JP2015516996A - Urea compounds for improving the solid properties of polyamide resins - Google Patents

Abstract

The present invention provides a compound of formula (I) for improving at least one solid property of a polyamide resin wherein x is 1, 2 or 3, R1 and R2 are hydrogen, linear C1-C7-alkyl. Branched C3-C10-alkyl, unsubstituted or substituted C3-C12-cycloalkyl, unsubstituted or substituted C3-C12-cycloalkyl-C1-C4-alkyl, unsubstituted or substituted aryl And Z is C3 -C10 -alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C1 -C4 -Alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted heteroarylene-C1-C4-alkylene-heteroarylene, unsubstituted Is substituted C5-C8-cycloalkylene, unsubstituted or substituted C5-C8-cycloalkylene-C1-C4-alkylene-C5-C8-cycloalkylene, unsubstituted or substituted heterocycloalkylene, and unsubstituted Or selected from substituted heterocycloalkylene-C 1 -C 4 -alkylene-heterocycloalkylene]. Said solid properties are preferably selected from mechanical properties and gloss.

Description

  The present invention relates to the use of urea compounds to improve the solid properties of polyamide resins. More particularly, the present invention relates to the use of urea compounds to improve the mechanical properties and gloss of polyamide resins.

Polyamide (PA) is a well-known and commercially available polymer, and because of its very good performance characteristics and low cost, in many applications such as automotive, aircraft, mechanical engineering, electrical, electronic, sports and leisure industries It is used. In many cases, modification of the polyamide resin is sought in order to impart advantageous properties to articles molded from polyamides or from compositions containing polyamides, which are mechanical properties such as enhanced Elastic modulus, tensile stress at break, tensile strain at break, or notched impact toughness, and appearance, such as improved surface gloss. In particular, it is desirable that the polyamide resin has good mechanical properties at high temperatures, for example, when it is higher than the glass transition temperature _TG . These polyamides can be used for the production of mechanically stressed parts that are exposed to high temperatures in use. For the production of thin parts, the good stiffness / toughness properties of polyamide resins are also required.

  It is known that the mixing of talc in a polyamide resin improves the rigidity and bending strength of the polyamide resin. However, this results in a decrease in tensile properties and impact toughness.

JP5320501 is a polyamide resin, barium stearate as a release agent, and a formula (R ¹ —NHC (O) NH) ₂ X wherein X is a divalent hydrocarbon group and R ¹ is 9 A polyamide resin composition having enhanced flow properties, crystallization properties and release properties is described, comprising a bisurea compound of an aliphatic hydrocarbon group having ˜40 carbon atoms. The combination of barium stearate and a bisurea compound imparts high resistance to release distortion to an injection moldable polyamide resin.

  Accordingly, there is a constant need for polyamide resins with improved solid properties to expand the range of performance. The solid properties include mechanical properties and gloss properties, such as surface gloss properties. In particular, there is a great need for polyamide resins that exhibit good mechanical properties.

  Surprisingly, it has now been found that urea compounds of the formula I defined below are suitable for improving the solid properties of polyamide resins.

［式中、
ｘは１、２または３であり、
Ｒ¹およびＲ²は互いに独立して、水素、直鎖のＣ₁〜Ｃ₇−アルキル、分枝鎖のＣ₃〜Ｃ₁₀−アルキル、非置換または置換されたＣ₃〜Ｃ₁₂−シクロアルキル、非置換または置換されたＣ₃〜Ｃ₁₂−シクロアルキル−Ｃ₁〜Ｃ₄−アルキル、非置換または置換されたアリール、および非置換または置換されたアリール−Ｃ₁〜Ｃ₄−アルキルから選択され、且つ、
ＺはＣ₃〜Ｃ₁₀−アルカンジイル、非置換または置換されたアリーレン、非置換または置換されたアリーレン−Ｃ₁〜Ｃ₄−アルキレン−アリーレン、非置換または置換されたヘテロアリーレン、非置換または置換されたヘテロアリーレン−Ｃ₁〜Ｃ₄−アルキレン−ヘテロアリーレン、非置換または置換されたＣ₅〜Ｃ₈−シクロアルキレン、非置換または置換されたＣ₅〜Ｃ₈−シクロアルキレン−Ｃ₁〜Ｃ₄−アルキレン−Ｃ₅〜Ｃ₈−シクロアルキレン、非置換または置換されたヘテロシクロアルキレン、および非置換または置換されたヘテロシクロアルキレン−Ｃ₁〜Ｃ₄−アルキレン−ヘテロシクロアルキレンから選択される］
の少なくとも１種の尿素化合物の使用に関する。特に、固体特性は、機械的特性および光沢から選択される。 Accordingly, the present invention provides a formula I for improving the solid state properties of polyamide resins.

[Where:
x is 1, 2 or 3;
R ¹ and R ² are independently of each other hydrogen, straight chain C ₁ -C ₇ -alkyl, branched C ₃ -C ₁₀ -alkyl, unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl. , unsubstituted or substituted C ₃ -C ₁₂ - cycloalkyl -C ₁ -C ₄ - selected from alkyl - alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl -C ₁ -C ₄ And
Z is C ₃ -C ₁₀ -alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C ₁ -C ₄ -alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted Heteroarylene-C ₁ -C ₄ -alkylene-heteroarylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene-C ₁ -C ₄ - alkylene -C ₅ -C ₈ - cycloalkylene, unsubstituted or substituted heterocycloalkylene, and unsubstituted or substituted heterocycloalkylene -C ₁ -C ₄ - alkylene - is selected from heterocycloalkylene]
The use of at least one urea compound. In particular, the solid properties are selected from mechanical properties and gloss.

  The present invention also provides a method for improving the solid material properties of a polyamide resin, said method comprising adding to the polyamide resin at least one urea compound of formula I as defined above.

  In the terminology of the present invention, “solid property of polyamide resin” is to be understood as the property of polyamide in the solid state. The solid properties are preferably selected from gloss and mechanical properties. Mechanical properties include, for example, modulus of shear and tensile properties such as yield stress, yield strain, tensile strain at break, tensile stress at break, tensile modulus and notched impact toughness.

The inventive use of the urea compound of formula I involves at least one of the following advantages compared to a composition without said addition:
-Improvement of at least one mechanical property, in particular notched impact toughness, tensile stress at break, tensile strain at break, Young's modulus (elastic modulus) and shear modulus;
-Enhanced gloss.

  As used herein, the term “semicrystalline” describes a polyamide polymer that exhibits an X-ray pattern with sharp shape features in the crystalline region and diffusive shape features in the amorphous region.

For the purposes of the present invention, a set name is used for the definition of the variable shown in the formula, together with a set name that generally and representatively represents the substituent in question. C _n -C _m - definition of shows each of the respective in the substituents or substituted ingredients possible number of carbon atoms.

The term “C ₁ -C ₄ -alkyl” as used herein refers to a straight or branched alkyl group having 1 to 4 carbon atoms. Examples are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl and tert-butyl.

The term “straight chain C ₁ -C ₇ -alkyl” as used herein refers to a straight chain alkyl group having 1 to 7 carbon atoms. Examples are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and n-heptyl.

The term “branched C ₃ -C ₁₀ -alkyl” as used herein refers to a branched alkyl group having from 3 to 10 carbon atoms. Examples are iso-propyl, 2-butyl, iso-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 -Methylpropyl, 1-ethyl-2-methylpropyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, -Methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1 -Propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl And that kind of thing.

