KR20140144704A - Urea compounds for improving the solid state properties of polyamide resins - Google Patents

Abstract

상기 식 중,
x는 1, 2 또는 3이고;
R¹ 및 R²는 수소, 선형 C₁∼C₇-알킬, 분지형 C₃∼C₁₀-알킬, 비치환 또는 치환 C₃∼C₁₂-사이클로알킬, 비치환 또는 치환 C₃∼C₁₂-사이클로알킬-C₁∼C₄-알킬, 비치환 또는 치환 아릴, 및 비치환 또는 치환 아릴-C₁∼C₄-알킬로부터 선택되며;
Z는 C₃∼C₁₀-알칸디일, 비치환 또는 치환 아릴렌, 비치환 또는 치환 아릴렌-C₁∼C₄-알킬렌-아릴렌, 비치환 또는 치환 헤테로아릴렌, 비치환 또는 치환 헤테로아릴렌-C₁∼C₄-알킬렌-헤테로아릴렌, 비치환 또는 치환 C₅∼C₈-사이클로알킬렌, 비치환 또는 치환 C₅∼C₈-사이클로알킬렌-C₁∼C₄-알킬렌-C₅∼C₈-사이클로알킬렌, 비치환 또는 치환 헤테로사이클로알킬렌, 및 비치환 또는 치환 헤테로사이클로알킬렌-C₁∼C₄-알킬렌-헤테로사이클로알킬렌으로부터 선택된다.
고체 상태 특성은 기계적 특성과 광택으로부터 선택되는 것이 바람직하다.The present invention relates to the use of one or more urea compounds of the general formula I to improve one or more of the solid state properties of polyamide resins:
(I)

Wherein,
x is 1, 2 or 3;
R ¹ and R ² are independently selected from hydrogen, 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 -alkyl, C ₁ -C ₄ -alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl-C ₁ -C ₄ -alkyl;
Z is a 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 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-heterocycloalkylene.
The solid state property is preferably selected from mechanical properties and gloss.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a urea compound for improving the solid state property of a polyamide resin,

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

BACKGROUND OF THE INVENTION Polyamides (PA) are widely used as commercial polymers for use in a number of different fields, such as automotive, aerospace, mechanical engineering, electrical, electronics, sports and leisure industries, in that their performance characteristics are very good and cost- It is known. For example, favorable mechanical properties such as increased modulus of elasticity, tear tensile stress, tear tensile strain or notch impact toughness, and improved properties of molded articles made of a composition comprising the polyamide resin Measures to improve the appearance of the polyamide resin, for example, to give an improved surface gloss, have been proposed. Particularly, the polyamide resin has excellent mechanical properties at a high temperature, for example, a temperature higher than the glass transition temperature T _G. Such polyamides could be used in the manufacture of parts that would be mechanically stressed, such as exposed to high temperatures during use. The excellent stiffness / toughness of the polyamide resin is also a property required in connection with the manufacture of thin wall components.

It is known that incorporation of talc into a polyamide resin improves the stiffness and bending strength of the polyamide resin. These results, however, result in lower tensile properties and impact toughness.

Japanese Patent No. 5320501 discloses a polyamide resin, a barium stearate (releasing agent) and a compound represented by the formula (R ¹ -NHC (O) NH) ₂ X, wherein X is a divalent A hydrocarbon group, and R < ¹ > is an aliphatic hydrocarbon group having 9 to 40 C atoms. When the barium stearate and the bisurea compound are mixed, the injection-moldable polyamide resin becomes more resistant to ejection distortion.

Therefore, polyamide resins with improved solid state properties are constantly being sought to broaden the performance spectrum. Solid state properties include mechanical properties and gloss, e.g., surface gloss. Particularly, polyamide resins having excellent mechanical properties are desperately required.

It has surprisingly been found that the urea compounds of formula I, defined below, are suitable for improving the solid state properties of polyamide resins.

The invention therefore relates to the use of one or more urea compounds of the general formula (I) for improving the solid state properties of polyamide resins:

(I)

Wherein,

x is 1, 2 or 3;

R ¹ and R ² independently represent hydrogen, linear C ₁ ~C ₇ - alkyl, branched C ₃ ~C ₁₀ - alkyl, substituted or unsubstituted 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;

Z is a 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 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-heterocycloalkylene. Particularly solid state 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, comprising the step of adding at least one urea compound of formula I as defined above to the polyamide resin.

In the term of the present invention, "solid state property of polyamide resin" is understood to be a characteristic of polyamide in solid state. The solid state properties are preferably selected from gloss and mechanical properties. Mechanical properties include, for example, stress modulus and tensile properties, such as yield stress, yield strain, tear tensile strain, tear tensile stress, tensile modulus and notch impact toughness.

 The unique use of urea compounds of formula I involves one or more of the following advantages over compositions in which this compound is not added:

- improvement of one or more mechanical properties, in particular notched impact toughness, tear tensile stress, tear tensile strain, Young's modulus (elastic modulus) and shear modulus;

- Increased gloss.

The term "semi-crystalline " as used herein refers to the case where the polyamide polymer exhibits an X-ray pattern having diffuse features characteristic of amorphous regions and sharp features characterized by crystalline regions.

For purposes of the present invention, the generic terms are used to define the variables defined by the formulas, in which case the generic terms generally and typically represent the substituents in question. The definition of C _{n to} C _m gives the possible number of each carbon atom in each substituent or substituent moiety.

As used herein, the term "C ₁ ~C ₄ - alkyl", it means a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Examples thereof include methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl and tert-butyl.

The term "linear C ₁ -C ₇ -alkyl" as used herein refers to straight-chain alkyl groups having from 1 to 7 carbon atoms. Examples thereof include 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 thereof include isopropyl, 2-butyl, iso-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- Propyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, Dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 Ethyl-2-methylpropyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, Methylheptyl, 5-methylheptyl, 1-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethyl Hexyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl and 2-propylpentyl.

The term "C ₁ -C ₁₀ -alkyl" as used herein refers to a straight or branched alkyl group having from 1 to 10 carbon atoms. C ₁ ~C ₁₀ - Examples of the alkyl C ₁ ~C ₄ - alkyl and branched C ₃ ~C ₁₀ - Apart from the ones exemplified for the alkyl, n- pentyl, n- hexyl, n- heptyl, n- Octyl, n-nonyl, and n-decyl.

