JP2000239256A - Hindered amine, resin composition, polyurethane fiber and production of polyurethane fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a specified organic group more than a specified amount and solubility of less than a specified value in acidic solvents, exerting excellent stabilizing effect when compounded in resins or fibers and so useful as a resin stabilizer. SOLUTION: This compound includes a univalent organic group of formula I (R is a 1-4C alkyl; R1 is H, a 1-4C alkyl or a 1-4C alkoxy) and/or a bivalent organic group of formula II and has <=5.0×10-3 eq/L solubility in acidic solvents wherein the total amount of the above mentoned organic group is >=1.3 mol per 1 kg objective compound. The compound is obtained e.g. as a hindered amine by following steps; mixing and agitating 60 pts.wt. 2,2,6,6-tetramethyl-4- piperidylmethacrylate, 40 pts.wt. cyclohexylmethacrylate and 213 pts.wt. N,N- dimethylmethacrylate at 60 deg.C, adding thereinto 1 pts.wt. 2,2'-azobis(isobutylonitrile), reacting for 2 h and cooling down to room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel hindered amine compound exhibiting a sufficient stabilizing effect even after various kinds of processing, a resin composition containing the hindered amine compound and sufficiently stabilized even after various kinds of processing, The present invention relates to a polyurethane resin and a polyurethane fiber which are sufficiently stabilized even after various processings containing the hindered amine compound, and a method for producing the polyurethane fiber.

[0002]

2. Description of the Related Art Polyalkyl-substituted piperidine derivatives are called hindered amine compounds and are widely used as stabilizers in various resins because of their high effect of stabilizing resin materials. Hindered amine compounds are generally used to suppress deterioration due to light (ultraviolet light). Hindered amine compounds having various structures are widely used depending on the resin to be stabilized, the purpose, the use, and the like. Among resins, polyurethane is more likely to be degraded by various factors than other resins, and it is essential to incorporate a stabilizer. Furthermore, among the polyurethane compositions, the polyurethane fiber has a large surface area per unit weight, and thus is more likely to deteriorate. Among the deterioration factors of polyurethane, nitrogen oxides (NO _x ) cause discoloration even in a very small amount. Therefore, development of an effective stabilizer has been awaited. Among the stabilizers, hindered amine compounds have a high effect of suppressing NO _x discoloration of polyurethane,
Many proposals have been made so far.

[0003] However, even a product stabilized by blending a hindered amine compound often loses the stabilizing effect of the hindered amine compound due to subsequent secondary processing or the like. As an example, dyeing processing on fibers can be mentioned.
There are various methods for fiber dyeing depending on the target fiber and application. Among them, treatment is often performed in an acidic aqueous solution. Since the hindered amine compound is an amine, that is, a basic compound, it forms a salt with an acid in an acidic aqueous solution. Therefore, in the dyeing process, one of the reasons that the stabilizing effect is lost is that the hindered amine compound forms a water-soluble salt and drops off from the fiber. This phenomenon is remarkable in a low-molecular-weight hindered amine compound, but can also occur in a high-molecular-weight hindered amine compound having a molecular weight of thousands to tens of thousands.
If the amount of hindered amino groups in the molecule is increased in order to increase the stabilizing effect, it is easier to remove the acid by the acid treatment. That is, there is a close relationship between the concentration of the hindered amino group in the molecule and the dropout property, and it was not possible to achieve both dropout resistance and a high stabilizing effect.

[0004] Many proposals have been made to react a hindered amine compound with a polymer constituting a resin in order to fundamentally prevent shedding. For example, examples of polyurethane include JP-A-53-1294, JP-A-53-39395, and JP-A-5-155977. However, JP-A-53-1
When a hindered amine compound is reacted with a resin polymer as proposed in Japanese Patent Publication No. 294, JP-A-53-39395, etc., the physical properties of the resin are considerably impaired as compared with the case where the reaction is not carried out. For example, when a hindered amine group is introduced into a polymer terminal using a hindered amine compound as a terminal terminator in polymer polymerization, if the number of terminal groups derived from the hindered amine compound is increased to improve the stabilizing effect, the molecular weight of the polymer is inevitably increased. Inevitably decreases. Therefore, the improvement of the physical properties by increasing the molecular weight and the improvement of the stabilization effect by increasing the number of terminal groups derived from the hindered amine compound are fundamentally contradictory, and the physical properties and chemical stabilization are contradictory. It was not possible to achieve both effects and effects. When a compound having a hindered amino group as a side chain is incorporated into a polymer main chain as proposed in JP-A-5-155977, the polymer molecular weight does not depend on the amount of the hindered amine compound introduced. However, there is a disadvantage that the synthesis of the hindered amine compound and the polymerization reaction of the polymer become complicated. Even if a polymer having a hindered amino group as a side chain is obtained, the interaction between polymer molecules is affected by the presence of a large substituent such as a hindered amino group in the side chain, and the physical The disadvantages still affect the properties.