The term “C ₁ -C ₁₀ -alkyl” as used herein refers to a straight or branched alkyl group having 1 to 10 carbon atoms. C ₁ -C ₁₀ - Examples for _{alkyl, C 1 ~C 4 - C 3} ~C 10 alkyl and branched - Outside those described for the alkyl, n- pentyl, n- hexyl, n- heptyl , N-octyl, n-nonyl and n-decyl.

The term “C ₃ -C ₁₀ -alkanediyl” (also referred to as C ₃ -C ₁₀ -alkylene), as used herein, is a straight or branched chain having 3 to 10 carbon atoms. Saturated alkyl groups of the chain, wherein one of the hydrogen atoms in those groups is replaced by a further bonding position. Examples for linear C ₃ -C ₆ -alkanediyl are propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl. Examples for branched C ₃ -C ₆ -alkanediyl are propyl-1,1-diyl, butyl-1,1-diyl, 1-methylethane-1,2-diyl, 1,2-dimethylethane- 1,2-diyl, 1-ethylethane-1,2-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl and the like.

The term “C ₃ -C ₁₂ -cycloalkyl” as used herein refers to 3 to 12 carbon atoms (═C _{3 to} C ₁₂ -cycloalkyl), frequently 5 to 10 carbon atoms. carbon atoms - represents a single or bicyclic or tricyclic hydrocarbon group having (C ₅ -C ₁₀ cycloalkyl). Examples of monocyclic groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic groups having 7 to 8 carbon atoms are bicyclo [2.2.1] hexyl, bicyclo [2.2.1] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2 2.2.2] octyl and bicyclo [3.2.1] octyl. Examples of tricyclic groups include 1-adamantyl, 2-adamantyl and homoadamantyl. C ₃ -C ₁₂ -cycloalkyl may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^a , said R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen.

The term “C ₅ -C ₈ -cycloalkylene” (also referred to as C ₅ -C ₈ -cycloalkanediyl), as used herein, is each a cycloalkyl group as defined above. Wherein one hydrogen atom of the cycloalkyl ring is replaced by one additional binding site to form a divalent component. C ₅ -C ₈ -cycloalkylene may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^b , said R ^b is C ₁ -C ₁₀ - is selected from alkyl or halogen.

The term “C _n -C _m -cycloalkyl-C _o -C _p -alkyl” as used herein refers to a cycloalkyl group as defined above having _n to _m carbon atoms. Which is attached to the rest of the molecules having o to p carbon atoms as defined above via an alkylene group. Examples are cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl and the like. When C _n -C _m -cycloalkyl-C _o -C _p -alkyl is substituted, the cycloalkyl component is one or more, for example 1, 2 or 3 identical or different groups R ^a. Wherein R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen.

The term “aryl” as used herein refers to a C ₆ -C ₁₄ -monoaromatic group such as phenyl, naphthyl, anthracenyl and phenanthrenyl. Aryl may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^a , said R ^a being C ₁ -C ₁₀ -Selected from alkyl or halogen. Preferably aryl is phenyl.

The term “arylene”, as used herein, is each an aryl group as defined above, wherein one hydrogen atom at any position of the aryl is replaced by one additional attachment site. , Showing what forms a divalent component. Arylene may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^b , said R ^b being C ₁ -C ₁₀ -Selected from alkyl or halogen. Preferably aryl is phenylene.

  The term “phenylene” refers to 1,2-phenylene (o-phenylene), 1,3-phenylene (m-phenylene) and 1,4-phenylene (p-phenylene).

The term “heteroaryl” (“monocyclic or bicyclic 5-10 membered heteroaromatic ring”) as used herein refers to monocyclic or heterocyclic 5, 6 or 7 members. Monocyclic heteroaromatic groups having 5 or 6 ring members that may be fused to the ring, and thus have a total number of ring members of 8 to 10, each of 1 of those ring members 2, 3 or 4, preferably 1, 2 or 3, independently of one another, are those heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur. A heteroaryl group can be attached to the remainder of the molecule through a carbon ring member or through a nitrogen ring member. Homocyclic or fused heterocyclic is, C ₅ -C ₇ - cycloalkyl, heterocyclyl and phenyl, 6- or 7-membered. A heteroaryl may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^a , said R ^a being C ₁ -C Selected from ₁₀ -alkyl or halogen. Preferably aryl is phenyl.

  Examples for monocyclic 5-6 membered heteroaromatic rings are triazinyl, pyrazinyl, pyrimidyl, pyridanyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, Contains isothiazolyl and isoxazolyl.

  Examples for 5 or 6 membered heteroaromatic rings fused to a phenyl ring (or for phenyl rings fused to 5 to 6 membered heteroaromatic rings) are quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl Benzofuryl, benzthienyl, benzo [b] thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl and benzimidazolyl. Examples for 5-6 membered heteroaromatic rings fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolidinyl, dihydroisoindolyl, dihydroquinolinyl, dihydroisoquinolinyl, chromenyl, chromanyl And that kind of thing.

The term “heteroarylene” as used herein is a heteroaryl group as defined above wherein one hydrogen atom at any position of the heteroaryl is replaced by one additional attachment site. And the one forming a divalent component. A heteroarylene may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^b , said R ^b being C ₁ -C Selected from ₁₀ -alkyl or halogen.

The term “heterocyclyl” refers to non-aromatic, saturated or partially unsaturated 5 or 6 ring members, and 1, 2, 3 or 4, preferably 1, 2 or 3 heteroatoms. Including a heterocyclic ring as a member. The heterocyclic group may be attached to the rest of the molecule via a carbon ring member or via a nitrogen ring member. Examples for non-aromatic rings are pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl , Oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, piperanyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, dihydrothiopyranyl, Includes tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like. Examples for heterocyclic rings that also contain one or two carbonyl groups as ring members are pyrrolidine-2-onyl, pyrrolidine-2,5-dionyl, imidazolidin-2-onyl, oxazolidine-2-onyl, thiazolidine-2 -Including onyl and its species. A heterocyclyl may be unsubstituted or substituted by one or more, for example 1, 2 or 3, identical or different groups R ^a , said R ^a being C ₁ -C _10. -Selected from alkyl or halogen. Preferably aryl is phenyl.

  The term “halogen” refers to fluorine, chlorine, bromine or iodine.

  Depending on the substitution pattern, the compounds of the formula I used according to the invention can have one or more chiral centers, in which case they exist as a mixture of enantiomers or diastereomers. The present invention provides the use according to the invention of the pure enantiomers or diastereomers of compounds I or mixtures thereof.

  Polyamide polymers are to be understood herein as homopolymers, copolymers, blends and grafts of synthetic long chain polyamides having amide groups that repeat within the polymer backbone as the main component.