As used herein, the term "C ₃ -C ₁₀ -alkanediyl" (also referred to as C ₃ -C ₁₀ -alkylene) refers to a straight or branched saturated alkyl group having from 3 to 10 carbon atoms, One of the hydrogen atoms of such groups is substituted by an additional bond position. Examples of linear C ₃ -C ₆ -alkanediyl are propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl. Examples of branched C ₃ -C ₆ -alkanediyl include propyl-1,1-diyl, butyl-1,1-diyl, 1-methylethane- 1,2-diyl, 1,2- 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 a single ring, bicyclic or tricyclic hydrocarbon radical (= C ₃ -C ₁₂ -cycloalkyl) having 3 to 12 carbon atoms, Refers to a single ring, bicyclic or tricyclic hydrocarbon radical (= C ₅ -C ₁₀ -cycloalkyl) having from 1 to 10 carbon atoms. Examples of the single ring radical having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals having 7 to 8 carbon atoms include bicyclo [2.2.1] hexyl, bicyclo [2.2.1] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.2] [3.2.1] octyl. Examples of tricyclic radicals include 1-adamantyl, 2-adamantanyl, and homo-adamantyl. C ₃ -C ₁₂ -cycloalkyl may be substituted or unsubstituted by one or more, for example one, two or three, of the same or different radicals R ^a , and R ^a is 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, refers to a cycloalkyl radical in each case as defined above, Refers to a cycloalkyl radical in which one hydrogen atom is replaced by one further bond position to form a bivalent moiety. C ₅ -C ₈ -cycloalkylene may be unsubstituted or substituted by one or more, for example one, two or three, of the same or different radicals R ^b and R ^b is a C ₁ -C _10- Alkyl or halogen.

As used herein, the term "C _{n to} C _m -cycloalkyl-C _{o to} C _p -alkyl" refers to an alkyl group having from 0 to p carbon atoms, as defined above, Refers to a cycloalkyl group having from n to m carbon atoms as defined above. Examples thereof include cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl and the like. When C _n -C _m -cycloalkyl-C _o -C _p -alkyl is substituted, the cycloalkyl moiety may have one or more, for example one, two or three, radicals R ^{a, the} same or different, and R ^a is C ₁ -C ₁₀ -alkyl or halogen.

The term "aryl ", as used herein, refers to a C ₆ -C ₁₄ carboaromatic group, such as phenyl, naphthyl, anthracenyl and phenanthrenyl. The aryl may be substituted or unsubstituted by one or more, for example one, two or three, radicals R ^a, which are the same or different, and R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen. Preferably the aryl is phenyl.

The term "arylene" as used herein refers to an aryl radical as defined above, wherein one hydrogen atom at any position of the aryl is substituted by one further bond position to form a di-valent moiety. Arylene may be substituted or unsubstituted by one or more, for example one, two or three, of the same or different radicals R ^b and R ^b is selected from C ₁ -C ₁₀ -alkyl or halogen. Preferably the 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- to 10-membered heteroaromatic ring") as used herein means a 5- or 6-membered ring having 5, 6 or 7 carbon atoms, Refers to a monovalent heteroaromatic radical that can have 8 to 10 total ring members when fused to the ring, and in each case 1, 2, 3 or 4, preferably 1, 2 or 3, 3 are independently of each other a heteroatom selected from the group consisting of oxygen, nitrogen and sulfur. Heteroaryl radicals can be attached to the remainder of a molecule through a carbon ring or nitrogen ring source. Carbocyclic or heterocyclic fused ring is C ₅ ~ C ₇ - are selected from cycloalkyl, 5-, 6- or 7-membered heterocyclyl and phenyl. The heteroaryl may be substituted or unsubstituted by one or more, for example one, two or three, of the same or different radicals R ^a and R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen. Preferably the aryl is phenyl.

Examples of monovalent 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, Oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl, and isoxazolyl.

Examples of 5- to 6-membered heteroaromatic rings (or phenyl rings fused to 5- to 6-membered heteroaromatic rings) fused to a phenyl ring include quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, Benzofuryl, benzthienyl, benzo [b] thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl and benzimidazolyl. Examples of 5- to 6-membered heteroaromatic rings fused to the cycloalkenyl ring include dihydroindolyl, dihydroindolinyl, dihydroisoindolinyl, dihydroquinolinyl, dihydroisoquinolinyl, chromenyl, and chroma Neal and others.

The term "heteroarylene" as used herein refers to a heteroaryl radical as defined above, wherein one of the hydrogen atoms at any position in the heteroaryl is substituted by one further bond position to form a bivalent moiety . The heteroarylene may be unsubstituted or substituted by one or more, for example one, two or three, of the same or different radicals R ^b and R ^b is selected from C ₁ -C ₁₀ -alkyl or halogen.

The term "heterocyclyl" refers to a nonaromatic saturated or partially unsaturated double bond having 5 or 6 ring members and 1, 2, 3 or 4, preferably 1, 2 or 3 heteroatoms (ring members) Includes a summoning loop. Heterocycle radicals can be attached to the remainder of a molecule through a carbon ring or nitrogen ring source. Examples of non aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, Thiazolinyl, thiazolidinyl, isothiazolidinyl, oxazolidinyl, thiazolyl, thiazolinyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolidinyl, isoxazolidinyl, thiazolinyl, isothiazolidinyl, Thienyl, thiopyranyl, dihydrothiopyranyl, tetrahydrofuranyl, thiazolyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, Thiopyranyl, morpholinyl, thiazinyl, and the like. Examples of heterocycle rings containing one or two carbonyl rings as ring members include pyrrolidine-2-onyl, pyrrolidine-2,5-diynyl, imidazolidin-2-onyl, oxazolidine 2-onyl and thiazolidin-2-onyl and the like. The heterocyclyl may be substituted by one or more, for example one, two or three, of the same or different radicals R ^a , and R ^a is selected from C ₁ -C ₁₀ -alkyl or halogen. Preferably the aryl is phenyl.

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

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

The polyamide polymers herein will be understood to be homopolymers, copolymers, blends and grafts of synthetic long chain polyamides having repeating amide groups within the polymer backbone as essential components.

Examples of the polyamide homopolymers include nylon-6 (PA 6, polycaprolactam), nylon-7 (PA 7, polyenantolactam or polyheptanoamid), nylon-10 (PA 10, polydecanoamide) Nylon-12 (PA 12, polydodecanolactam), nylon-4,6 (PA 46, polytetramethylene adipamide), nylon-6,6 (PA 66, , Polyhexamethyleneadipamide), nylon-6,9 (PA 69, a polycondensation product of 1,6-hexamethylenediamine and azelaic acid), nylon-6,10 (PA 610, 1,6-hexamethylenediamine And polycondensation products of 1,10-decanedioic acid), nylon-6,12 (PA 612, a polycondensation product of 1,6-hexamethylenediamine and 1,12-dodecanedioic acid), nylon-10,10 PA 1010, a polycondensation product of 1,10-decamethylene diamine and 1,10-decanedicarboxylic acid), PA 1012 (polycondensation product of 1,10-decamethylene diamine and dodecanedicarboxylic acid) or PA 1212 (1,12 - dodecamethylenediamine and dodecandicarboxylic acid There is the polycondensation product).

The polyamide copolymer may comprise polyamide building blocks in varying proportions. Examples of polyamide copolymers include nylon 6/66 and nylon 66/6 (PA 6/66 and PA 66/6, i.e., copolyamides made from PA 6 and PA 66 building blocks (i.e., caprolactam, hexamethylenediamine and Copolyamide made from dipropan)). PA 66/6 (90/10) may contain 90% of PA 66 and 10% of PA 6. A further example is nylon 66/610 (PA 66/610 made from hexamethylenediamine, adipic acid and sebacic acid).