[0005] Regarding resins other than polyurethane, many proposals have been made to react a hindered amine compound with a polymer constituting the resin. For example, Japanese Unexamined Patent Publication No.
262870, JP-A-6-207142, JP-A-6-240220, and JP-A-6-264029 each disclose a polymerizable hindered amine compound monomer having a carbon-carbon double bond by polymerizing a resin constituting a resin. Stabilized resins obtained by copolymerization with monomers have been proposed. The polymerizable hindered amine compound monomer proposed in these examples can be relatively easily copolymerized with the polymer constituting the resin, but the resin to be copolymerized comprises a vinyl monomer. There was a disadvantage that it was limited to polymers.

[0006] Also, many proposals have been made to use a copolymer of a polymerizable hindered amine compound monomer and another polymerizable monomer as a resin stabilizer. For example, JP-A-5-112725, JP-A-9-3133, JP-A-10-46141 and the like can be mentioned. Although these proposals have improved dropout properties against heat, neutral water, and warm water, none of them have been considered for acid treatment, and have the same problems as the high-molecular-weight hindered amine compounds described above. I was holding it. JP-A-10-46141 proposes a polymer or copolymer of a polymerizable hindered amine compound monomer as a stabilizer for suppressing yellowing during storage of clothes. However, in this proposal, the hindered amine compound is added to a molded product such as clothing by post-processing, instead of being molded as a product after blending the hindered amine compound with the resin. In this method, a stabilized product can be obtained as a final product, but there is a drawback that no effect can be obtained with respect to stability during processing up to that time. In particular, in the case of clothes, since processing from fibers to final products often takes a long time, this is a problem that cannot be ignored. In the case of a resin that is particularly susceptible to deterioration such as polyurethane, the stability of the resin itself is required.
Therefore, it is necessary that the stabilizer is blended even in the stage of the primary product up to the final product, and that the stabilizer does not lose its effect in post-processing such as secondary processing.

[0007]

As described above, although the hindered amine compound has a high stabilizing effect as a resin stabilizer, its stabilizing effect is lost by secondary processing such as dyeing. There was a case. Until now, it is a hindered amine compound as a stabilizer for resins, fibers, and especially fibers that require dyeing under acidic conditions, and has a satisfactory stabilizing effect even after processing without impairing the characteristics of the resin itself. What was shown had not yet been obtained. Also, chemically bonding the hindered amine compound to the polymer constituting the resin was excellent in stability even after secondary processing,
Physical properties had major drawbacks. Therefore, a stabilizer that can be blended with the resin as a stabilizer independent of the polymer that constitutes the resin, and that exhibits excellent stabilizing effects not only on products but also on processed products that have undergone various processes such as dyeing Development was awaited. Particularly when the resin is polyurethane, the interaction between molecules greatly contributes to its excellent physical properties, and the introduction of a heterogeneous structure in the polymer chain significantly impairs the physical properties. since the NO _x such highly susceptible to discoloration degradation by the importance of stabilizers such as above it was very high. Since the present invention can be compounded as a stabilizer independent of the polymer constituting the resin, it does not impair the properties of the resin at all, and has an excellent stabilizing effect even after various processes such as dyeing. An object of the present invention is to provide a hindered amine compound as a resin stabilizer described above, a resin containing the hindered amine compound, especially a polyurethane resin and a polyurethane fiber containing the hindered amine compound, and a method for producing the same.

[0008]

Means for Solving the Problems The present inventors have provided a hindered amine compound for solving the above problems.
As a result of intensive studies on various compound compositions and properties, it has been found that the solubility of the hindered amine compound in an acidic solution is closely related to the problem of the present invention. Further, they have found that introducing an appropriate amount of a hydrophobic group having a specific structure into a hindered amine compound is effective for achieving the object. Furthermore, a hindered amine compound obtained by copolymerizing a polymerizable monomer having a specific structure having a hindered amino group and a polymerizable monomer having a specific structure having a hydrophobic group at an appropriate composition ratio, The present invention has been found to be an effective means, and the present invention has been completed.

That is, the present invention provides a compound represented by the following general formula (1) in one molecule:

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]
A monovalent organic group represented by

Or the following general formula (2):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. A hindered amine compound having at least one kind of one or more kinds of organic groups (A1) selected from the group consisting of divalent organic groups represented by the formula (a): A1) is 1.3
mol or more, and (b) a solubility in an acidic solution of 5.0 × 10 ⁻³ eq / l or less, a hindered amine compound,

Further, in one molecule, the following general formula (3):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]
A monovalent organic group represented by

And the following general formula (4):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or more monovalent and / or divalent organic groups (A) selected from the group consisting of divalent organic groups represented by
2) and one or more monovalent and / or divalent organics selected from the group consisting of a saturated cycloalkyl group having 5 to 10 carbon atoms and a saturated cycloalkylene group having 5 to 10 carbon atoms A compound having at least one group (C1), wherein the weight fraction of the organic groups (A2) and (C1) in the molecule is represented by the following formulas (1) and (2): 40 ≦ W _A2 + W _C1 ≦ 70 Equation (1) 0.6 ≦ (W _A2 ÷ W _C1 ) ≦ 3 Equation (2) [In the above equation, W _A2 represents the weight% of the organic group (A2), and W _C1 represents the organic group (C1). % By weight. Hindered amine compound,

And the following general formula (5):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom or a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
Represents any one of 0 alkoxy groups. X ¹ is a —O— group,
Or a -NH- group. 1 selected from the group represented by
A kind or a mixture of two or more kinds of polymerizable hindered amine compound monomer components (A3);