  Examples of polyamide homopolymers are nylon-6 (PA6, polycaprolactam), nylon-7 (PA7, polyenantolactam or polyheptanoamide), nylon-10 (PA10, polydecanamide), nylon-11 (PA 11, polyundecanolactam), nylon-12 (PA12, polydodecanolactam), nylon-4,6 (PA46, polytetramethylene adipamide), nylon-6,6 (PA66, polyhexamethylene) Adipamide), nylon-6,9 (PA 69, polycondensation product of 1,6-hexamethylenediamine and azelaic acid), nylon-6,10 (PA610, 1,6-hexamethylenediamine and 1 , 10-decanedioic acid polycondensation product), nylon-6,12 (PA 612, 1,6-hexane) Polycondensation product of methylene diamine and 1,12-dodecanedioic acid), nylon 10,10 (PA 1010, polycondensation product of 1,10-decane diamine and 1,10-decanedicarboxylic acid), PA 1012 (Polycondensation product of 1,10-decane methylenediamine and dodecanedicarboxylic acid) or PA 1212 (polycondensation product of 1,12-dodecane methylenediamine and dodecanedicarboxylic acid).

  The polyamide copolymer can include polyamide constituent units in various proportions. Examples of polyamide copolymers are made from nylon 6/66 and nylon 66/6 (PA 6/66, PA 66/6; PA 6 and PA 66 building blocks, ie made from caprolactam, hexamethylenediamine and adipic acid Copolyamide). PA 66/6 (90/10) can contain 90% PA66 and 10% PA6. A further example is nylon 66/610 (made from PA 66/610, hexamethylenediamine, adipic acid and sebacic acid).

  The polyamide further includes a partially aromatic polyamide. Partially aromatic polyamides are usually derived from aromatic dicarboxylic acids, such as terephthalic acid or isophthalic acid, and linear or branched aliphatic diamines. Examples are PA 9T (formed from terephthalic acid and nonanediamine), PA 6T / 6I (formed from hexamethylenediamine, terephthalic acid and isophthalic acid), PA 6T / 6, PA 6T / 6I / 66 and PA 6T / 66. .

  Polyamides further include aromatic polyamides such as poly-meta-phenylene-isophthalamide (Nomex®) or poly-para-phenylene-terephthalamide (Kevlar®).

  Polyamides can in principle be prepared by two methods. In the polymerization from dicarboxylic acids and diamines, and in the polymerization from amino acids or their derivatives, such as aminocarbonitriles, aminocarboxamides, aminocarboxylate esters or aminocarboxylate salts, the amino and carboxyl end groups of the starting monomer or starting oligomer are Reacts with each other to form an amide group and water. Subsequently, water can be removed from the polymer. In polymerization from carboxamide, the amino and amide end groups of the starting monomer or starting oligomer react with each other to form an amide group and ammonia. Subsequently, ammonia can be removed from the polymer. This polymerization reaction is usually known as polycondensation.

  Polymerization from lactams as starting monomers or starting oligomers is usually known as polyaddition.

  Polyamides further comprise copolymers made of polyamide and of further segments, for example in the form of diols, polyesters, ethers etc., in particular in the form of polyesteramides, polyetheresteramides or polyetheramides. For example, in a polyether amide, the polyamide segment can be any commercially available polyamide, preferably PA 6 or PA 66, and the polyether is usually polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

  The polyamide is preferably a semicrystalline polyamide selected from aliphatic polyamides, partially aromatic polyamides and mixtures thereof. According to a particular embodiment, the polyamide resin is PA 6, PA 7, PA 10, PA 11, PA 12, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 6/66, PA 66/6. PA 66/610 and mixtures thereof. According to a more particular aspect, the polyamide is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66. In particular, the polyamide is PA 6.

  The explanations given below as preferred embodiments of the variables (substituents) and subscripts of the compounds of formula I are valid on their own and preferably in combination with each other. It is known to those skilled in the art that x is 2 or 3 and Z may be the same or different.

An embodiment of the present invention relates to a use or method in which the variables R ¹ , R ² , Z and x each independently or in combination have the following meanings in compounds of the formula I:
x is 1, 2 or 3;
R ¹ and R ² are independently of each other straight chain C ₁ -C ₇ -alkyl, branched C ₃ -C ₁₀ -alkyl, unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl, non- unsubstituted or substituted C ₃ -C ₁₂ - cycloalkyl -C ₁ -C ₄ - is selected from alkyl - alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl -C ₁ -C ₄ ,and,
Z is C ₃ -C ₁₀ -alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C ₁ -C ₄ -alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted Heteroarylene-C ₁ -C ₄ -alkylene-heteroarylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene-C ₁ -C _{It is selected from 4} -alkylene-C ₅ -C ₈ -cycloalkylene, unsubstituted or substituted heterocycloalkylene, and unsubstituted or substituted heterocycloalkylene-C ₁ -C ₄ -alkylene-heterocycloalkylene.

A preferred embodiment of the present invention relates to the use and method in the compounds of formula I when the variables R ¹ , R ² , Z and x each independently or in combination have the following meanings:
x is 1, 2 or 3, preferably 1 or 2, in particular 1;
R ¹ and R ² independently of one another, hydrogen, a branched C ₃ -C ₁₀ - alkyl, C ₅ -C ₁₂ - cycloalkyl, C ₅ -C ₁₂ - cycloalkyl, C ₅ -C ₁₂ - Each ring in the last four groups selected from C ₁ -C ₄ -alkyl, aryl and aryl-C ₁ -C ₄ -alkyl is unsubstituted or has one or more Substituted by the same or different groups R ^a , wherein R ^a is selected from C ₁ -C ₁₀ -alkyl and halogen. More preferably, R ¹ and R ² independently of one another are hydrogen, branched C ₃ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ Each ring in the last four groups selected from ˜C ₁₂ -cycloalkyl-C ₁ -C ₄ -alkyl, phenyl and phenyl-C ₁ -C ₄ -alkyl is unsubstituted or Or substituted by one or more identical or different groups R ^a , wherein R ^a is selected from C ₁ -C ₁₀ -alkyl and halogen. In particular, R ¹ and R ² are, independently of one another, hydrogen, branched C ₃ -C ₁₀ -alkyl (attached to the skeleton via the secondary or tertiary carbon atom of the alkyl group). , unsubstituted or 1 or 2 radicals C which is substituted by R ^a ₅ ~C ₁₀ - is selected from phenyl substituted by cycloalkyl, and unsubstituted or 1 or 2 radicals R ^a. Suitable examples for R ¹ and R ² are hydrogen, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 1-methylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2-methylbutyl 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 2-adamantyl, homoadamantyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, 1-cyclopentylethyl, 2-cyclopentylethyl, cyclohexylmethyl , 1-cyclohexylethyl, 2-cyclohexylethyl, 1 or 2 C ₁ -C ₄ - cyclopentyl substituted by alkyl, one or two C ₁ -C ₄ - cyclohexyl which is substituted by alkyl, phenyl, tolyl or 3 , 4-Dimethylpheny It is le. In particular, R ¹ and R ² are hydrogen, isopropyl, tert-butyl, 1-methylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2-methylbutyl, 1,5-dimethylhexyl, 1,1,3 , 3-tetramethylbutyl and 1-adamantyl.

