximide) (Saytex® BN-451), bis- (hexachlorocycloentadeno) cyclooctane, PTFE, tris- (2, 3-Dibromopropyl) -isocyanurate and ethylene-bis-tetrabromophthalimide.

The aforementioned organic halogen flame retardant is usually combined with an inorganic oxide synergist. The most common for this use is zinc oxide or antimony oxide, such as Sb ₂ O ₃ or Sb ₂ O ₅ . Boron compounds are also suitable.

Typical inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AlOOH), magnesium dihydroxide (MDH), zinc borate, CaCO ₃ , (organically modified) layered silicic acid Salts, layered double hydroxides (organically modified), and mixtures thereof.

  The aforementioned additional flame retardant class advantageously comprises from about 0.5% to about 60.0% by weight of an organic polymer substrate in the composition of the present invention; for example from about 1.0% to about 40.0%; For example, from about 5.0% to about 35.0% by weight based on the total weight of the polymer or composition.

  According to another embodiment, the present invention relates to a composition further comprising a so-called anti-dripping agent as a further component.

  These anti-dripping agents reduce the melt flow of the thermoplastic polymer and suppress the formation of droplets at high temperatures. Various references, such as US Pat. No. 4,263,201, describe the addition of anti-dripping agents to flame retardant compositions.

  Suitable additives that inhibit the formation of droplets at high temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibers, glass spheres, and the like.

  The addition of polysiloxanes of different structures has been proposed in various references; see US Pat. Nos. 6,660,787, 6,727,302 or 6,730,720. See

  The stabilizer is preferably halogen free and is a mono-nitroxyl stabilizer, nitrone stabilizer, amine oxide stabilizer, benzofuranone stabilizer, phosphite and phosphonite stabilizer, quinone metide stabilizer and 2,2'-alkylidene bisphenol stabilizer. Selected from the group consisting of acrylate esters.

  As mentioned above, the composition according to the present invention comprises pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling aids, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, One or more conventional additives selected from further light stabilizers and mixtures thereof, in particular pigments, phenolic antioxidants, calcium stearate, zinc stearate, 2-hydroxy-benzophenone, 2- (2′-hydroxyphenyl) -It may further contain a UV absorber of benzotriazole and / or 2- (2-hydroxyphenyl) -1,3,5-triazine group.

  Preferred further additives of the composition as defined above are processing stabilizers such as the phosphites and phenolic antioxidants mentioned above, and light stabilizers such as benzotriazole. Preferred specific antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol-tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate] (IRGANOX 1010), tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (IRGANOX 3114), 1,3,5-trimethyl-2,4 6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (IRGANOX 245), And Ν, Ν'-hexane-1,6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (IRGANOX 1098). Specific processing stabilizers include tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168), 3,9-bis (2,4-di-tert-butylphenoxy) -2,4, 8,10-tetraoxa-3,9-diphosphaspiro- [5.5] undecane (IRGAFOS 126), 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra- tert-butyl-1,1′-biphenyl-2,2′-diyl)] phosphite (IRGAFOS 12), and tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4, 4'-diylbisphosphonite (IRGAFOS P-EPQ) is mentioned. Specific light stabilizers include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN 234), 2- (5-chloro (2H ) -Benzotriazol-2-yl) -4- (methyl) -6- (tert-butyl) phenol (TINUVIN 326), 2- (2H-benzotriazol-2-yl) -4- (1,1,3) , 3-tetramethylbutyl) phenol (TINUVIN 329), 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (sec-butyl) phenol (TINUVIN 350), 2,2 '-Methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (T NUVIN 360), and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN 1577), 2- (2'-hydroxy- 5′-methyl-phenyl) benzotriazole (TINUVIN P), 2-hydroxy-4- (octyloxy) benzophenone (CHIMAS-SORB 81), 1,3-bis-[(2′-cyano-3 ′, 3 ′ -Diphenylacryloyl) oxy] -2,2-bis-{[(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] methyl} -propane (UVINUL 3030, BASF), ethyl-2-cyano-3 , 3-diphenyl acrylate (UVINUL 3035, BASF), and (2-ethylhexyl) -2-silane Ano-3,3-diphenyl-acrylate (UVINUL 3039, BASF).

  The aforementioned additives are preferably included in an amount of 0.01 to 10.0%, in particular 0.05 to 5.0%, based on the weight of the polymer substrate of component c).