And the following general formula (6):

Embedded image [In the above general formula, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a saturated cycloalkyl group having 5 to 10 carbon atoms. Y ¹ represents a —O— group or a —NH— group. ]
A hindered amine compound obtained by copolymerizing as an essential component one or a mixture of two or more polymerizable monomer components (C2) selected from the group represented by the following components: The weight fraction of A3) and the component (C2) is expressed by the following formulas (3) and (4): 80 ≦ (W _A3 + W _C2 ) ≦ 100 Formula (3) 0.5 ≦ (W _A3 ÷ W _C2 ) ≦ 2 0.3 Formula (4) [In the above formula, W _A3 is the weight% of the component (A3),
W _C2 represents the weight percentage of component (C2). Hindered amine compound,

And the following general formula (7):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ represents a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
Represents any one of 0 oxyalkylene groups. X ² is -O
— Or —NH— group. A polymerizable hindered amine compound monomer component (A4) of one kind or a mixture of two or more kinds selected from the group represented by

And the following general formula (8):

Embedded image [In the above general formula, R ⁹ represents a hydrogen atom or a methyl group. R ¹⁰ represents a linear or branched saturated alkyl group having 10 to 30 carbon atoms. Y ² represents a —O— group or a —NH— group. A hindered amine compound obtained by copolymerizing, as an essential component, one or a mixture of two or more polymerizable monomer components (D1) selected from the group represented by:
The weight fraction of the component (A4) and the component (D1) in the hindered amine compound is expressed by the following formulas (5) and (6); 80 ≦ W _A4 + W _D1 ≦ 100 Formula (5) 0.3 ≦ (W _A4 ÷) W _D1 ) ≦ 2.3 Expression (6) [wherein W _A4 is the weight% of the component (A4),
W _D1 represents the weight percentage of component (D1). A hindered amine compound that satisfies the following formula: A hindered amine compound, which forms a salt with one or more compounds selected from the group consisting of:
A resin composition containing the hindered amine compound, the resin composition wherein the resin is polyurethane, and the resin composition comprising a phosphite compound; and a polyurethane fiber containing the hindered amine compound; and A polyurethane elastic fiber characterized by containing a phosphite-based antioxidant; and a method of producing a polyurethane fiber characterized by blending the hindered amine compound into polyurethane and spinning the polyurethane fiber.
A method of producing a polyurethane fiber, wherein the hindered amine compound and the phosphite compound are blended into a polyurethane and spun.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the first aspect of the present invention, the monovalent and / or divalent organic group (A1) has the general formula (1)
And one or more monovalent and / or divalent organic groups selected from the group consisting of a monovalent organic group represented by and a divalent organic group represented by the general formula (2). is there. Organic group (A
When 1) is a monovalent organic group, it is preferable that the compound is bonded to another site in the compound at the 4-position of the piperidine ring in the general formula (1). R ¹ in the above general formula (1) is any ^one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Is more preferable. When the organic group (A1) is a divalent organic group, it is preferable that the organic group (A1) is bonded to other positions in the compound at the first and fourth positions of the piperidine ring in the general formula (2). Preferred examples of the organic group (A1) include the following structural formulas (9) to (11);

[0018]

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[0019]

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[0020]

Embedded image And the group represented by These organic groups may be composed of only one type of organic group or may be composed of a mixture of two or more types of organic groups within the range specified as described above. Further, it may be composed of a mixture of a monovalent organic group and a divalent organic group. Among them, it is most preferable that the organic group (A1) comprises the organic group represented by the general formula (9). It is necessary that the number of organic groups (A1) per 1 kg of the hindered amine compound is 1.3 mol or more. If the number of organic groups (A1) is smaller than this, the number of effective sites contributing to stabilization in the compound decreases, and the stabilizing effect is lost. Organic group (A
As the number of 1) is smaller, the amount of the hindered amine compound must be increased to obtain the same effect, which is economically disadvantageous. Hindered amine compound 1k
2.0 mol as the number of organic groups (A1) per g
Above is more preferable in terms of stabilizing effect.

The solubility of the hindered amine compound in the present invention in an acidic solution is measured by the following method. (Measurement of Base Amount per kg of Hindered Amine Compound) 0.0200 g of the hindered amine compound is accurately weighed. When the hindered amine compound is in a solution state, the hindered amine compound may be once separated from the solution and then weighed, or the solution amount such that the weight of the hindered amine compound becomes a predetermined amount as it is in the solution is weighed. Is also good. As a method for separating the hindered amine compound, any known method such as reprecipitation, recrystallization, and evaporation of the solvent can be used. The weighed hindered amine compound is dissolved in 100 ml of the solvent. It is desirable that the solvent used is one that dissolves the hindered amine compound well, does not exhibit basicity itself, and is miscible with water. Examples of such solvents include methanol, ethanol,
Examples thereof include lower alcohol solvents such as propanol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and ether solvents such as tetrahydrofuran and dioxane. Among these solvents, those in which the hindered amine compound to be measured is soluble can be appropriately selected and used. Using a potentiometric titrator (COMTITE-980 / Hiranuma Sangyo Co., Ltd.), the hindered amine compound solution was mixed with a 1 / 100N hydrochloric acid aqueous solution using a glass electrode (GE-101 / Hiranuma Sangyo Co., Ltd.) and a reference electrode (R).
E-101 / Hiranuma Sangyo Co., Ltd.). The end point in the titration curve is defined as the titer. The amount of base per kg of the hindered amine compound is calculated by the following formula (7).
Can be determined by: B _A = V × F × 10 ^-2 ÷ 0.0200 Formula (7) [where B _A is the amount of base (eq / kg) per kg of the hindered amine compound, and V is the titer (ml).
And F represents a factor of a 1 / 100N hydrochloric acid aqueous solution. (Preparation of acidic solution) 1.200 g of acetic acid and 0.250 g of anhydrous sodium acetate are accurately weighed and dissolved in 1 l of pure water using a volumetric flask. (Measurement of solubility of hindered amine compound in acidic solution)
From the amount of base per kg of the hindered amine compound, the weight of the sample for the solubility test was determined to be 5.0 × 10 ^{−5 in} total base amount.
It is determined by the following equation (8) so as to be mol. w _A = (5 × 10 ⁻² ) ÷ B _A Formula (8) [In the above formula, w _A is the weight (g) of the hindered amine compound, and B _A is the amount of base (eq / kg) per kg of the hindered amine compound. Respectively. ]