Z is C ₅ -C ₈ -alkylene, C ₅ -C ₇ -cycloalkylene, C ₅ -C ₇ -cycloalkylene-CH ₂ -C ₅ -C ₇ -cycloalkylene, phenylene or phenylene-CH ₂ -phenylene. Where each ring in the last four groups mentioned is unsubstituted or substituted by one or two identical or different groups R ^b , said R ^b being C ₁ -C _10- Alkyl or halogen. Z is preferably 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, cis 1,2-cyclopentanediyl, trans 1,2-cyclopentanediyl, cis 1,3-cyclopentanediyl, Trans 1,3-cyclopentanediyl, wherein the last four groups mentioned are unsubstituted or one or two C ₁ -C ₄ -alkyl groups, cis 1,2-cyclohexanediyl , Trans 1,2-cyclohexanediyl, cis 1,3-cyclohexanediyl, trans 1,3-cyclohexanediyl, cis 1,4-cyclohexanediyl, trans 1,4-cyclohexanediyl, where the last mentioned are six groups are unsubstituted or 1 or two C ₁ -C ₄ - alkyl group, 1,2-phenylene , 1,3-phenylene, having a 1,4-phenylene, where the last three groups mentioned may be unsubstituted or substituted with one or two C ₁ -C ₄ - having an alkyl group;

The # is an attachment point to an internal nitrogen atom in the urea component;
In particular, Z is trans-1,4-cyclohexanediyl. In particular, when x is 2, each Z has the same meaning.

Preferred embodiments of the invention relate to the use and methods in the compounds of formula I where R ¹ and R ² have different meanings. A preferred embodiment of the present invention relates to the use and methods in the compounds of formula I when R ¹ and R ² have the same meaning.

A particularly preferred embodiment of the invention relates to the use and method in the compounds of formula I when the variables R ¹ , R ² , Z and x have the following meanings:
R ¹ and R ² have the same meaning and are selected from 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl;
Z is trans 1,4-cyclohexanediyl; and x is 1.

A further particularly preferred embodiment of the present invention is for compounds of formula I wherein the variables R ¹ and R ² are both hydrogen, Z is trans 1,4-cyclohexanediyl and x is 1. , Use and methods.

In a particularly preferred embodiment of the invention, the polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, and in the compound of formula I R ¹ and R ² is the same and is selected from tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl, and Z is trans 1,4 -Relates to use and process when cyclohexylene and x is 1.

In a further particular embodiment of the invention, the polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, and R ^{1 in} the compound of formula I And R ² are both hydrogen, Z is trans 1,4-cyclohexylene, and x is 1.

  Compounds of formula I are known in the art or can be prepared analogously to standard methods in the art or as outlined in the experimental section of this application.

  A compound of formula I where x is 1 is also referred to as bisurea compound I. A compound of formula I where x is 2 is also referred to as trisurea compound I. A compound of formula I where x is 3 is also referred to as tetraurea compound I.

For example, compounds of formula I where x is 1 and R ¹ and R ² have the same meaning can be prepared as outlined in Schemes 1 and 2 below.

In Scheme 1, Z and R ¹ are as defined. The diamine compound of formula II reacts with 2 equivalents of isocyanate III to produce the compound of formula I in good yield. The reaction is usually performed in an organic solvent. A suitable solvent is a polar aprotic solvent such as tetrahydrofuran.

  Alternatively, a bisurea compound of formula I can be prepared by reacting a diisocyanate compound of formula IV with an amine of formula V. The reaction is usually performed in an organic solvent. A suitable solvent is a polar aprotic solvent such as tetrahydrofuran.

In Scheme 2, Z and R ¹ are as defined above.

Compounds of formula I where x is 1 and R ¹ and R ² have different meanings can be prepared as outlined in Scheme 3 below.

In Scheme 3, Z, R ¹ and R ² are as defined above. Treatment of amine compounds of formula VI and VIa with isocyanates VII and III, respectively, produces compounds of formula I in good yield. The reaction is usually performed in an organic solvent. A suitable solvent is a polar aprotic solvent such as N-methylpyrrolidone.

Tris-urea compounds of formula I, ie compounds of formula I where x is 2 and R ¹ has the same meaning as R ² can be prepared as outlined in Scheme 4.

In Scheme 4, Z and R ¹ are as defined above. Hal is halogen and Hal ′ is halogen. Preferably, Hal and Hal ′ are chlorine.

  In step i) of Scheme 4, diamine II reacts with 1 equivalent of isocyanate III to produce amine compound X. The reaction can be performed analogously to the procedure described in Scheme 1. In step ii) of Scheme 4, the amine compound X is reacted with a carbonyl dihalide of formula XI to produce the trisurea compound I.

Tris-urea compounds of formula I, ie compounds of formula I where x is 2 and R ¹ has the same meaning as R ² can be prepared as outlined in Scheme 5.

In Scheme 5, R ¹ is as defined above and Z is as defined above, preferably cycloalkylene or arylene.

  In step i) of Scheme 5, amine compound XII reacts with isocyanate compound XIII to produce dinitro compound XIV. The reaction can be carried out analogously to the method described in scheme 4, step i). In step ii) of Scheme 5, dinitro compound XIV is reduced to diamino compound XV. The reduction can be performed using hydrazine hydrate in the presence of a Pd / C catalyst. In step iii) of Scheme 5, the reaction between diamino compound XV and 2 equivalents of isocyanate compound III yields trisurea compound I.

Tetraurea compounds of formula I, ie compounds of formula I where x is 3 and R ¹ has the same meaning as R ² can be prepared as outlined in Scheme 6.

In Scheme 6, R ¹ and Z are as defined above. R ¹ can have the same or different meanings. Z can have the same or different meanings. Amino compound XI reacts with diisocyanate compound IV analogously to the procedure described in Scheme 2.

Polyamide resins are often one or more additional ingredients such as colorants, antioxidants, UV absorbers, light stabilizers, reinforcing materials, fillers, antifogging agents, mold release agents, biocides, Contains components selected from antistatic agents and flow modifiers. Examples of additional ingredients that can be included in the compositions of the present invention include:
1. Colorant The term colorant includes dyes and pigments. The pigment may be an organic or inorganic pigment known in the art. Examples for suitable pigments are colored pigments, nacreous pigments, for example effect pigments or pigments based on liquid crystal polymers.

  The colorant may be a dye. Also considered as colorants are organic compounds that exhibit fluorescence in the visible region of the electromagnetic spectrum, such as fluorescent dyes or fluorescent brighteners. The colorant can have additional properties, such as electrical conductivity, or can be magnetic shielding.

  Suitable dyes are all dyes that are soluble in the polyamide polymer composition. Examples of suitable dyes are azo dyes, pyrazolone dyes, anthraquinone dyes, perinone dyes, perylene dyes, indigo and thioindigo dyes, and azomethine dyes.

2. Antioxidant 2.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2 , 6-Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol , Linear or branched in the side chain, for example 2,6-di-nonyl-4-methylphenol 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadeca-1'-yl) phenol, 2,4-dimethyl- 6- (1′-methyltridec-1′-yl) phenol, and mixtures thereof.

  2.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di -Dodecylthiomethyl-4-nonylphenol.

  2.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-Di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

  2.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

  2.5. Hydroxylated thiodiphenyl ethers such as 2,2′-thiobis (6-tert-butyl-4-methylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (6-tert-butyl) -3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'- Bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

  2.6. Alkylidene bisphenols such as 2,2′-methylene bis (6-tert-butyl-4-methylphenol), 2,2′-methylene bis (6-tert-butyl-4-ethylphenol), 2,2′-methylene bis [ 4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (6-tert-butyl) -4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenone 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis- (3-tert-butyl- 5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis- (5- tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis- [3,3-bis- (3′-tert-butyl- 4′-hydroxyphenyl) butyrate], bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3′-tert-butyl-2′-hydroxy-5 ′) -Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-) -Tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5 -Tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

  2.7. O-, N-, and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5- Dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl -3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl Mercaptoacetate.