The polyamide further comprises a partially aromatic polyamide. The 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 (made of terephthalic acid and nonanediamine), PA 6T / 6I (made of hexamethylenediamine, terephthalic acid and isophthalic acid), PA 6T / 6, PA 6T / 6I / 66 and PA 6T / 66 .

The polyamides additionally include aromatic polyamides such as poly-meta-phenylene-isophthalamide (Nomex®) or poly-para-phenylene-terephthalamide (Kevlar®) do.

The polyamides can in principle be prepared by two methods. In the polymerization of amino acids or derivatives of these amino acids, such as aminocarbonitrile, aminocarboxamide, aminocarboxylate esters or aminocarboxylate salts, as well as the polymerization of dicarboxylic acids and diamines, amino and carboxyl of the starting monomers or starting oligomers The terminal groups react with each other to produce an amino group and water. Water may then be removed from the polymer. In the polymerization from carboxamide, the amino and amide terminal groups of the starting monomer or starting oligomer react with each other to produce amide groups and ammonia. The ammonia can then be removed from the polymer. Such a polymerization reaction is generally known as a condensation reaction.

Polymerization from lactam as the starting monomer or starting oligomer is usually known as the medium addition.

The polyamides are copolymers made from polyamides and copolymers made from fragments having additional segments such as diols, polyesters and ethers, in particular polyesters, polyesters, And fragments having the form of an esteramide or polyetheramide. For example, in polyetheramide, the polyamide segment may 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 semi-crystalline polyamide selected from aliphatic polyamides, partially aromatic polyamides, and mixtures thereof. According to a specific embodiment, the polyamide resin is selected from 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 specific embodiment, 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 following, as to the preferred embodiments relating to the variables (substituents) and the indices of the compounds of formula (I), are effective per se as well as preferably together with each other. It is apparent to those skilled in the art that x is 2 or 3 and Z can be the same or different.

Embodiments of the invention relate to uses and methods wherein, in the compounds of formula I, the variables, R ¹ , R ² , Z and x, when taken individually or together, have the following meanings:

x is 1, 2 or 3;

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 -alkyl, -Cycloalkyl-C ₁ -C ₄ -alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl-C ₁ -C ₄ -alkyl;

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, 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 heterocycloalkyl alkylene, and unsubstituted or substituted heterocycloalkyl alkylene -C ₁ ~C ₄ - alkylene-heterocycle selected from alkylene.

Preferred embodiments of the present invention are directed to uses and methods wherein the variables in the compounds of formula I, i.e. R ¹ , R ² , Z and x, when taken individually or together, have the following meanings:

x is 1, 2 or 3, preferably 1 or 2, especially 1;

R ¹ and R ² are, independently of each other, hydrogen, branched C ₃ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl-C ₁ ~C ₄ - alkyl, aryl and -C ₁ ~C ₄ - doedoe selected from alkyl, wherein each ring is not the same or is optionally substituted by one or more different radicals R ^a and the last of the four by way of example the radical , R is ^a C ₁ ~C ₁₀ - selected from alkyl and halogen.

More preferably, R ¹ and R ² are, independently of each other, hydrogen, branched C ₃ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ -C ₁₂ -cycloalkyl C ₁ -C ₄ -alkyl, phenyl and phenyl-C ₁ -C ₄ -alkyl, wherein each ring of the four last-mentioned radicals is optionally substituted by one or more identical or different radicals R ^a , is not substituted, R is ^a C ₁ ~C ₁₀ - is selected from alkyl and halogen. In particular, R ¹ and R ² independently of one another are hydrogen, branched C ₃ -C ₁₀ -alkyl which is bonded to the backbone through a secondary or tertiary carbon atom of the alkyl group, a radical R ^a substituted or unsubstituted by one or two C ₅ -C ₁₀ -cycloalkyl, and phenyl which is unsubstituted or substituted by one or two 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, Cyclohexyl, cyclopentylmethyl, 1-cyclopentyl, 1-cyclohexylmethyl, 1-cyclohexylmethyl, Ethyl, 2-cyclopentylethyl, cyclohexylmethyl, 1-cyclohexylethyl, 2-cyclohexylethyl, cyclopentyl (substituted by one or two C ₁ -C ₄ -alkyl), cyclohexyl Or by two C ₁ -C ₄ -alkyl), phenyl, tolyl or 3,4-dimethylphenyl. Particularly, R ¹ and R ² are independently selected from the group consisting of hydrogen, isopropyl, tert-butyl, 1-methylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2-methylbutyl, , 3-tetramethylbutyl and 1-adamantyl.

[식 중, #는 우레아 부분 중 내부 질소 원자에의 결합 점임]을 지닌다. 특히 Z는 트랜스-1,4-사이클로헥산디일이다. 특히 만일 x가 2이면, 각각의 Z는 동일한 의미를 갖는다.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 of the four last-mentioned radicals is unsubstituted or substituted by one or two identical or different radicals R ^b and R ^b is a C ₁ -C ₁₀ -alkyl Or halogen. Z is preferably 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, cis-1,2-cyclopentanediyl, trans- Cyclopropanediyl, trans-1,3-cyclopentanediyl, wherein the last four radicals are unsubstituted or substituted by one or two C ₁ -C ₄ -alkyl groups, cis- _1, 2-cyclo Cyclohexanediyl, trans-1, 3-cyclohexanediyl, cis-1, 4-cyclohexanediyl, trans-1, 4-cyclo has a hexane-diyl, at this time, the group 6 and the last time exemplified is unsubstituted or substituted with 1 or 2 C ₁ ~C ₄ - alkyl group, 1,2-phenylene, 1,3-phenylene, 1,4- Phenylene, wherein the three last-mentioned groups are unsubstituted or substituted by one or two C ₁ -C ₄ -alkyl groups;

[Wherein # is the point of attachment of the urea moiety to the internal nitrogen atom]. In particular, Z is trans-1, 4-cyclohexanediyl. Especially if x is 2, then each Z has the same meaning.

Preferred embodiments of the present invention are directed to uses and methods wherein R ¹ and R ² in the compounds of formula (I) have different meanings. Further preferred embodiments of the invention relate to uses and methods, wherein R ¹ and R ² in the compounds of formula (I) have the same meaning.

Particularly preferred embodiments of the present invention relate to uses and methods wherein the variables R ¹ , R ² , Z and x in the compounds of formula (I) 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;

x is 1.

Particularly preferred further embodiments of the present invention relate to uses and methods wherein the variables R ¹ and R ² in the compounds of formula I are both hydrogen and Z is trans-1,4-cyclohexanediyl, x is one.

Particularly preferred embodiments of the present invention relate to uses and methods wherein the polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66, In the compound of I, R ¹ and R ² are the same and are selected from tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, 1,1,3,3-tetramethylbutyl and 1-adamantyl Being; Z is trans-1,4-cyclohexylene; x is one.