The hindered amine compound having the weight determined by the above equation (8) is accurately weighed, and sealed in a glass ampoule together with 5 ml of the acidic solution prepared as described above. The ampoule is heat-treated at 100 ° C. for 1 hour and opened after cooling. Dissolve 3 ml of the ampoule in an ampoule filtered with a filter having a pore size of 0.45 μm and 1 ml of a 1 / 10N aqueous sodium hydroxide solution in 100 ml of a solvent. As the solvent to be used, the same solvent as that used in the above-mentioned measurement of the amount of base can be used. The mixed solution is subjected to neutralization titration with a 1 / 100N hydrochloric acid aqueous solution using a potentiometric titrator. As a blank, 3.6 × 10 ⁻³ g of acetic acid and ^0.1 % of anhydrous sodium acetate were used.
3 ml of distilled water containing 75 × 10 ⁻³ g and 1 ml of a 1 / 10N aqueous sodium hydroxide solution are dissolved in 100 ml of a solvent, and titrated in the same manner. In the titration, the point at which all the bases (hindered amine compound, sodium acetate, and sodium hydroxide) in the liquid to be titrated were all titrated is defined as an end point,
Determine the titer. The solubility of the hindered amine compound in the acidic solution is determined from the titer of the sample solution and the blank solution as the amount of base dissolved per liter (1 liter) of the acidic solution by the following equation (9). S _A = (V _S −V _B ) ÷ 300 Equation (9) [where S _A is the solubility (eq / l) of the hindered amine compound in the acidic solution, and V _S is the sample solution 3
The ml of titer (ml), V _B is the titration of the blank solution 3ml (ml), B _A is the hindered amine compound 1k
The amount of base per gram (eq / kg) is shown. ]

In the hindered amine compound according to the first aspect of the present invention, the solubility in the acidic solution determined as described above must be 5.0 × 10 ⁻³ eq / l or less. The smaller the solubility, the better, but 2.5 ×
If it is 10 ^-3 eq / l or less, more preferable characteristics are exhibited.

In the second aspect of the present invention, the organic group (A2) of the hindered amine compound is a monovalent organic group represented by the general formula (3) and a divalent organic group represented by the general formula (4). One or more selected from the group consisting of
Is a divalent and / or divalent organic group. In the general formula (3), R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Or an alkoxy group having 1 to 10 carbon atoms,
Among them, a hydrogen atom or a methyl group is more preferred from the viewpoint of a stabilizing effect. When the organic group (A2) is a divalent organic group, it is preferable that the organic group (A2) is bonded to other positions in the compound at the first and fourth positions of the piperidine ring in the general formula (4). Preferred examples of the organic group (A2) include groups represented by the above structural formulas (9) to (11). These organic groups may be composed of only one type of organic group or may be composed of a mixture of two or more types of organic groups within the range specified as described above. Further, it may be composed of a mixture of a monovalent organic group and a divalent organic group.
Above all, it is most preferable that the organic group (A2) comprises only the organic group represented by the structural formula (9).

The organic group (C1) of the hindered amine compound according to claim 2 of the present invention is selected from the group consisting of a saturated cycloalkyl group having 5 to 10 carbon atoms and a saturated cycloalkylene group having 5 to 10 carbon atoms. One or more monovalent and / or divalent organic groups selected. When the carbon number of the organic group is small, the effect of each group is small, and when the carbon number is large, the number as the group is small, and as a result, the effect is small, and a sufficient stabilizing effect after processing cannot be obtained. As the organic group (C1), a saturated cycloalkyl group having 5 to 15 carbon atoms is particularly preferable. The cycloalkyl group in the present invention represents a group having one or more closed rings in which a plurality of carbon atoms are covalently bonded to each other. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. In the cycloalkyl group, the number of carbon atoms forming a ring may be three or more, but is more preferably five or six. The carbon atom forming the ring may have a linear or branched alkyl chain having 1 to 5 carbon atoms as a substituent. The number of alkyl groups as substituents in the cycloalkyl group is not particularly limited, but it is essential that the total number of carbon atoms be 5 to 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable from the viewpoint of the stabilizing effect that all cycloalkyl groups are constituted by covalent bonds and do not include an unsaturated bond such as a double bond or a triple bond. The organic groups (C1) may all be the same group, or may be composed of two or more types. The following general formulas (12) to (21) as examples of the organic group (C1);

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

Embedded image [In the above general formulas (12) to (21), Z represents any one of a hydrogen atom, a linear or branched saturated alkyl group having 1 to 5 carbon atoms, and a bonding site to another site in the hindered amine compound. Represents. However, the total number of carbon atoms in the formula does not exceed 10, and the number of bonding sites with other sites in the hindered amine compound in Z is 1 or 2. And the like. Among them, preferred are cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, etc., and most preferred are cyclohexyl group, isobornyl group. Group.