  Incorporation of the above-defined components into the polymer component is a known method such as dry blending in the form of a powder or wet mixing in the form of a solution, dispersion or suspension in an inert solvent, water or oil, for example. Is implemented. Additive components a) and b) and any further additives, for example before or after molding, or by applying dissolved or dispersed additives or additive mixtures to the polymer material, and then solvent or suspension / The dispersant can be incorporated with or without evaporation. They can be added directly to processing equipment (eg extruders, internal mixers), for example as a dry mixture or powder, or as a solution or dispersion or suspension or melt.

  Addition of the additive component to the polymer substrate can be carried out in a conventional mixer where the polymer is melted and mixed with the additive. Suitable machines are known to those skilled in the art. They are mainly mixers, kneaders and extruders.

  The process is preferably carried out in the extruder by introducing additives during processing.

  Particularly preferred processors are single-screw extruders, counter-rotating and co-rotating twin-screw extruders, planetary gear extruders, ring extruders or kneaders. A processor with at least one gas removal compartment can be used, to which a vacuum can be applied.

  Suitable extruders and kneaders are described, for example, in Handbuch der Kunststoffextension, Vol. 1 Grundlagen, Editors F.M. Hensen, W.H. Knappe, H.M. Potente, 1989, pp. 3-7, ISBN: 3-446-14339-4 (Vol. 2 Extractionsangern 1986, ISBN 3-446-14329-7).

  For example, the screw length is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the screw is preferably 10 to 600 revolutions / minute (rpm), preferably 25 to 300 rpm.

  Maximum throughput depends on screw diameter, rotational speed and thrust. The methods of the present invention can also be practiced by varying the described parameters or employing a meter that delivers a dose at a level below maximum throughput.

  If multiple components are added, they can be premixed or added individually.

  Additive component a) and any further additives can also be sprayed onto the polymer substrate b). The additive mixture is diluted so that other additives such as the conventional additives described above, or melts thereof, can be sprayed onto the polymer substrate together with these additives. Addition by spraying during the deactivation of the polymerization catalyst is particularly advantageous; in this case, the generated steam can be used for deactivation of the catalyst. In the case of spherical polymerised polyolefins, it may be advantageous, for example, to apply the additives according to the invention by spraying, optionally together with other additives.

  Additive components a) and b) optional further additives are also present, for example at concentrations at which about 1.0% to about 40.0%, preferably 2.0% to about 20.0% by weight are incorporated into the polymer. Can be added to the polymer in the form of a masterbatch ("concentrate") containing the ingredients. The polymer does not necessarily have the same structure as the polymer to which the additive is finally added. In such operations, the polymer can be used in the form of powders, granules, solutions, and suspensions, or in the form of a lattice.

  Incorporation can occur before or during the molding operation. The materials containing the inventive additives described herein are preferably molded articles, such as rotationally molded articles, injection molded articles, profiles and the like, and in particular the production of fibers, melt-spun nonwovens, films or foams. Used for.

  Components a) and b) are added to the polymer substrate c), 0.1 to 45.0% by weight for component a), preferably 0.1 to 30.0% by weight and 0.05 to 5 for component b). Mix at a concentration of 0.0 mass%, preferably 0.1-2.0 mass%.

  Preferred ratios of components a): b) are in the range of 50: 1 to 1: 5, preferably 20: 1 to 1: 2.

および式

（式中、ｎは１〜１５である）
の化合物
からなる群から選択される少なくとも１つのテトラアルキルピペリジン誘導体ＩＩＩｃまたはＩＩＩｄ；ならびに
ｃ）ポリオレフィンホモポリマーおよびオレフィンの互いとの、またはビニルモノマーとのコポリマーからなる群から選択される熱可塑性ポリマー
を含む組成物、特に難燃剤組成物に関する。 Particularly preferred embodiments of the present invention are:
a) a salt of a phosphinic acid represented by structural formula (I) or (II), wherein
One of R ¹ and R ² represents hydrogen or C ₁ -C ₈ alkyl; or R ¹ and R ² both represent C ₁ -C ₈ alkyl; and R ³ represents C ₁ -C ₁₀ alkylene , C ₂ -C ₁₀ alkylene interrupted by phenylene, phenylene, (C ₁ -C ₄ alkyl) _1-3 phenylene, or phenyl-C ₁ -C ₄ alkylene);
b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine,
N, N′-bis (3-amino of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine Reaction product with propyl) ethylenediamine),
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,
2,4′-Hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine endcapped 2,4- An oligomeric compound which is a condensation product with dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine;
Compound of formula

And expression

(In the formula, n is 1 to 15)
At least one tetraalkylpiperidine derivative IIIc or IIId selected from the group consisting of: and c) a thermoplastic polymer selected from the group consisting of polyolefin homopolymers and copolymers of olefins with each other or with vinyl monomers It is related with the composition containing, especially a flame retardant composition.