  2.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5 -Methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) ) Phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

  2.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5 -Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

  2.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6 -Bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4 -Hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) iso Anurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

  2.11. Benzyl phosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl 3,5-di-tert -Butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid salt.

  2.12. Acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

  2.13. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexane Diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis ( Hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2 2] octane.

  2.14. β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (Hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2 2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8 , Ester with 10-tetraoxaspiro [5.5] undecane.

  2.15. β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaun Decanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, ester with 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane

  2.16. 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene Glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundeca Esters with diol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

  2.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene Diamide, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyl) hydrazide, N, N′-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard® XL-1, supplier Uniroyal).

  2.18. Ascorbic acid (vitamin C).

  2.19. Amine-based antioxidants such as N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N, N′-bis (1,4-dimethyl) Pentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N′-bis (1-methylheptyl) -p-phenylenediamine, N, N′-dicyclohexyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N′-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N′-phenyl-p- Phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N′-phenyl- -Phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p- Phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine For example, p, p′-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino Feno Bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N, N, N ′ , N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ′, 3′-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl / tert-octyldiphenylamine mixtures, monoalkylated and Dialkylated nonyldiphenylamine mixtures, monoalkylated and dialkyl Mixtures of dodecyl diphenylamine, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamine, mixtures of monoalkylated and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4 -Benzothiazine, phenothiazine, monoalkylated and dialkylated tert-butyl / tert-octylphenothiazine, monoalkylated and dialkylated tert-octyl-phenothiazine, N-allylphenothiazine, N, N, N ', N' -Tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) -hexamethylenediamine, bis (2,2,6, 6-tetramethylpiperi 4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

  3. UV absorbers and light stabilizers.

3.1. 2- (2′-hydroxyphenyl) benzotriazole, such as 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′- Hydroxyphenyl) benzotriazole, 2- (5′-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl ) Benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5′-) Methylphenyl) -5-chlorobenzotriazole, 2- (3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- ( 2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (Α, α-Dimethylbenzyl) -2′-hydroxyphenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chloro Benzotriazole, 2- (3′-tert-butyl-5 ′-[2- (2-ethylhexyloxy) -carbonylethyl] -2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-tert -Butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl) 2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) Benzotriazole, 2- (3′-tert-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxy-phenyl) benzotriazole, 2- (3′-dodecyl-2′- Hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-iso-octyloxycarbonylethyl) phenyl) benzotriazole, 2'-methylene-bis -[4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'- ert- butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H- benzotriazole, the transesterification reaction product of a polyethylene glycol _{300; [R-CH 2 CH} 2 -COO-CH ₂ CH ₂ ] ₂ , wherein R = 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2- [2′-hydroxy-3 ′-(α, α-dimethylbenzyl) -5 ′-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2′-hydroxy-3 ′-(1,1,3,3-tetramethylbutyl) ) -5 ′-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

  3.2. 2-hydroxybenzophenone, such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy- 4,4′-Dimethoxy derivative.

  3.3 Esters of substituted and unsubstituted benzoic acids such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert -Butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate Octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

  3.4. Acrylates such as ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, Butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

  3.5. Nickel compounds, such as nickel complexes of 2,2′-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol], such as 1: 1 or 1: 2, further comprising Ligands such as with or without n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, monoalkyl of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid An ester, for example a nickel salt of a methyl or ethyl ester, a ketoxime, for example a nickel complex of 2-hydroxy-4-methylphenylundecylketoxime, a nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, With or without additional ligands

  3.6. Steric hindered amine stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4- Condensation product of hydroxypiperidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2 Linear or cyclic condensates with 6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpipe Radinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-penta) Methylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3 , 8-Triazas B [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-) Tetramethyl-piperidyl) succinate, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5 A linear or cyclic condensate with triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6 ′, 6-tetramethylpiperidyl) -1,3,5- Condensate of triazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethyl Piperidyl) -1,3,5-triazine and 1, Condensate with 2-bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] ldecane -2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2, 6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadodecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N′- The condensation product of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropy Condensation products of (amino) ethane with 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96- 6]); 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine and N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine Product (CAS registration number [192268-64-7]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospi [4,5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin Reaction product, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene], N, N′-bis-formyl-N , N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxy-methylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine Diesters, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin-copolymer and 2,2,6 6- Reaction product with tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

  3.7. Oxamides such as 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2, 2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5 -Tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides , And a mixture of o- and p-ethoxy-disubstituted oxanilides.

  3.8. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2 -Hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4 , 6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2 -[2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- ( Dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2- Droxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy- 4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5 -Triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenol) Nyl) -1,3,5-triazine.

  4). Metal deactivators such as N, N′-diphenyloxamide, N-salicyral-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis (3,5 -Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N′-diacetyladipoyl dihydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide.

  5. Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphos Bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol Triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [ d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6) -Methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12 -Methyl-dibenz [d, g] -1,3,2-dioxaphosphocine, 2,2 ', 2 "-nitrilo- [triethyltris (3,3', 5,5'-tetra-tert- Butyl-1,1′-biphenyl-2,2′-diyl) phosphite], 2-ethylhexyl (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2 '-Diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphirane.

6). Phosphorus-containing acids, salts of phosphorus-containing acids, esters of phosphorus-containing acids or their derivatives
Phosphorus-containing acids include phosphorous oxo acids such as phosphoric acid, phosphonic acid and phosphinic acid. Suitable salts of phosphorus-containing acids are alkali metal salts, alkaline earth metal salts or transition metal salts. Of these, calcium, barium, magnesium, sodium, potassium, manganese and aluminum salts are preferred. Sodium phosphinate (also known as NaPO ₂ H ₂ , sodium hypophosphite), manganese bisphosphinate (also known as Mn (H ₂ PO ₂ ) ₂ , manganese hypophosphite (II)), aluminum phosphinate ( Al (H ₂ PO ₂ ) ₃ ) and mixtures thereof are particularly preferred. Phosphonic acid esters, half esters and mixtures thereof, in particular esters, half esters or mixtures thereof of hydroxyphenylalkylphosphonic acids, such as those disclosed in WO 2007006647, in particular calcium bis [monoethyl (3,5-di-tert -Butyl-4-hydroxybenzyl) phosphonate] (Irgamod® 195, commercially available from BASF SE), or diethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (Irgamod® 295) And commercially available from BASF SE).

  7). Hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkyl derived from hydrogenated tallowamine Hydroxylamine.

  8). Nitrones such as N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone (Tridecyllntronone), N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha- Heptadecyl nitrones, N-octadecyl-alpha-hexadecyl nitrones, nitrones derived from N, N-dialkylhydroxylamines derived from hydrogenated tallow amines.

  9. Thio synergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

  10. Peroxide scavengers, such as esters of P-thiodipropionic acid, such as esters of lauryl, stearyl, myristyl or tridecyl, mercaptobenzimidazole, or zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl Disulfide, pentaerythritol tetrakis- (p-dodecyl mercapto) propionate.

  11. Polyamide stabilizers such as combinations of copper salts with iodides and / or phosphorus compounds, and divalent manganese salts.

  12 Basic co-stabilizers such as melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids such as calcium stearate, stearin Zinc acid, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. The polyamide resin preferably does not contain barium stearate.

  13. Other additives such as plasticizers, lubricants, flow control agents, flameproofing agents, mold release agents and swelling agents.