The hindered amine compound according to the second aspect of the present invention is a compound having one or more organic groups (A2) and (C1) in the molecule. Weight fraction of organic group (A2) and organic group (C1) in the hindered amine compound
Is required to be in the range of 40 to 70% by weight. If the amount is less than this, the stabilizing effect becomes small and a large amount of a stabilizer is required, which is economically disadvantageous. If the amount is larger than this, the stabilizing effect before various types of processing is relatively improved, but the stabilizing effect after various types of processing is lost. A more preferred range is from 50 to 60% by weight. In addition, the ratio of the weight fraction of the organic group (A2) to the weight fraction of the organic group (C1) is 0.6 to 3
Need to be between If it is smaller than 0.6, the stabilizing effect before processing becomes small, and if it is larger than 3, the stabilizing effect after various kinds of processing is lost. A more preferred range is from 1.0 to 2.5. The weight fraction of the organic groups (A2) and (C1) is expressed as a ratio of the total formula weight of each organic group to the molecular weight. When the hindered amine compound is a polymer compound having a repeating unit, the calculation can also be performed for the repeating unit.

The hindered amine compound according to claim 3 of the present invention comprises one or more polymerizable hindered amine compound monomer components (A3) selected from the group represented by the general formula (5), A hindered amine compound obtained by copolymerizing, as an essential component, one or a mixture of two or more polymerizable monomer components (C2) selected from the group represented by the formula (6); ) And the weight fraction of component (C2) are between 80 and 100% by weight, and the weight ratio of component (A) to weight fraction of component (C2)
It is necessary that the ratio of the weight fractions in 3) satisfies both that is between 0.5 and 2.3. The weight fraction of each component is represented by a ratio of the total weight derived from each component to the weight of the hindered amine compound. The weight of each component in the hindered amine compound can be determined by using any known method for analyzing a polymer. Examples of the quantification include, but are not limited to, quantification of each component by ¹ H-NMR, quantification of a hindered amine component by neutralization titration, and the like. When it is difficult to determine the amount from the hindered amine compound, the weight% of the charged components can be used instead. If the sum of the weight fractions of the component (A3) and the component (C2) is less than 80% by weight, the stability before and after various processes cannot be well expressed in a well-balanced manner. More preferably, it is in the range of 95 to 100% by weight. Component (A3) based on the weight fraction of component (C2)
If the weight fraction ratio is less than 0.3, the stabilizing effect before processing becomes small, and if the stabilizing effect is to be obtained sufficiently, the blending amount must be increased, which is economically disadvantageous. Becomes
On the other hand, when the ratio is larger than 2.3, the stabilizing effect before processing is sufficiently obtained, but the stabilizing effect after various types of processing is not obtained. Especially, it is especially preferable that it is in the range of 1.0 to 1.6.

R ³ in the general formula (5) is a hydrogen atom or a methyl group, more preferably a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 10 carbon atoms.
Of these, a hydrogen atom and a methyl group are more preferred, and a hydrogen atom is most preferred from the viewpoint of a stabilizing effect. X ¹ in the general formula (5) is -O-
Or an -NH- group, more preferably an -O- group. Polymerizable hindered amine compound monomer component (A
3) is 1 selected from the group represented by the general formula (5).
It is a kind or a mixture of two or more kinds, and each of R ³ , R ⁴ and X ¹ may be mixed with a different group, or each may be a single group. The most preferred combination is R
³ is a methyl group, R ⁴ is a hydrogen atom, and X ¹ is —O
-A group. Preferred examples of the polymerizable hindered amine compound monomer component (A3) include 2,2,6,
6-tetramethyl-4-piperidyl methacrylate,
2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, N- (2,2,
6,6-tetramethyl-4-piperidyl) -methacrylamide, N- (1,2,2,6,6-pentamethyl-4)
-Piperidyl) -methacrylamide, N- (2,2,
6,6-tetramethyl-4-piperidyl) -acrylamide, N- (1,2,2,6,6-pentamethyl-4-)
Piperidyl) -acrylamide. Among them, particularly preferred is 2,2,6,6-tetramethyl-4-
Piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6
6-pentamethyl-4-piperidyl methacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl acrylate. Most preferred is 2,2,6,6
-Tetramethyl-4-piperidyl methacrylate. As the component (A3), compounds in the range of the compounds specified as described above can be mixed and used at an arbitrary composition ratio. Especially, it is preferable to use only 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