  The following examples illustrate the invention but should not be construed as limiting its scope.

Example
Components and Reagents Used Moplen® HF500 N: commercial grade polypropylene (Basell, Germany);
Tinuvin® NOR371 (NOR1): commodity (Ciba Inc., Switzerland);
Flamestab® NOR116 (NOR2): commercial product (Ciba Inc., Switzerland);
Exolit OP® 1240: diethylphosphinic acid aluminum salt (Clariant, Switzerland).

Test methods for assessing flame retardancy
"Flammability of Plastic Materials for Parts in Devices and Appliances", 5 th edition, UL94 test of October 29, 1996. The UL94V test scores are collected in the following table (time is displayed for one sample):

ｎ．ｃ：分類なし

n. c: No classification

Preparation of the polymer composition / extrusion Reference composition according to Examples 1-4 and the composition of the invention according to Examples 1-4: polypropylene homopolymer (MOPLEN HF500N), co-rotating twin screw extruder ZSK25 (Coperion Werner) & Pfleiderer) at a temperature T _{max of} 230 ° C., a throughput speed of 4 kg / h and a rotational speed of 100 revolutions per minute (rpm). To MOPLEN HF500N, a basic level stabilizing composition (0.05% Ca stearate + 0.5% IRGANOX® B225 was added; IRGANOX® B225 was added to IRGAFOS® 168 and IRGANOX® Trademark) 1010))) as well as the additives listed in Table 1.

  After cooling in a water bath, the polymer strand is granulated. UL94-V test specimens according to DIN 4102-B2 (125 × 12.5 mm, thickness = 1.6 mm bar) and 1.0 mm plaques are produced by injection molding at 230 ° C. on an Arburg 370S injection molding machine. A film according to DIN 4102-B2 is obtained by compression molding.

After testing the polymer compositions for 48 hours at 23 ° C. and 50% relative humidity, the test samples are examined for their flame retardant behavior according to the UL94-V standard.

  After the test sample is exposed to deionized water at 70 ° C. for 7 days, a further UL94-V test is performed (leaching test). The test bar is then dried in a vacuum oven at 105 ° C. for 24 hours. The results obtained after leaching are shown in Table 2.

Table 1
UL94V (1.6 mm) test results obtained with polypropylene homopolymers containing different flame retardant compositions

^a）ＵＬ９４試験基準にしたがって、着火した試験バーからしたたり落ちる燃焼ドリップが試験バーの下に置かれた綿に着火する試験の回数（５回の試験のうち）。

^a) Number of tests (out of 5) in which the burning drip dripping from the ignited test bar ignites the cotton placed under the test bar according to UL94 test standards.

  From the above results, it can be concluded that the polymer composition according to the present invention exhibits excellent flame retardancy along with self-extinguishing properties. Although no reference composition containing one additive exhibits significant flame retardant behavior, the inventive combination of a phosphinate and a representative sterically hindered N-alkoxyamine provides efficient flame retardant properties. I will provide a.

Table 2
Properties and UL94V (1.6 mm) results of polypropylene homopolymer test bars containing flame retardant compositions of the present invention after leaching at 70 ° C. in deionized water for 7 days.

^a）ＵＬ９４試験基準に従って、着火した試験バーからしたたり落ちた燃焼ドリップが試験バーの下に置かれた綿に着火する試験の回数（５回の試験のうち）。

^a) Number of tests (out of 5) in which the burning drip from the ignited test bar ignites the cotton placed under the test bar in accordance with UL94 test standards.

  From the results shown in Table 2, it can be concluded that representative polymer compositions according to the present invention are characterized by excellent leaching resistance to water. After the leaching test, essentially no changes in mass loss and sample thickness are observed. Example 3 of the present invention shows that the UL94V-2 rating is maintained during the leaching test.