Particularly preferred further embodiments of the present invention relate to uses and methods wherein the polyamide resin is selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6 and PA 6/66 , R < ¹ > and R < ² > in the compounds of formula (I) are both hydrogen; Z is trans-1,4-cyclohexylene; x is one.

The compounds of formula I are known in the art or may be prepared analogously to standard methods in the art or may be prepared as outlined in the experimental part of the present application.

The compounds of formula (I) wherein x is 1 are also referred to as bisurea compound I.

The compounds of formula (I) wherein x is 2 are also referred to as trisurea compound I.

The compounds of formula (I) wherein x is 3 are also referred to as tetra-urea compound I.

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

[Reaction Scheme 1]

In the above Reaction Scheme 1, Z and R ¹ are as defined. The diamine compound of formula (II) reacts with 2 equivalents of isocyanate of formula (III), resulting in a compound of formula (I) in good yield. The reaction is usually carried out in an organic solvent. Suitable solvents are polar aprotic solvents, such as tetrahydrofuran.

Alternatively, the bisurea compound of formula (I) may be prepared via the reaction of a diisocyanate compound of formula (IV) and an amine of formula (V). The reaction is usually carried out in an organic solvent. Suitable solvents are polar aprotic solvents, such as tetrahydrofuran.

[Reaction Scheme 2]

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

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

[Reaction Scheme 3]

In the above Reaction Scheme 3, Z, R ¹ and R ² are as defined above. When each of the amine compounds of formulas VI and VIa is each treated with an isocyanate of formula VII and III, the compound of formula I is produced in good yield. The reaction is usually carried out in an organic solvent. Suitable solvents are polar aprotic solvents, for example N-methylpyrrolidone.

Tris-urea compound of formula I, i.e., x is 2 and R ¹ are the compounds of formula I having the same meaning as R ² can be prepared as described schematically in Scheme 4.

[Reaction Scheme 4]

In the above Reaction 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, the diamine of formula II is reacted with 1 equivalent of the isocyanate of formula III, resulting in the amine compound of formula X. The reaction may proceed analogously to the procedure described in Scheme 1. [ In step ii) of Scheme 4, the amine compound of formula X is reacted with a halide of the carbonyl of formula XI, resulting in the trisurea compound of formula I as a result.

Compounds of formula I in which x is 2 and R ¹ has the same meaning as R ² may also be prepared as outlined in Scheme 5.

[Reaction Scheme 5]

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

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

Compounds of formula I in which x is 3 and R ¹ has the same meaning as R ² can be prepared as outlined in Scheme 6.

[Reaction Scheme 6]

In Scheme 6, R ¹ and Z are as defined above. R ¹ may have the same or different meanings. Z may have the same or different meanings. The amino compound of formula (XI) is reacted with a diisocyanate compound of formula (IV) in the same manner as described in scheme (2).

The polyamide resins of the present invention often contain one or more additional components selected from, for example, colorants, antioxidants, UV absorbers, light stabilizers, reinforcing agents, fillers, anti-fogging agents, release agents, biocides, antistatic agents and rheology control agents . Examples of additional ingredients that may be included in the compositions of the present invention include the following:

1. Colorant

The term colorant includes dyes and pigments. The pigments may be organic or inorganic pigments as are known in the art. Examples of suitable pigments are color pigments, pearlescent pigments, for example pigments based on effect pigments or liquid crystal polymers.

The colorant may be a dye. What is considered as a colorant similarly to the above is an organic compound which exhibits fluorescence in the visible portion of the electromagnetic spectrum, such as a fluorescent dye or a fluorescent whitening agent. The colorant may also have additional properties, for example electrical conductivity, or may have magnetic shielding properties.

Suitable dyes are all dyes soluble in the polyamide polymer composition. Examples of suitable dyes include 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-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl- -Methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- Methylphenol, nonylphenols whose side chain is linear or branched, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'- Phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl- mixture.

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

2.3. Hydroquinone and alkylated hydroquinone such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5- 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 and bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

2.4. Tocopherol, such as alpha-tocopherol, beta -tocopherol, gamma -tocopherol, delta-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) Thiobis- (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert- amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

2.6. Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert- Methylenebis (4-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'- Methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6- , 2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) Bis [6- (alpha, alpha -dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6- Hydroxybenzyl) -4-methylphenol,

(5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl (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- butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert- .

2.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl- 3,5-di-tert-butylbenzylmercaptoacetic acid salt, tris (3,5-di-tert-butyl-4-hydroxy Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso (4-tert- butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, Octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid salt.

2.8. Hydroxybenzyl malonate, for example, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl- Butyl 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- Butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert- Benzyl) phenol.

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

2.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di- tert -butyl-4-hydroxybenzylphosphonate Butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5 Calcium salt of monoethyl ester of di-tert-butyl-4-hydroxybenzylphosphonic acid.

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

2.13. butylphenyl) propionic acid with a mono- or polyhydric alcohol such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-di (tert- Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso-hexane, hexane diol, 1,9-nonanediol, ethylene glycol, 3-thiophenecarboxylic acid, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, , 6,7-trioxabicyclo [2.2.2] octane.

2.14. (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, 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-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane, 4-hydroxymethyl- 6,7-trioxabicyclo [2.2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1- dimethylethyl] -2,4,8,10-tetraoxa Spiro [5.5] undecane.

2.15. (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N ', N'-tetramethyluronium hexafluorophosphate, 3-thiophenecarboxylic acid, bis- (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- hydroxymethyl- Esters of oxabicyclo [2.2.2] octane.

2.16. Di-tert-butyl-4-hydroxyphenylacetic acid and mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, Di (ethylene glycol), ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, - (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Cyclo [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 N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] Oxamide (Uniroyal < RTI ID = 0.0 > Naugard < / RTI > XL-1).

2.18. Ascorbic acid (vitamin C)

2.19. Amine based antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'- (1-ethylhexyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -phenyl Phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) Phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'- Phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- Phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octyldiphenylamine, such as p, p'-di-tert-octyldiphenylamine, -Aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, Bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ' , 3'-dimethylbutyl) phenyl] amines, tert-octylated N-phenyl-1-naphthylamines, mixtures of 1 alkylated and 2 alkylated tert-butyl / tert-octyldiphenylamines, Mixtures of phenylamines, mixtures of 1-alkylated and 2-alkylated dodecyldiphenylamines, mixtures of 1-alkylated and 2-alkylated isopropyl / isohexyldiphenylamines, mixtures of 1-alkylated and 2-alkylated tert-butyldiphenylamines, 2,3 Dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, 1 N, N ', N'-tetraphenylthiophenothiazine, a mixture of 1-alkylated and 2-alkylated tert-butyl / tert-octylphenothiazine, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) -hexamethylenediamine, bis (2,2,6,6,6-tetramethylpiperid- -Tetramethylpiperid-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, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- , 3'-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3'- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxy) benzotriazole, (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, -5- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) -5- chlorobenzotriazole, 2- (2'-tert-butyl-2'-hydroxy-5'- (2-octyl) phenyl) benzotriazole, (2-ethylhexyloxy) carbonylethyl] -2 ' -hydroxyphenyl) benzotriazole , 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- Methylbenzene [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2-ylphenol], 2- [3'-tert -butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl] -2H- benzotriazole with the transesterification reaction product of 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-yl-phenyl, 2- [2 ' and De-hydroxy -3 '- (α, α- dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole jolim; 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (?,? - dimethylbenzyl) phenyl] benzotriazole.