R ⁵ in the general formula (6) is a hydrogen atom or a methyl group, more preferably a methyl group. R ⁶ is
It is one or more monovalent organic groups selected from the group consisting of saturated cycloalkyl groups having 5 to 10 carbon atoms and derivatives thereof. When the carbon number of the organic group is small, the effect of each group is small, and when the carbon number is large, the number as the group is small, and as a result, the effect is small, and a sufficient stabilizing effect after processing cannot be obtained. The cycloalkyl group in the present invention represents a group having one or more closed rings in which a plurality of carbon atoms are covalently bonded to each other. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. In R ⁶ , the number of carbon atoms forming a ring may be three or more, but is more preferably 5 or 6. The carbon atom forming the ring may have a linear or branched alkyl chain having 1 to 5 carbon atoms as a substituent. Although the number of alkyl groups as a substituent in the cycloalkyl group is not particularly limited, the total number of carbon atoms is 5 to 5.
It is essential that it be 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable from the viewpoint of the stabilizing effect that all cycloalkyl groups are constituted by covalent bonds and do not include an unsaturated bond such as a double bond or a triple bond. The bonding site to X ² in R ⁶ may be either a carbon atom on the cycloalkyl group or an alkyl group present as a substituent of the cycloalkyl group. As specific examples of R ⁶ , the following general formulas (22) to (22)
(31);

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

Embedded image[In the above general formulas (22) to (31), Z is hydrogen
Straight-chain or branched saturated alkyl having 1 to 5 atoms and carbon atoms
Kill group, Y¹Represents one of the binding sites. However,
The total number of carbon atoms in the formula does not exceed 10,
Y out of Z¹And the number of binding sites is 1. ]
Groups and the like. Among them, preferred groups
And cyclopentyl, cyclohexyl, cyclohep
Tyl, cyclooctyl, cyclononyl, cyclode
Sil group, decahydronaphthyl group, norbornyl group, vol
And an isobornyl group. Most preferred
These are a cyclohexyl group and an isobornyl group. the above
Y in the general formula (6)¹Is a -O- group or a -NH- group
More preferred is an -O- group. Polymerizable monomer component
The minute (C2) is selected from the group represented by the general formula (6).
A mixture of one or more of^Five, R⁶, Y ¹
Are mixed with different groups, or all are
It may be one group. The most preferred combination is
R^FiveIs a methyl group, and R⁶Is a cyclohexyl group,
Y¹Is a -O- group. Polymerizable monomer component
As a preferred example as (C2), cyclopentylmeth
Tacrylate, cyclohexyl methacrylate, cyclo
Heptyl methacrylate, cyclooctyl methacrylate
G, cyclononyl methacrylate, cyclodecyl methacrylate
Relate, decahydronaphthyl methacrylate, norbo
Lunyl methacrylate, bornyl methacrylate, iso
Bornyl methacrylate, cyclopentyl acrylate
G, cyclohexyl acrylate, cycloheptyl
Relate, cyclooctyl acrylate, cyclononyl
Acrylate, cyclodecyl acrylate, decahydro
Naphthyl acrylate, norbornyl acrylate,
Lunyl acrylate, isobornyl acrylate, N-
Cyclopentyl-methacrylamide, N-cyclohexyl
Ru-methacrylamide, N-cycloheptyl-methacryl
Amide, N-cyclooctyl-methacrylamide, N
-Cyclononyl-methacrylamide, N-cyclodecyl
-Methacrylamide, N-decahydronaphthyl-methac
Rilamide, N-norbornyl-methacrylamide, N
-Bornyl-methacrylamide, N-isobornyl-meth
Tacrylamide, N-cyclopentyl-acrylamido
, N-cyclohexyl-acrylamide, N-cyclo
Heptyl-acrylamide, N-cyclooctyl-act
Lilamide, norbornyl methacrylate, norborny
Ruacrylate, N-norbornyl-methacrylami
, N-norbornyl-acrylamide, N-cyclono
Nyl-acrylamide, N-cyclodecyl-acrylia
Mid, N-decahydronaphthyl-acrylamide, N-
Norbornyl-acrylamide, N-bornyl-acryl
And N-isobornyl-acrylamide.
It is. Particularly preferred examples include cyclohexyl methacrylate.
Relate, cyclohexyl acrylate, isobornyl
Methacrylate, isobornyl acrylate, and the like.
The most preferred example is cyclohexyl methacrylate
is there.

In claim 3 of the present invention, the most preferable combination of the polymerizable hindered amine compound monomer component (A3) and the polymerizable monomer component (C2) is
2,2,6,6-tetramethyl-4-piperidyl methacrylate and cyclohexyl methacrylate.