  14 Benzofuranone and indolinone, for example US-A-4325863; US-A-4338244; US-A-5175312; US-A-521652; US-A-5252643; DE-A-4316611; DE- A-4316622; DE-A-4316676; those disclosed in EP-A-058939, or EP-A-0591022, or 3- [4- (2-acetoxyethoxy) phenyl] -5 , 7-Di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3′-bis [5,7-Di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) Benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7- Di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4 -Dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

  15. Fillers or reinforcements include, for example, glass fibers in the form of glass cloth, glass mats or filament glass roving, chopped glass, glass beads and wollastonite. Glass fibers can be mixed in both short glass fiber form and continuous fiber (roving) form.

  16. Antistatic agents such as amine derivatives, such as N, N-bis (hydroxyalkyl) -alkylamines or -alkyleneamines, polyethylene glycol esters and ethers, ethoxylated carboxylic esters and carboxamides, and glycerol monostearate and distearate, and Mixture of.

  17. The biocide may be an insecticide or fungicide.

  At least one compound of the formula I is 0.001 to 5% by weight, preferably 0.01 to 3% by weight, for example 0.001 to 3%, 0.01 to 2%, based on the weight of the polyamide resin. , 0.01-1.5% or 0.025-1%.

  The weight ratio of the compound of formula (I) to the optional components mentioned above (if present) is preferably 1: 100 to 100: 1, such as 1:90 to 90: 1, 1:80 to 80: 1, 1 : 70-70: 1, 1: 60-60: 1, 1: 50-50: 1, 1: 40-40: 1, 1: 30-30: 1, 1: 20-20: 1, 1:10 -10: 1, 1: 5-5: 1, 1: 4-4: 1, 1: 3-3: 1, 1: 2-2: 1 or 1: 1.

According to the present invention, a method for improving the material properties of at least one solid of a polyamide resin, comprising:
a) preparing a polyamide;
b) providing at least one urea compound of formula I as defined above;
c) A process is provided comprising the step of mixing the urea compound of formula I into the polyamide.

The polyamide is preferably selected from aliphatic polyamide homopolymers, aliphatic polyamide copolymers, partially aromatic polyamides and mixtures thereof as defined above. Polyamide resins are as defined above with other ingredients or additives such as colorants, antioxidants, UV absorbers, light stabilizers, reinforcing materials, fillers, antifogging agents, mold release agents, biocides. , Antistatic agents and flow modifiers can be included. In the urea compounds of the formula I, the radicals R ¹ , R ² , Z and the subscript x preferably have one of the preferred meanings. The urea compound of formula I is present in an amount of 0.001-5% by weight, preferably 0.01-3% by weight, more preferably 0.05-2% by weight, based on the weight of the polymer resin. Good.

  The method of the present application provides a polyamide resin with improved solid properties. In particular, solid properties selected from mechanical properties and gloss are improved. The polyamide resin produced by the method of the present invention has improved tensile properties and notched impact toughness. The tensile properties are preferably selected from yield stress, yield strain, tensile strain at break, tensile stress at break, modulus of elasticity and shear modulus.

  At least one compound of formula I and optional further components can be added to the polyamide resin individually or mixed with one another. If desired, the individual additives can be mixed with one another, for example in the melt (melt mixing), before being mixed into the polyamide polymer.

  Incorporation of the compound of formula I into the polyamide resin and optional incorporation of the conventional components described above can be accomplished by any known method. This mixing, for example by dry mixing, extruding a mixture of various ingredients, adding conventional masterbatch technology, additive concentrates, adding additives mixed in polymer carriers, eg fillers And that kind of thing can be done.

  Mixing can be carried out in any heatable vessel equipped with a stirrer, for example a sealing device, for example a kneader, a mixer or a stirring vessel. Examples of processing of the composition according to the invention are injection blow molding, extrusion, blow molding, extrusion blow molding, rotational molding, in mold decoration (back injection), slush molding, injection molding, co-injection molding, Forming, compression molding, pressing, film extrusion (cast film; blown film), spinning (woven fabric, non-woven fabric), stretching (uniaxial, biaxial), annealing, deep drawing, calendering, mechanical deformation, sintering , Coextrusion. Mixing is preferably carried out in the extruder or in the kneader according to methods known in the literature.

  It is not important whether the treatment is carried out in an inert atmosphere or in the presence of oxygen.

  Polyamide resins containing compounds of Formula I are molded into molded articles using any suitable melt processing technique such as injection molding, extrusion, blow molding, injection blow molding, thermoforming and the like can do.

  The polyamide resin comprising the compound of formula I is usually a film, fiber, sheet, pipe, semi-finished product, granule, container, blow molded article or monofilament. The film may be a single layer film or a multilayer film or fiber.

  A polyamide article comprising a compound of formula I is characterized by high strength, high stiffness, high notched impact toughness, good tensile strain at break, excellent tensile stress at break, excellent elastic modulus and excellent shear modulus, This is particularly important for use in the fields of optics, automobiles, aircraft, electrical / electronics, sports and leisure, the mechanical engineering industry or aggressive media.

  Without limiting the generality of the above, articles formed from polyamide resins containing compounds of formula I are tough, have good shape stability at high temperatures, and have low tensile stress at break and Housings such as gears, housings such as filter housings or solenoid valve housings, current heaters, drooping cable attachments, electrically insulating parts such as fuel and / or oil tanks or reservoirs, windows, lids, spectacle frames frame), glasses, lenses for engineering equipment, viewing windows for heating devices, filter cups for the treatment of drinking water, bottles, flowmeters for gas or liquid media, clock cases, watch cases, automotive accessories, lamps Case, reflector for lamp, backlit switch, surgical material, case Cartridge or decorative parts, can include a sporting goods or packaging material.

  The surface gloss is measured according to DIN 67530 (measurement angles 20 ° and 60 °). Yield stress, yield strain, tensile stress at break, tensile strain at break, and Young's modulus are measured according to EN ISO 527-2. Charpy notched impact toughness is measured in accordance with DIN EN ISO 179-2 and by injection at Notch S, 23 ° C. The storage modulus G ′ and the loss modulus G ″ were measured at a temperature in the range of 15.1 to 197.3 ° C. according to ISO 6721-7.

  The invention will now be described in further detail by the following examples. However, the purpose of the following examples is illustrative only and is not intended to limit the invention thereto.

Preparation of compounds of formula I 1.1 Compounds of formula I when x = 1 and R ¹ = R ² Example 1: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (tert -Butyl) urea)
A solution of tert-butyl isocyanate (3.90 g, 0.039 mol) in dry tetrahydrofuran (THF) (50 mL) was slowly added to trans-1,4-diaminocyclohexane (2.10 g, 0.019 mol) in dry THF ( (100 mL) in an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from N, N-dimethylformamide (DMF) and dried under high vacuum.

MS (70 eV): 312 (M ^<+> ).

Example 2: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (cyclohexyl) urea)
A solution of cyclohexyl isocyanate (5.49 g, 0.044 mol) in dry THF (50 mL) is slowly added to a solution of trans-1,4-diaminocyclohexane (2.51 g, 0.022 mol) in dry THF (100 mL). In an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from DMF and dried under high vacuum.

MS (70 eV): 364 (M ^<+> ).