Claims (11)

a) A salt of phosphinic acid having the formula

(In the above formula,
One of R ¹ and R ² represents hydrogen and the other represents C ₁ -C ₈ -alkyl; or R ¹ and R ² both represent C ₁ -C ₈ -alkyl;
M is (C ₁ -C ₄ -alkyl) ₄ N, (C ₁ -C ₄ -alkyl) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₄ N, (C ₂ -C ₄ -alkyl OH) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₂ N (CH ₃ ) ₂ , (C ₂ -C ₄ -alkyl OH) ₂ NHCH ₃ , (C ₆ H ₅ ) ₄ N, (C ₆ H ₅ ) ₃ NH, (C ₆ H ₅ CH ₃ ) ₄ N, (C ₆ H ₅ CH ₃ ) ₃ NH, NH ₄ , melamine, guanidine, alkali metal ion or alkaline earth metal ion, or aluminum ion, zinc ion, iron Represents ions or boron ions;
m is a number from 1 to 3, indicating the number of positive charges on M; and
n is a number of 1 to 3 and represents the number of phosphinic acid anions corresponding to M ^{m +} )
A salt of phosphinic acid represented by
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine, 1-acyloxy-2,2,6,6 -tetraalkylpiperazine , 1-hydroxy-2,2,6,6-tetraalkylpiperazine, 1-alkoxy-2,2,6,6-tetraalkylpiperazine, and 1 A tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the group consisting of acyloxy-2,2,6,6- tetraalkylpiperazine ;
And c) a composition comprising a polymer substrate . A composition according to claim 1, comprising:
The phosphinic acid salt of component a) above has the formula

Represented by the
Composition. A composition according to claim 1 or 2,
a) The following formula

Aluminum salt of phosphinic acid represented by;
b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine and A tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6- tetraalkylpiperidine ;
And c) a composition comprising a thermoplastic polymer substrate. The composition according to any one of claims 1 to 3, comprising:
Component b) includes at least one tetraalkylpiperidine derivative, wherein the tetraalkylpiperidine derivative is
The following formula

Of 2,2,6,6-tetraalkylpiperidine-1-oxide ;
The following formula

Of 1-hydroxy-2,2,6,6-tetraalkylpiperidine ;
The following formula

Of 1-alkoxy-2,2,6,6-tetraalkylpiperidine ;
And
The following formula

1-acyloxy-2,2,6,6-tetraalkylpiperidine ( wherein each of the above formulas,
One of R _a and R _b represents hydrogen or N-substituted group, and the other is either represents O substituents or C substituent; or, R _a and R _b are both hydrogen, the O substituent or C substituent and table;
R is, C ₁ -C ₂₀ - alkyl, C ₅ -C ₆ - or represents cycloalkyl, or, C ₂ -C ₂₀ with further substituents - alkyl, C ₅ -C ₆ - cycloalkyl or C ₂ ~ the C ₂₀ alkenyl and table;
Ac is to display the acyl group of C ₁ -C ₂₀ carboxylic acid; and,
R ₁ to R ₄ each are C ₁ -C ₄ - alkyl were table; and,
R ₅ and R ₆ are, independently of one another, hydrogen or, C ₁ -C ₄ - alkyl, C ₁ -C ₃ - Represents a substituent selected from the group consisting of alkyl, phenyl and phenyl; or, R ₅ And R ₆ together represent oxo)
Selected from the group consisting of :
Composition. A composition according to claim 4, wherein
The Te tiger alkyl piperidine derivatives IIIa component b), IIIb, as IIIc or IIId,
One of R _a and R _b represents hydrogen or N-substituted group, and the other is either represents O substituents or C substituent; or, R _a and R _b are both hydrogen, the O substituent or C substituent and table;
R is, C ₁ -C ₈ - alkyl, C ₅ -C ₆ - or represents cycloalkyl, or, C ₂ -C ₈ having further substituents - alkyl, C ₅ -C ₆ - cycloalkyl or C ₂ ~ the C ₈ alkenyl and table;
Ac is, to display the acyl group of C ₁ -C ₈ carboxylic acid; and,
R ₁ to R ₄ are, Ri methyl der respectively; and,
R ₅ and R ₆ each represent hydrogen,
Including at least one tetraalkylpiperidine derivative,
Composition. A composition according to claim 4, wherein
The Te tiger alkyl piperidine derivatives IIIa component b), IIIb, as IIIc or IIId,
One of R _a and R _b represents hydrogen or N-substituted group, and the other is either represents O substituents or C substituent; or, R _a and R _b are both, O-substituted to display the group or C substituent;
R is, C ₁ -C ₈ - alkyl, C ₅ -C ₆ - or represents cycloalkyl, or, C ₂ -C ₈ substituted by a hydroxy - alkyl, C ₅ -C ₆ - cycloalkyl or C ₂ ~ the C ₈ alkenyl and table;
Ac is to display the acyl group of C ₁ -C ₈ carboxylic acid; and,
R ₁ to R ₄ are, Ri methyl der respectively; and,
R ₅ and R ₆ each represent hydrogen
Including at least one tetraalkylpiperidine derivative,
Composition. A composition according to claim 4, wherein
Component b) contains at least one tetraalkylpiperidine derivative IIIc or IIId, where the tetraalkylpiperidine derivative IIIc or IIId is
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine ;
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine ;
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine ;
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine ;
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine ;
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine ;
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate ;
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate ;
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine ;
N, N′-bis (3-amino of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine Reaction product with propyl) ethylenediamine) ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine ;
2,4′-Hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine endcapped 2,4- An oligomeric compound which is a condensation product of dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine ;
The following formula