3.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

3.3. Esters of substituted and unsubstituted benzoic acids such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert- butylbenzoyl) resorcinol, Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid salt, hexadecyl 3,5-di-tert- butyl-4-hydroxybenzoic acid Butyl-4-hydroxybenzoic acid salt, 2-methyl-4,6-di-tert-butylphenyl 3,5-di- salt.

3.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxy cinnamate, methyl α- Methyl-p-methoxy cinnamate, butyl? -Cyano-? -Methyl-p-methoxy cinnamate, methyl? -Carbomethoxy-p-methoxy cinnamate and N- Methoxy -? - cyanovinyl) -2-methylindoline.

3.5. Nickel complexes of nickel compounds, for example 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], for example, addition ligands such as n-butylamine, triethanol A 1: 1 or 1: 2 complex with or without an amine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, a monoalkyl ester such as the nickel salt of a methyl or ethyl ester, Nickel salt of hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complex of ketoxime such as 2-hydroxy-4-methylphenyl undecylketoxime, 1-phenyl -4-lauroyl-5-hydroxypyrazole.

3.6. Steric hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl Butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Condensates of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetramethyl -4-piperidyl) linear or cyclic condensates of hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetra Methyl-4-piperidyl) nitrilotriacetic acid salt, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylic acid salt, 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4- (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy- Tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane- , Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5- Or cyclic condensates, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) (3-aminopropylamino) ethane, a condensate of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) , Condensates of 5-triazine and 1,2-bis (3-aminopropylamino) ethane, condensates of 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8- Spiro [4.5] decane-2,4-dione, 3-dodecyl (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6- Methyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, Condensates of N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5- Bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino- 2,2,6,6-tetramethylpiperidine Condensation product (CAS registration 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-tetramethylpiper Condensation of Dean (CAS Registry Number [192268-64-7]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl- ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, The reaction product of 7,9,9-tetramethyl-2-cyclohexyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1- (1, 2, 6, 6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'- Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride and -olefin copolymers with 2,2,2- The reaction product of 6,6-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- Ethoxy-5-tert-butyl-2'-ethoxanilide and a mixture of this with 2-ethoxy-2'-ethyl-5,4'-di-tert- butoxanilide, o- And p-methoxy-2-substituted oxanilides, and mixtures of o- and p-ethoxy-2-substituted oxanilides.

3.8. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxy) -4,6-bis Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 2- (2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy- Hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- (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-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- 2- (2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyl] Oxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

4. Metal deactivators such as N, N'-diphenyl oxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-diacetyl adipoyl dihydrazide, N, N'- '- bis (salicyloyl) thiopropionyl dihydrazide.

5. The use of phosphites and phosphonites such as triphenyl phosphates, diphenyl alkyl phosphates, phenyl dialkyl phosphates, tris (nonylphenyl) phosphates, trilauryl phosphates, trioctadecyl phosphates, (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, diisodecyloxypenta (pentaerythritol diphosphite) (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite, bis (2,4,6-tris (tert- butylphenyl) pentaerythritol 2 Tris (2,4-di-tert-butylphenyl) 4,4'-biphenylene 2 phosphonite, 6-isooctyloxy-2,4,8,10 - tetra-tert- (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di -tert-butyl-6-methylphenyl) ethylphosphate, 6-fluoro-2,4,8,10-tetra- 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl- -Ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphorane.

6. Phosphorus containing acids, salts of phosphorus containing acids, esters of phosphorus containing acids or derivatives thereof:

Phosphorus containing acids include phosphorous oxo acids such as phosphoric acid, phosphonic acid and phosphinic acid. Suitable salts of phosphorus containing acids include 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 bisphosphate (also known as Mn (H ₂ PO ₂ ) ₂ , manganese (II) hypophosphite), aluminum phosphinate _{Al (H 2 PO 2) 3} ) and mixtures thereof are particularly preferred. in addition, the phosphonic acid ester, and its half-esters and mixtures, in particular hydroxyphenyl alkyl phosphonic acid ester, and its half ester, or a mixture, for example, WO Especially those described in US 2007006647, especially those in which calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] (Irgamod® 195, available from BASF SE) (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (commercially available from EIgalmode® 295, BASF) is particularly preferred.

7. Hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N , N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, hydrogenated urea amine derived N, N-dialkylhydroxylamine.

8. Nitrones such as N-benzyl-alpha-phenylnitron, N-ethyl-alpha-methylnitron, N-octyl-alpha-heptylnitron, N-lauryl- Alpha-heptadecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl- Octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitron, N-octadecyl-alpha-hexadecylnitronone, hydrogenated urea amine derived N, N-dialkylhydroxylamine derived nitrone .

9. Thiosynergists, such as dilauryl thiodipropionate or distearyliodipropionate.

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

11. Polyamide stabilizers, for example copper salts with iodides and / or phosphorus compounds, and salts of divalent manganese.

12. A composition comprising a basic co-stabilizer, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and alkaline earth Metal salts such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. It is preferable that the polyamide resin does not contain barium stearate.

13. Other additives such as plasticizers, lubricants, flow control agents, flame retardants, mold release agents and foaming agents.

14. Benzofuranones and indolinones, for example in US-A-4,325,863; US-A-4,338,244; US-A-5,175,312; US-A-5,216,052; US-A-5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; Phenyl-5,7-di-tert-butylbenzofuran-2-one, 5 < RTI ID = 0.0 > , 7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran- (4-ethoxyphenyl) benzofuran-2-one, 5,7-di-tert-butyl-3- 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran- Butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert- Dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

15. Fillers or reinforcing agents include, for example, glass fabric, glass mat or filament glass roving in the form of glass fibers, chopped glass, glass beads and wollastonite. Glass fibers can be incorporated in the form of both short glass fibers and long fibers (roving).

16. Antistatic agents, for example amine derivatives, for example N, N-bis (hydroxyalkyl) -alkylamines or -alkyleneamines, polyethylene glycol esters and ethers, ethoxylated carboxyl esters and carboxamides, glycerol mono Stearates and distearates, and mixtures thereof.

17. Biocides can be pesticides or microbes.

One or more compounds of formula I may be present in an amount of from 0.001 to 5% by weight, preferably from 0.01 to 3% by weight, such as from 0.001 to 3% by weight, from 0.01 to 2% by weight, from 0.01 to 1.5% by weight, 0.025 to 1% by weight.

The weight ratio of the compound of formula I to (if present) any of the foregoing components is preferably from 1: 100 to 100: 1, for example from 1: 90 to 90: 1, from 1:80 to 80: 1: 60 to 60: 1, 1: 50 to 50: 1, 1: 40 to 40: 1, 1: 30 to 30: : 1, 1: 5 to 5: 1, 1: 4 to 4: 1, 1: 3 to 3: 1, 1: 2 to 2: 1 or 1: 1.