Example 3: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (iso-propyl) urea)
A solution of isopropylamine (1.25 g, 0.022 mol) in dry THF (50 mL) is slowly added to a solution of trans-1,4-cyclohexane diisocyanate (1.75 g, 0.011 mol) in dry THF (100 mL). In an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from DMF and dried under high vacuum.

MS (70 eV): 284 (M ^<+> ).

Example 4: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (1-ethylpropyl) urea)
A solution of 3-aminopentane (2.20 g, 0.025 mol) in dry THF (50 mL) is slowly added to trans-1,4-cyclohexane diisocyanate (2.00 g, 0.012 mol) in dry THF (100 mL). To the solution under an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from DMF and dried under high vacuum.

MS (70 eV): 340 (M ^<+> ).

Example 5: 1,1 ′-(cis-1,4-cyclohexylene) bis (3- (cyclohexyl) urea)
A solution of isocyanatocyclohexane (3.25 g, 0.026 mol) in dry THF (50 mL) was slowly added to cis-1,4-cyclohexanediamine (1.50 g, 0.013 mol) in dry THF (100 mL). To the solution was added under an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from MeOH and dried under high vacuum.

Melting point: 252 ° C
MS (70 eV): 364 (M ^<+> ).

Example 6: 1,1 ′-(cis-1,4-cyclohexylene) bis (3- (tert-butyl) urea)
A solution of tert-butyl isocyanate (2.57 g, 0.026 mol) in dry THF (50 mL) is slowly added to cis-1,4-cyclohexanediamine (1.50 g, 0.013 mol) in dry THF (100 mL). To the solution under an inert atmosphere. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional dry THF. The resulting white solid was recrystallized from MeOH and dried under high vacuum.

Melting point: 319 ° C
MS (70 eV): 312 (M ^<+> ).

  The compounds of Examples 7-13 were prepared similarly.

Example 7: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (1,1-dimethylpropyl) urea)
MS (70 eV): 340 (M ^<+> ).

Example 8: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (tert-octyl) urea)
MS (70 eV): 426 (M ^<+> ).

Example 9: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (1,5-dimethylhexyl) urea)
MS (70 eV): 425 (M ^<+> ).

Example 10: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (1-adamantyl) urea)
MS (70 eV): 468 (M ^<+> ).

Example 11: 1,1 ′-(trans-1,4-cyclohexylene) bis (3-n-butylurea)
Melting point: 358 ° C
MS (70 eV): 312 (M ^<+> ).

Example 12: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (n-propyl) urea)
MS (70 eV): 284 (M ^<+> ).

Example 13: 1,1 ′-(trans-1,4-cyclohexylene) bis (3- (ethyl) urea)
MS (70 eV): 256 (M ^<+> ).

Example 14: (4-Ureidocyclohexyl) urea trans-1,4-diaminocyclohexane (2.10 g, 0.019 mol) was dissolved in water (40 mL). The solution was brought to pH 5-7 by the addition of HCl. 3.30 g of potassium cyanate was slowly added with stirring. The resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and washed with additional water. The resulting white solid was dried under high vacuum.

1.2 Compounds of Formula I when x = 1 and R ¹ is Different from R ² Example 15: 1-tert-Butyl-3- [4- (cyclohexylcarbamoylamino) cyclohexyl] ure 15.1 Trans-1- A solution of (4-aminocyclohexyl) -3-cyclohexylurea trans-1,4-diaminocyclohexane (6.15 g, 0.054 mol) in dry THF (500 mL) was placed in a cooling bath (isopropyl alcohol / dry ice). Cool to −40 ° C. under inert atmosphere. Isocyanatocyclohexane (6.75 g, 0.054 mol) in dry THF (100 mL) was added slowly with vigorous stirring. The resulting mixture was stirred for an additional 24 hours at room temperature. The precipitated white solid was filtered, suspended in water and acidified to pH 2 (HCl). The clear solution that appeared was filtered again and the filtrate was brought to pH 8 (NaOH), where trans-1- (4-aminocyclohexyl) -3-cyclohexylurea precipitated as a white solid.

15.2 1-tert-butyl-3- [4- (cyclohexylcarbamoylamino) cyclohexyl] urea tert-butyl isocyanate (1.17 g, 0.012 mol) in dry N-methyl-2-pyrrolidone (NMP) (50 mL) The solution in was slowly added to a solution of trans-1- (4-aminocyclohexyl) -3-cyclohexylurea (2.83 g, 0.012 mol) in dry NMP (100 mL) under an inert atmosphere. The resulting mixture was heated to 70 ° C. and stirred for 24 hours. The solution was precipitated in 1M HCl and filtered off. The resulting white solid was washed with THF, recrystallized from DMF and dried under high vacuum.

Melting point: 325 ° C
MS (70 eV): 338 (M ^<+> ).

1.3 Compound of Formula I when x = 2 and R ¹ = R ² Example 16

16.1 Trans-1- (4-aminocyclohexyl) -3-cyclohexylurea Trans-1,4-diaminocyclohexane (6.15 g, 0.054 mol) was added to the flame-dried Schlenk tube and THF ( In 500 mL) under an argon atmosphere. The solution was cooled to −40 ° C. in a cooling bath (isopropyl alcohol / dry ice) and cyclohexyl isocyanate (6.75 g, 0.054 mmol) diluted in THF (100 mL) was slowly added with vigorous stirring. Added. The reaction mixture was stirred for 12 hours at room temperature. The white solid that precipitated out was filtered off, suspended in water and acidified to pH 2 (HCl). The clear solution that appeared was filtered again and the filtrate was brought to pH 8 (NaOH), where trans-1- (4-aminocyclohexyl) -3-cyclohexylurea precipitated as a white solid.

16.2

  The flask was filled with trans-1- (4-aminocyclohexyl) -3-cyclohexylurea in THF and bubbled into phosgene. After the reaction was complete, excess phosgene and solvent were removed under reduced pressure to yield the title compound.

1.4 Compound of Formula I when x = 3 and R ¹ = R ² Example 17

  Trans-1- (4-aminocyclohexyl) -3-cyclohexylurea (3.2 g, 13 mol) was added to the flame-dried Schlenk tube and dissolved in NMP under an argon atmosphere. Trans-1,4-cyclohexane diisocyanate (1 g, 6 mmol) diluted in NMP was added slowly with vigorous stirring. The resulting mixture was heated to 80 ° C. and stirred for 12 hours. The solution was precipitated in 1M HCl and filtered off. The resulting white solid was washed with THF and dried under vacuum for 2 hours (70 ° C., 100 mbar).

MS (70 eV): 265 (M ^<+> ).

  Unless otherwise stated, the following general procedures were used in the examples.

Mixing procedure:
The polyamide pellets and the urea compound of formula I were accurately weighed at a concentration of 1.0% by weight. Thereafter, the composition was tumble mixed. The above mixture was then compounded in a co-rotating twin screw compounder (ZSK18) at a rotational speed of 300 rpm, a melting temperature of 260 ° C. and a throughput of 6 kg per hour. A neat polyamide was treated in the same manner to produce a blank control sample.

The following polyamides were used:
Ultramid® B27, available from BASF SE (Germany), PA 6 grade.

injection molding:
Injection molding was carried out at a melting temperature of 260 ° C. in an injection molding machine having a screw diameter of 30 mm. The melt was injected into a mold having a mold temperature of 80 ° C. The holding pressure was 600 bar. The prepared sample was a standard tensile test piece conforming to DIN EN ISO 527-2, Typ 1A, and a Charpy test piece conforming to ISO 179-2 / 1 eA (F).