Compound;
And
The following formula

Compound (in the above formulas, n is 1 to 15)
Selected from the group consisting of :
Composition. A composition according to claim 1, comprising:
a) A salt of phosphinic acid having the formula

(In the above formula,
One of R ¹ and R ² represents hydrogen and the other represents C ₁ -C ₈ -alkyl; or R ¹ and R ² both represent C ₁ -C ₈ -alkyl;
M is (C ₁ -C ₄ -alkyl) ₄ N, (C ₁ -C ₄ -alkyl) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₄ N, (C ₂ -C ₄ -alkyl OH) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₂ N (CH ₃ ) ₂ , (C ₂ -C ₄ -alkyl OH) ₂ NHCH ₃ , (C ₆ H ₅ ) ₄ N, (C ₆ H ₅ ) ₃ NH, (C ₆ H ₅ CH ₃ ) ₄ N, (C ₆ H ₅ CH ₃ ) ₃ NH, NH ₄ , melamine, guanidine, alkali metal ion or alkaline earth metal ion, or aluminum ion, zinc ion, iron Represents ions or boron ions;
m is a number from 1 to 3, indicating the number of positive charges on M; and
n is a number of 1 to 3 and represents the number of phosphinic acid anions corresponding to M ^{m +} )
A salt of phosphinic acid represented by
b) a tetraalkylpiperidine derivative,
1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine ;
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine ;
Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine ;
1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine ;
1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine ;
1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine ;
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate ;
Bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate ;
2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2- Hydroxyethylamino) -s-triazine ;
N, N′-bis (3-amino of 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine Reaction product with propyl) ethylenediamine) ;
2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine ;
2,4′-Hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -s-triazine endcapped 2,4- An oligomeric compound which is a condensation product of dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine ;
The following formula

Compound;
and
The following formula

Compound (in the above formulas, n is 1 to 15)
It is selected from the group consisting of lutein tiger alkyl piperidine derivative of at least one;
And c) a thermoplastic polymer selected from the group consisting of polyolefin homopolymers and copolymers of olefins with each other or with vinyl monomers ,
Composition. A composition according to any one of 請 Motomeko 1 to 8, a composition for use as a flame retardant. a) A salt of phosphinic acid having the formula

(In the above formula,
One of R ¹ and R ² represents hydrogen and the other represents C ₁ -C ₈ -alkyl; or R ¹ and R ² both represent C ₁ -C ₈ -alkyl;
M is (C ₁ -C ₄ -alkyl) ₄ N, (C ₁ -C ₄ -alkyl) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₄ N, (C ₂ -C ₄ -alkyl OH) ₃ NH, (C ₂ -C ₄ -alkyl OH) ₂ N (CH ₃ ) ₂ , (C ₂ -C ₄ -alkyl OH) ₂ NHCH ₃ , (C ₆ H ₅ ) ₄ N, (C ₆ H ₅ ) ₃ NH, (C ₆ H ₅ CH ₃ ) ₄ N, (C ₆ H ₅ CH ₃ ) ₃ NH, NH ₄ , melamine, guanidine, alkali metal ion or alkaline earth metal ion, or aluminum ion, zinc ion, iron Represents ions or boron ions;
m is a number from 1 to 3, indicating the number of positive charges on M; and
n is a number of 1 to 3 and represents the number of phosphinic acid anions corresponding to M ^{m +} )
A salt of phosphinic acid represented by
And b) 2,2,6,6-tetraalkylpiperidine-1-oxide, 1-hydroxy-2,2,6,6-tetraalkylpiperidine, 1-alkoxy-2,2,6,6-tetraalkylpiperidine And a mixture comprising a tetraalkylpiperidine derivative selected from the group consisting of 1-acyloxy-2,2,6,6- tetraalkylpiperidine . A method for imparting flame retardancy to a polymer substrate, on the polymer substrate, comprising the step of adding a mixture as claimed in claim 10, methods.