According to the present invention there is provided a process for improving one or more properties of a solid state material of a polyamide resin comprising the steps of:

a) providing a polyamide;

b) providing at least one urea compound of formula I as defined above; And

c) incorporating the urea compound of formula I into the polyamide.

The polyamides are preferably selected from aliphatic polyamide homopolymers, aliphatic polyamide copolymers, partially aromatic polyamides, and mixtures thereof, as defined above. The polyamide resin may contain other ingredients or additives such as colorants, antioxidants, UV absorbers, light stabilizers, reinforcing agents, fillers, anti-fogging agents, release agents, biocides, antistatic agents and rheology control agents . ≪ / RTI > In the urea compounds of formula I, the radicals R ¹ , R ² , Z and the exponent x preferably have one of the preferred meanings. The urea compound of formula I may be present in an amount of from 0.001 to 5% by weight, preferably from 0.01 to 3% by weight, more preferably from 0.05 to 2% by weight, based on the weight of the polymer resin.

A polyamide resin having improved solid state properties is provided by the method of the present invention. Particularly the solid state properties selected from mechanical properties and gloss are improved. The polyamide resin prepared by the method of the present invention has improved tensile properties and notch impact toughness. The tensile properties are preferably selected from yield stress, yield strain, tear tensile strain, tear tensile stress, elastic modulus and shear modulus.

One or more compounds of formula I and any additional components may be added to the polyamide resin individually or in combination. If desired, the individual additives may be mixed with one another before incorporation into the polyamide polymer, for example, as a melt (melt blend).

The incorporation of the compound of formula (I) into the polyamide resin and any incorporation of conventional components into the polyamide resin can be accomplished by any known method. Such incorporation can be achieved, for example, by dry blending, extrusion of a mixture of various components, conventional masterbatch manufacturing techniques, addition of additive concentrates, addition of additives, such as the addition of fillers mixed in a polymer carrier ≪ / RTI >

The incorporation can be carried out in any heatable container equipped with a stirring device, for example a sealing device, such as a kneader, mixer or stirring vessel. Examples of processing the composition according to the present invention include injection blow molding, extrusion, blow molding, extrusion blow molding, rotational molding, in-mold decoration (back injection), slush (Molding), injection molding, co-molding, forming, compression molding, compression, film extrusion (cast film; blown film) Annealing, deep drawing, calandering, mechanical deformation, sintering, co-extrusion. The incorporation is preferably carried out in an extruder or kneader according to methods known in the literature.

It does not matter whether the processing takes place in an inert atmosphere or in the presence of oxygen.

The polyamide resins comprising the compounds of formula (I) can be made into shaped articles using any suitable melt processing techniques, such as injection molding, extrusion, blow molding, injection blow molding and thermoforming. The polyamide resins comprising the compounds of formula (I) are usually films, fibers, sheets, pipes, semi-finished products, granules, containers, blow molded articles or monofilaments. The film may be a single layer film or a multilayer film or fiber.

Polyamide articles comprising a compound of formula I are characterized by exhibiting high strength, high stiffness, high notch impact toughness, high tear tensile strain, tear tensile stress, modulus of elasticity and shear modulus, Aerospace, electrical / electronics, sports and leisure, mechanical engineering or in the field of aggressive media.

Without intending to limit the generality of the foregoing, the articles made from polyamide resins containing the compounds of formula (I) are particularly suitable for use in machine parts with toughness, excellent dimensional stability at high temperatures, Such as gears, housings such as filter housings or solenoid valve housings, electric heaters, trailing cable attachments, electrical insulating parts such as fuel and / or oil tanks or reservoirs, A lens for a technical device, a viewing glass for a heating technique, a filter cup for treating a beverage, a flow meter for a bottle, a gas or a liquid medium, a watch case , A watch case, an automobile accessory, a lamp case, a reflector for a lamp, a switch for illuminating a backlight, a surgical material al, cartridges or decorative parts, or packaging materials.

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

Hereinafter, the present invention will be described in more detail by the following embodiments. It is to be understood, however, that the intention is not to limit the invention to the embodiments described below, but merely to illustrate the invention.

Preparation of compounds of formula (I)

I.1 Compounds of formula (I) wherein x is 1 and R ¹ and R ² are the same

Example 1: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (tert-butyl) urea)

A solution of tert-butyl isocyanate (3.90 g, 0.039 mol) in anhydrous tetrahydrofuran (THF) (50 mL) was added to a solution of trans-1,4-diaminocyclohexane 0.0 > g, < / RTI > 0.019 mol). At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from N, N-dimethylformamide (DMF) and then dried under high vacuum.

MS (70 eV): 312 (M < ^{+ &} gt ^; ).

Example 2: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (cyclohexyl) urea)

A solution of cyclohexyl isocyanate (5.49 g, 0.044 mol) in anhydrous THF (50 mL) under inert atmosphere was treated with trans-1,4-diaminocyclohexane (2.51 g, 0.022 mol) in dry THF (100 mL) Lt; / RTI > At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from DMF and then dried under high vacuum.

MS (70 eV): 364 (M ^< ^{+ &} gt ^; ).

Example 3: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (isopropyl) urea)

A solution of isopropylamine (1.25 g, 0.022 mol) in anhydrous THF (50 mL) under inert atmosphere was treated with trans-1, 4-cyclohexane diisocyanate (1.75 g, 0.011 mol) in dry THF (100 mL) Lt; / RTI > At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from DMF and then dried under high vacuum.

MS (70 eV): 284 (M ^< ^{+ &} gt ^; ).

Example 4: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (1-ethylpropyl) urea)

A solution of 3-aminopentane (2.20 g, 0.025 mol) in anhydrous THF (50 mL) under an inert atmosphere was treated with trans-1, 4-cyclohexane diisocyanate (2.00 g, 0.012 mol) in dry THF ) In < / RTI > At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from DMF and then dried under high vacuum.

MS (70 eV): 340 (M ^< ^{+ &} gt ^; ).

Example 5: Synthesis of 1,1 '- (cis-1,4-cyclohexylene) bis (3- (cyclohexyl) urea)

A solution of isocyanatocyclohexane (3.25 g, 0.026 mol) in anhydrous THF (50 mL) under an inert atmosphere was treated with cis-1,4-cyclohexanediamine (1.50 g, 0.013 mol) in anhydrous THF (100 mL) Lt; / RTI > At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from MeOH and then dried under high vacuum.

Melting point: 252 DEG C

MS (70 eV): 364 (M ^< ^{+ &} gt ^; ).

Example 6: Synthesis of 1,1 '- (cis-1,4-cyclohexylene) bis (3- (tert-butyl) urea)

A solution of tert-butyl isocyanate (2.57g, 0.026mol) in anhydrous THF (50ml) under an inert atmosphere was treated with cis-1,4-cyclohexanediamine (1.50g, 0.013mol) in dry THF (100ml) Lt; / RTI > At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional dry THF. The resulting white solid was recrystallized from MeOH and then dried under high vacuum.