  Compositions comprising the compounds of formula I listed in Table I below, reference, and comparative compositions were prepared as described above, and the sample thickness was set to 4.0 mm.

Table I

^* N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], CAS 23128-74-7
^** Ceasit AV, powder flow aid, manufactured by Baerlocher IC Composition of the present invention CC Comparative composition

Table II: Selected optical properties of compositions comprising compounds of formula I, reference compositions and comparative compositions

  The use of the compounds of formula I improves the gloss of the polyamide compositions with which they are mixed compared to compositions without such additions.

Table III: Tensile properties of compositions comprising compounds of formula I, reference compositions and comparative compositions

  When the compound of formula I is used, the Young's modulus (elastic modulus) and the value of tensile strain at break increase compared to the composition without the addition.

Table IV: Charpy notched impact toughness of compositions comprising compounds of formula I, reference compositions and comparative compositions

  The polyamide resin composition containing the compound of formula I exhibits excellent notched impact toughness at 23 ° C. as compared to the composition without the above addition or with the addition of talc. The test sample had a thickness of 4 mm.

DMTA-Test Storage modulus G ′ (elastic response rate) and loss modulus G ″ (viscosity response rate) are measured according to Dynamic Mechanical Thermal Analysis (ISO 6721-7) DMTA). Measurements were made on a Rheometric RDA 1 instrument using dry test samples. The test sample had a length of 4.0 cm, a width of 1.0 cm, and a thickness of 0.1 cm (made of a press plate). Strain applied at the start: 0.2%, frequency 1 Hz, heating started at 15.1 ° C. in a nitrogen atmosphere (temperature increments of 5K). Prior to testing, the samples were preconditioned under vacuum for 3 days at 80 ° C.

Table V: Storage modulus G ′ and loss modulus G ″ of compositions comprising compounds of formula I and reference compositions

The glass transition temperature of neat polyamide (dry) as well as composition IC1 (dry) was 64 ° C. as measured by DTMA. As can be seen from the storage modulus and loss modulus, the change in stiffness of IC1 above _TG is less than that of the reference composition. Therefore, the rigidity of IC1 is higher than that of the reference composition in a temperature range above the glass transition temperature.

Claims (18)

Formula I for improving at least one of the solid properties of a polyamide resin

[Where:
x is 1, 2 or 3;
R ¹ and R ² are independently of each other hydrogen, straight chain C ₁ -C ₇ -alkyl, branched C ₃ -C ₁₀ -alkyl, unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl. , unsubstituted or substituted C ₃ -C ₁₂ - cycloalkyl -C ₁ -C ₄ - selected from alkyl - alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl -C ₁ -C ₄ And
Z is C ₃ -C ₁₀ -alkanediyl, unsubstituted or substituted arylene, unsubstituted or substituted arylene-C ₁ -C ₄ -alkylene-arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted Heteroarylene-C ₁ -C ₄ -alkylene-heteroarylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene, unsubstituted or substituted C ₅ -C ₈ -cycloalkylene-C ₁ -C ₄ - alkylene -C ₅ -C ₈ - cycloalkylene, unsubstituted or substituted heterocycloalkylene, and unsubstituted or substituted heterocycloalkylene -C ₁ -C ₄ - alkylene - is selected from heterocycloalkylene]
Use of at least one urea compound.   Use according to claim 1, wherein the solid property is selected from mechanical properties and gloss.   Use according to claim 2, wherein the mechanical properties are selected from tensile properties and notched impact toughness.   4. Use according to claim 3, wherein the tensile properties are selected from yield stress, yield strain, tensile strain at break, tensile stress at break, elastic modulus and shear modulus. R ¹ and R ² , independently of one another, are linear C ₁ -C ₇ -alkyl, branched C ₃ -C ₁₀ -alkyl, unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl, unsubstituted or substituted C ₃ -C ₁₂ - cycloalkyl -C ₁ -C ₄ - alkyl, unsubstituted or substituted aryl and unsubstituted or substituted aryl -C ₁ -C ₄ - is selected from alkyl The use according to claim 1. In formula I, R ¹ and R ² are independently of one another hydrogen, branched C ₃ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl-C _1. -C ₄ - alkyl, phenyl and phenyl -C ₁ -C ₄ - is selected from alkyl, each ring in the last four groups mentioned, which is unsubstituted or one or more of the same than, 6. Use according to any one of claims 1 to 5, alternatively substituted by ^a different group R ^a , wherein R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen. In Formula I, R ¹ and R ² are independently of each other hydrogen, a branched C ₃ -C ₁₀ -alkyl, attached to the backbone via the secondary or tertiary carbon atom of the alkyl group, non- substituted by substituted or 1 or 2 radicals R ^a the C ₅ -C ₁₀ - cycloalkyl, and is selected from phenyl unsubstituted or substituted by 1 or 2 radicals R ^a, of claims 1 to 6 Use of any one of Claims. Use according to any one of claims 1 to 7, wherein in formula I, R ¹ and R ² have the same meaning. In Formula I, Z is C ₅ -C ₈ - alkylene, C ₅ -C ₇ - cycloalkylene, C ₅ -C ₇ - cycloalkylene -CH ₂ -C ₅ -C ₇ - cycloalkylene, phenylene or phenylene -CH ₂ -Phenylene, wherein each ring in the last four groups mentioned is unsubstituted or substituted by one or two identical or different groups R ^b , said R ^b being C ₁ -C ₁₀ - is selected from alkyl and halogen, the use according to any one of claims 1 to 8. In formula I, C ₅ -C ₈ of Z is linear - alkylene or C ₅ -C ₇ - cycloalkylene, Use according to claim 9.   11. Use according to any one of claims 1 to 10, wherein in formula I, x is 1. In Formula I,
R ¹ and R ² are the same and are selected from hydrogen, tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl ,
Z is trans 1,4-cyclohexylene, and
x is 1,
12. Use according to any one of claims 1 to 11.   Use according to any of claims 1 to 12, wherein the polyamide resin is selected from aliphatic polyamide homopolymers, aliphatic polyamide copolymers, partially aromatic polyamides and mixtures thereof.   The polyamide polymer is PA 6, PA 7, PA 10, PA 11, PA 12, PA 66, PA 69, PA 610, PA 612, PA 1010, PA 6/66, PA 66/6, PA 66/610 and 14. A mixture according to any one of claims 1 to 13, preferably selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66 from mixtures thereof. use. The polyamide polymer is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, and in the compounds of formula I R ¹ and R ² are identical and Selected from hydrogen, tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl, and Z is trans 1,4-cyclohexylene The use according to claim 14, wherein x is 1.   The polyamide resin comprises a compound of formula I in an amount of 0.001 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.05 to 2% by weight, based on the weight of the polyamide resin. Use according to any one of claims 1 to 15, comprising   The polyamide resin is additionally selected from colorants, antioxidants, UV absorbers, light stabilizers, reinforcing materials, fillers, antifogging agents, mold release agents, biocides, antistatic agents and flow modifiers. 17. Use according to any one of claims 1 to 16, comprising at least one further additive.   A method for improving at least one of the solid properties of a polyamide resin, the polyamide resin comprising at least one urea compound of the formula I as defined in any one of claims 1 and 5-12. Said method comprising adding.