The hindered amine compound according to claim 4 of the present invention comprises one or more polymerizable hindered amine compound monomer components (A4) selected from the group represented by the general formula (7), A hindered amine compound obtained by copolymerizing, as an essential component, one or a mixture of two or more polymerizable monomer components (D1) selected from the group represented by the formula (8); ) And the weight fraction of component (D1) are between 80 and 100% by weight, and the ratio of the weight fraction of component (A4) to the weight fraction of component (D1) is between 0.3 and It is necessary to satisfy both of 2.3 and 2.3. The weight fraction of each component is represented by a ratio of the total weight derived from each component to the weight of the hindered amine compound. To determine the weight of each component in the hindered amine compound,
Any known method for analyzing a polymer can be used. Examples of quantification include, but are not limited to, quantification of each component by 1H-NMR, quantification of a hindered amine component by neutralization titration, and the like. When it is difficult to determine the amount from the hindered amine compound, the weight% of the charged components can be used instead. If the sum of the weight fractions of the component (A4) and the component (D1) is less than 80% by weight, the stability before and after various types of processing cannot be well-balanced. More preferably, it is in the range of 95 to 100% by weight. The component (A) relative to the weight fraction of the component (D1)
If the ratio of the weight fraction of 4) is smaller than 0.3, the stabilizing effect before processing becomes small, and if the stabilizing effect is to be sufficiently obtained, the compounding amount has to be increased, which is economical. Is also disadvantageous. On the other hand, when the ratio is larger than 2.3, the stabilizing effect before processing is sufficiently obtained, but the stabilizing effect after various types of processing is not obtained. Especially, it is especially preferable that it exists in the range of 0.7-1.6.

R ⁷ in the general formula (7) is a hydrogen atom or a methyl group, and more preferably a methyl group. R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 10 carbon atoms.
Of these, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is most preferable in terms of a stabilizing effect. X ² in the general formula (7) is a —O— group or a —NH— group, more preferably —O—.
-A group. The polymerizable hindered amine compound monomer component (A4) is one or a mixture of two or more selected from the group represented by the general formula (7), and each of R ⁷ , R ⁸ , and X ² is Although different groups may be mixed or all may be a single group, it is more preferable that they are all a single group. The most preferred combination is where R ⁷ is a methyl group, R ⁸ is a hydrogen atom, and X ² is a —O— group. Polymerizable hindered amine compound monomer component (A
Preferred examples of 4) include 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 2,2,6,6-
Tetramethyl-4-piperidyl acrylate, 1,2,2
2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, N- (2,2,6,6-tetramethyl-4-piperidyl) -methacryl Amide, N- (1,
2,2,6,6-pentamethyl-4-piperidyl) -methacrylamide, N- (2,2,6,6-tetramethyl-4-piperidyl) -acrylamide, N- (1,2,2
2,6,6-pentamethyl-4-piperidyl) -acrylamide. Among them, particularly preferred is 2,
2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4
-Piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate. Most preferred is 2,2,6,6-tetramethyl-4-piperidyl methacrylate. As the component (A4), compounds in the range of the compounds specified as described above can be used by mixing at an arbitrary composition ratio.
Most preferably, 6,6-tetramethyl-4-piperidyl methacrylate is used.

R ⁹ in the general formula (8) is a hydrogen atom or a methyl group, more preferably a methyl group. R ¹⁰ is
It is one or more monovalent organic groups selected from the group consisting of linear or branched saturated alkyl groups having 10 to 30 carbon atoms. When the carbon number of the organic group is small, the effect of each group is small, and when the carbon number is large, the number as the group is small, and as a result, the effect is small, and a sufficient stabilizing effect after processing cannot be obtained. Preferred examples of R10 include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl. Group, triacontyl group, isostearyl group and the like. More preferred examples include groups such as dodecyl, tetradecyl, hexadecyl and octadecyl. Y ² is —O— or —NH—, and more preferably —O—. The polymerizable monomer component (D1) is one or a mixture of two or more selected from the group represented by the general formula (8), and each of R ⁹ , R ¹⁰ , and Y ² is different. The groups may be mixed or all may be a single group, but all are preferably a single group. The most preferred combination is where R ⁹ is a methyl group, R ¹⁰ is an octadecyl group, and Y ² is a —O— group. Preferred examples of the polymerizable monomer component (D1) include dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, N-dodecyl methacrylamide, N- Tetradecyl methacrylamide, N-hexadecyl methacrylamide, N-octadecyl methacrylamide, N-dodecyl acrylamide, N
-Tetradecylacrylamide, N-hexadecylacrylamide, N-octadecylacrylamide, and the like.

In claim 4 of the present invention, the most preferable combination of the polymerizable hindered amine compound monomer component (A4) and the polymerizable monomer component (D1) is
2,2,6,6-tetramethyl-4-piperidyl methacrylate and stearyl methacrylate.

The hindered amine compound according to claims 3 and 4 of the present invention can be synthesized using the above-mentioned compound as a raw material. Within the scope of the present invention,
Any known polymerizable monomer outside the scope of the present invention may be copolymerized at the same time as long as the effect is not impaired. In addition, a known chain regulator may be added as needed at the time of the polymerization reaction. The polymerization reaction can be performed by any known method, but among them, a radical polymerization method is preferable, and furthermore, since the reaction is simple and easy to control, the raw material is prepared in a solvent in the presence of a radical polymerization initiator. The solution polymerization method of reacting is preferred. The polymerization solvent used is, for example, a hydrocarbon-based solvent such as toluene, benzene, or xylene, an ester-based solvent such as ethyl acetate or butyl acetate, a ketone-based solvent such as acetone or methyl ethyl ketone, methanol, ethanol, isopropanol, or n-butanol. Alcohol solvents, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphonamide, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc. Any solvent can be used as long as it does not react with radicals and dissolves the polymerizable monomer and the copolymer, such as an ether-based solvent.