Melting point: 319 DEG C

MS (70 eV): 312 (M < ^{+ &} gt ^; ).

The compounds of Examples 7 to 13 were prepared in a similar manner.

Example 7: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (1,1-dimethylpropyl) urea)

MS (70 eV): 340 (M ^< ^{+ &} gt ^; ).

Example 8: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (tert-octyl) urea)

MS (70 eV): 426 (M ^< ^{+ &} gt ^; ).

Example 9: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (1,5-dimethylhexyl) urea)

MS (70 eV): 425 (M ^< ^{+ &} gt ^; ).

Example 10: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (1-adamantyl) urea)

MS (70 eV): 468 (M ^< ^{+ &} gt ^; ).

Example 11: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3-n-butylurea)

Melting point: 358 DEG C

MS (70 eV): 312 (M < ^{+ &} gt ^; ).

Example 12: Synthesis of 1,1 '- (trans-1,4-cyclohexylene) bis (3- (n-propyl) urea)

MS (70 eV): 284 (M ^< ^{+ &} gt ^; ).

Example 13: Synthesis of 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 pH of the solution was adjusted to 5-7 by adding HCl to this solution. 3.3 g of potassium cyanate was slowly added thereto while stirring. At this time, the resulting mixture was heated to reflux and stirred for 24 hours. The precipitate was filtered and then washed with additional water. The resulting white solid was dried under high vacuum.

I.2. Compounds of formula (I) wherein x is 1 and R ¹ and R ² are different

Example 15: 1-tert-Butyl-3- [4- (cyclohexylcarbamoylamino) cyclohexyl] urea

15.1 trans-1- (4-aminocyclohexyl) -3-cyclohexylurea

A solution of trans-1,4-diaminocyclohexane (6.15 g, 0.054 mol) in anhydrous THF (500 mL) under an inert atmosphere was cooled to -40 ° C in a cooling bath (isopropyl alcohol / dry ice). To this was slowly added isocyanatocyclohexane (6.75 g, 0.054 mol) in anhydrous THF (100 mL) and stirred well. At this time, the resulting mixture was further stirred at room temperature for 24 hours. The precipitated white solid was filtered off, suspended in water and acidified to pH 2 (using HCl). At this time the clarified solution was filtered again and the pH of the filtrate was brought to 8 (using NaOH), where trans-1- (4-aminocyclohexyl) -3-cyclohexylurea was precipitated as a white solid.

15.2 1-tert-Butyl-3- [4- (cyclohexylcarbamoylamino) cyclohexyl] urea

A solution of tert-butyl isocyanate (1.17 g, 0.012 mol) in anhydrous N-methyl-2-pyrrolidone (NMP) (50 mL) under an inert atmosphere was added to a solution of trans-1- ( 4-aminocyclohexyl) -3-cyclohexylurea (2.83 g, 0.012 mol). The resulting mixture was heated to 70 < 0 > C and stirred for 24 hours. The solution was precipitated in 1M HCl and then filtered off. The resulting white solid was washed with THF, then recrystallized from DMF and then dried under high vacuum.

Melting point: 325 DEG C

MS (70 eV): 338 (M ^< ^{+ &} gt ^; ).

I.3 and x is 2, R ¹ and R ^2, the same compounds of formula (I)

Example 16:

16.1 trans-1- (4-aminocyclohexyl) -3-cyclohexylurea

Under an argon atmosphere, trans-1,4-diaminocyclohexane (6.15 g, 0.054 mmol) was dissolved in THF (500 mL) in a flame-dried shinkle flask. The solution was cooled to -40 ° C in a cooling bath (isopropyl alcohol / dry ice), and diluted cyclohexylisocyanate (6.75g, 0.054mmol) in THF (100ml) was slowly added thereto Lt; / RTI > The reaction mixture was stirred at room temperature for 12 hours. At this time, the precipitated white solid was filtered off, then suspended in water and acidified to pH 2 (using HCl). At this time the clarified solution was filtered again and the pH of the filtrate was brought to 8 (using NaOH), where trans-1- (4-aminocyclohexyl) -3-cyclohexylurea was precipitated as a white solid.

16.2

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

I.4 x is 3 and R ¹ and R ² are the same compounds of formula (I)

Example 17:

Under argon atmosphere, trans-1- (4-aminocyclohexyl) -3-cyclohexylurea (3.2 g, 13 mmol) was dissolved in NMP by placing it in a flame-dried Shinklit flask. To this was slowly added trans-1,4-cyclohexane diisocyanate (1 g, 6 mmol) diluted in NMP and stirred well. At this time, the resulting mixture was heated to 80 占 폚 and stirred for 12 hours. The solution was precipitated in 1M HCl and then filtered off. The resulting white solid was washed with THF and then dried under vacuum for 2 h (70 C, 100 mbar).

MS (70 eV): 265 (M ^< ^{+ &} gt ^; ).

Unless otherwise noted, the following general methods were applied in practical cases.

Mixing method:

The polyamide pellets and the urea compound of formula I were accurately weighed at a concentration of 1.0 wt%. The composition was then tumble-mixed. The above exemplified mixture was then blended in a co-rotating twin screw extruder (ZSK 18) (rotational speed = 300 rpm, melting temperature = 260 캜, throughput = 6 kg per hour). Blank control samples were prepared by treating the pure polyamides in the same manner.

The following polyamides were used:

- Ultramid® B27: PA grade 6 available from BASF SA, Germany.

Injection molding:

Injection molding was carried out in an injection molding machine having a melting temperature of 260 캜 and a shaft diameter of 30 mm. The melt was injected into the mold (mold temperature = 80 캜). The holding pressure was 600 bar. The test specimens produced were the standard tension bars according to DIN EN ISO 527-2, Typ 1A and the Charpy bar according to ISO 179-2 / 1eA (F).

Compositions, standards and comparative compositions comprising the compounds of formula I given in Table 1 below were prepared as described above, in which case the thickness of the specimen was determined to be 4.0 mm.

PA 6
[weight%] In Example 1
Manufactured
compound
[weight%] Antioxidant ^*
[weight%] calcium
Stearate ^** Talc
IT Extra standard 100 - - - - IC 1 99.0 1.0 - - - IC 2 98.20 1.0 0.3 0.5 - CC 1 99.20 - 0.3 0.5 - CC 2 99.00 - - - 1.0 CC 3 98.20 - 0.3 0.5 1.0 ^* N, N'- hexane-1,6-diyl-bis [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propanamide;
, CAS 23128-74-7
^** Ceasit AV, powder fluid adjuvant (Baerlocher)
IC The composition of the present invention
CC comparison composition

Selected optical properties of compositions, reference compositions and comparison compositions comprising a compound of formula (I) Polish 20 ° 60 ° standard 89.7 96.4 IC 1 119.3 116.5 CC2 95.8 99.2

When the compound of formula (I) was used, the gloss of the polyamide composition incorporating this compound was improved as compared to the gloss of the composition without this compound.

Tensile Properties of Compositions, Reference Compositions and Comparative Compositions Comprising Compounds of Formula I Yield stress Tear tensile stress Yield strain Fracture tensile strain Young's modulus [MPa] [MPa] [%] [%] [MPa] standard 80.43 47.67 4.08 21.87 3013 IC 1 88.31 55.28 3.88 14.38 3255 IC 2 89.84 50.71 3.95 12.43 3251 CC 1 88.58 54.7 3.79 9.91 3224 CC2 91.34 75.92 3.79 8.01 3614 CC3 93.38 77.86 3.76 7.98 3690

When the compound of formula (I) is used, the Young's modulus (elastic modulus) and the tear tensile strain value of the polyamide composition incorporating the compound are higher than the Young's modulus (elastic modulus) and the tear tensile strain value of the composition Respectively.

Charpy notch impact toughness of compositions, reference compositions and comparative compositions comprising compounds of formula (I) Impact toughness
[kJ / m 2] Standard Deviation
[kJ / m 2] Compared to PA 6
Relative change rate of impact toughness [%] standard 7.5 0.2 0.0 IC 1 8.6 0.4 14.4 CC2 6.5 0.3 -13.0

The polyamide composition comprising the compound of formula (I) was excellent in notched impact toughness at 23 占 폚 as compared with the composition containing no compound or containing talc. The thickness of the test specimen was 4 mm.

DMTA-test

The storage modulus G '(elastic modulus) and the loss modulus G "(viscous modulus) were measured by Dynamic Mechanical Thermal Analysis (DMTA, measured in accordance with ISO 6721-7). The dimensions of the test specimens were 4.0 cm in length, 1.0 cm in width, and 0.1 cm in thickness (manufactured by compression plate). The deformation conditions applied at the start of the measurement were: The test was carried out after preconditioning the samples for 3 days at 80 DEG C under vacuum (temperature step: 5 K) under a nitrogen atmosphere (heating start temperature 15.1 DEG C, frequency 1 Hz, strain 0.2% .

The glass transition temperature of pure polyamide (anhydrous) and composition IC1 (anhydrous), as measured by DTMA, was 64 占 폚. As can be seen from the storage elastic modulus and loss elastic modulus, at a temperature higher than T _G , the stiffness change of IC1 was smaller than the stiffness variation of the reference composition. I.e. the stiffness of IC1 in the temperature range above the glass transition temperature was greater than the stiffness of the reference composition.

Claims (18)

Use of a urea compound of one or more of the following formula (I) to improve one or more of the solid state properties of a polyamide resin:
(I)

Wherein,
x is 1, 2 or 3;
R ¹ and R ² independently represent hydrogen, linear C ₁ ~C ₇ - alkyl, branched C ₃ ~C ₁₀ - alkyl, substituted or unsubstituted 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;
Z is a 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 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-heterocycloalkylene. The use according to claim 1, wherein the solid state property is selected from mechanical properties and gloss. 3. Use according to claim 2, wherein the mechanical properties are selected from tensile properties and notch impact toughness. The use according to claim 3, wherein said tensile properties are selected from yield stress, yield strain, tear tensile strain, tear tensile stress, elastic modulus and shear modulus. 2. A compound according to claim 1, wherein R ¹ and R ² are, independently of one another, linear C ₁ -C ₇ -alkyl, branched C ₃ -C ₁₀ -alkyl, unsubstituted or substituted C ₃ -C ₁₂ -cycloalkyl, Substituted C ₃ -C ₁₂ -cycloalkyl-C ₁ -C ₄ -alkyl, unsubstituted or substituted aryl, and unsubstituted or substituted aryl-C ₁ -C ₄ -alkyl. 6. Compounds according to any one of claims 1 to 5, wherein R ¹ and R ² in the formula I are, independently of each other, hydrogen, branched C ₃ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₅ ~C ₁₂ - cycloalkyl, -C ₁ ~C ₄ - alkyl, phenyl or phenyl -C ₁ ~C ₄ - doedoe selected from alkyl, wherein each ring of the four last illustratively radicals are identical or different radicals R ^a the use will be an alkyl or selected from the halogen-no more than one substituted or not substituted by a, R ^a is C ₁ ~C _10. 7. A compound according to any one of claims 1 to 6 wherein R < ¹ > and R < ² > are independently of each other hydrogen, a branched C ₃ -C would cycloalkyl, and the radicals R 1 ^a dog or is a substituted or selected from the non-phenyl substituted by _2-10-alkyl, ^a radical R 1 or 2 that are not substituted or substituted by C ₅ ~C ₁₀ Usage. 8. The use according to any one of claims 1 to 7, wherein R < ¹ > and R < ² > Article according to any one of the preceding claims, in the above 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 - as a phenylene group, wherein each ring of the four last illustratively radicals are identical or different radicals R ^b 1 or 2 And R ^b is selected from C ₁ -C ₁₀ -alkyl and halogen. 10. The method of claim 9, wherein in the formula I Z is a linear C ₅ ~C ₈ - alkylene or C ₅ ~C ₇ - cycloalkylene would use. 11. The use according to any one of claims 1 to 10, wherein x in the formula (I) is 1. 12. Compounds according to any one of claims 1 to 11, wherein R ¹ and R ² are the same and are hydrogen, tert-butyl, 1,1-dimethylpropyl, 1,5-dimethylhexyl, , 3,3-tetramethylbutyl, and 1-adamantyl; Z is trans-1,4-cyclohexylene; wherein x is 1; 13. Use according to any one of claims 1 to 12, wherein the polyamide resin is selected from aliphatic polyamide homopolymers, aliphatic polyamide copolymers, partially aromatic polyamides and mixtures thereof. 14. The method of any one of claims 1 to 13 wherein the polyamide polymer is selected from the group consisting of PA 6, PA 7, PA 10, PA 11, PA 12, PA 66, PA 69, PA 610, PA 612, PA 1010, PA Preferably selected from PA 6, PA 11, PA 12, PA 66, PA 610, PA 66/6, and PA 6/66, from the group consisting of PA 6/66, PA 66/6, PA 66/610 and mixtures thereof For use. 15. The method of claim 14 wherein the polyamide polymer is a PA 6, PA 11, PA 12 , PA 66, PA 610, is selected from PA 66/6 and PA 6/66, R ¹ and R ² in the compound of formula I is And is 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; wherein x is 1; 16. The polyamide resin composition according to any one of claims 1 to 15, wherein the polyamide resin is used in an amount of 0.001 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.05 to 3% by weight, To 2% by weight of the composition. The polyamide resin composition according to any one of claims 1 to 16, wherein the polyamide resin is selected from the group consisting of a colorant, an antioxidant, a UV absorber, a light stabilizer, a reinforcing agent, a filler, a fogging agent, a mold release agent, a biocide, an antistatic agent, ≪ / RTI > further comprising one or more additional additives selected from the group consisting of: A method for improving one or more properties of a solid material of a polyamide resin, comprising the step of adding at least one urea compound of formula (I) as defined in any of claims 1 and 5 to a polyamide resin .