As the polymerization initiator to be used, those used as any known polymerization initiator can be used. Among them, 2,2′-azobis (2-diaminopropane) dihydrochloride, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4
-Dimethylvaleronitrile), 4,4′-azobis (4
-Cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis [2- (2-imidazoline-2)
-Yl) propane] dihydrochloride, 2,2'-azobis [2
-(2-Imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-
Methyl-N- [1,1-bis (hydroxymethyl) -2
-Hydroxyethyl] propionamide {, 2,2'-
Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) methyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2 '-Azobisisobutylamide dihydrate, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 2,2'-azobis [N-
(2-propenyl) -2-methylpropionamide],
An azo-based polymerization initiator such as 2,2'-azobis (2,4,4-trimethylpentane) is preferred. The concentration of the polymerizable monomer at the time of polymerization preparation is not particularly limited.
Preferably it is between ７０70% by weight. A solvent can be added at any time as the reaction proceeds. The amount of the polymerization initiator to be added can be freely changed according to the desired degree of polymerization. Although not particularly limited, a range of 0.01 to 2% by weight based on the polymerizable monomer is appropriate. The polymerization initiator may be added to the system as it is, or may be added after being dissolved in a polymerization solvent. Further, it may be added at once or may be added in several times. If necessary, a known chain regulator may be added.

The reaction temperature is not particularly limited, but may be 50 to 1
00 ° C is preferred. The reaction time is not particularly limited,
Preferably, it is 24 hours. The amount of the unreacted polymerizable monomer in the polymer composition is not particularly limited, but is preferably 20% by weight or less based on the weight of the polymer. If the amount of the unreacted polymerizable monomer in the hindered amine compound is too large, the polymerizable monomer itself may cause deterioration and the stabilizing effect may be impaired. The obtained copolymer can be used as a solution as it is, or can be used after being purified by any method such as reprecipitation, evaporation of a solvent, and column chromatography. Although the molecular weight of the hindered amine compound in the present invention is not particularly limited,
Preferably it is between 500,000. If it is smaller than 1,000, the mobility in the resin increases, and bleed out may occur. If it is larger than 500000, the physical properties of the resin may be adversely affected, and the stabilizing effect may be inferior to the case where the molecular weight is small.
A more preferred molecular weight range is from 2000 to 20,000.
It is between 0. Those having an appropriate molecular weight can be used depending on the use and purpose. The molecular weight can be measured by a known method such as a gel permeation chromatography method, a light scattering method, and an osmotic pressure method.

The hindered amine compound in the present invention is a group in which all or a part of the hindered amino group is composed of an organic carboxylic acid, carbon dioxide, a phosphoric acid compound, a phosphoric acid ester compound, a phosphorous acid compound, and a phosphite compound. One or more compounds selected from the above may form a salt. All or part of the hindered amino group of the hindered amine compound is formed into a salt with the above compound, thereby adjusting the basicity and solubility of the hindered amine compound without impairing the stabilizing effect inherent to the hindered amine compound. be able to.

Examples of the organic carboxylic acid include those having 1 to 10 carbon atoms.
Is preferred, and a saturated carboxylic acid is preferred. Further, monocarboxylic acids are preferable to polycarboxylic acids. Specific examples include formic acid, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, acetoacetic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, naphthoacetic acid, phenyl Acetic acid and the like can be mentioned.

The phosphoric acid compound means phosphoric acid or a salt of phosphoric acid with a basic compound such as an amine or a metal ion. The phosphorous acid compound refers to phosphorous acid or a salt of phosphorous acid with a base compound such as an amine or a metal ion. As the phosphoric acid ester compound, a phosphoric acid monoester compound or diester compound is preferable, but a high molecular compound which partially has a phosphoric acid monoester or diester structure may be used. As the phosphite compound, a phosphite monoester compound or a diester compound is preferable, but a high molecular compound and a compound having a phosphite monoester or diester structure in part may be used. Good. The phosphate compound and the phosphite compound may be partially a salt with a base compound such as an amine or a metal ion.

The hindered amine compound in the present invention can be used as a stabilizer for any known resin. Examples of the resin include polyurethane, polyamide, polyester, polyolefin, polystyrene, and a mixture of these resins. The resin containing the hindered amine compound of the present invention can be molded by any known method and can be processed by any known method. The use of the resin composition is not particularly limited, and examples thereof include fibers, films, molded articles, foams, artificial comparisons, elastomers, sheets, paints, adhesives, and nonwoven fabrics. The resin composition containing the hindered amine compound of the present invention is particularly excellent in fiber use. Examples of the fiber include chemical fibers such as polyurethane, polyester, polyamide, acrylic, acetate, rayon, polynosic, cupra, vinylon, polyethylene, polypropylene, vinylidene, and polyvinyl chloride. The hindered amine compound of the present invention,
Among them, it is suitable for polyurethane resin and polyurethane fiber, and is most suitable for polyurethane fiber.

The polyurethane used in the present invention may be polyether, polyester, polycarbonate, etc.
Known polyurethanes can be mentioned. Such polyurethanes include polyisocyanates, polymer diols,
If desired, it can be obtained by reacting a low molecular polyfunctional active hydrogen compound. Examples of the polyisocyanate include 4,4′-diphenylmethane diisocyanate, 1,4
-Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
One or a mixture thereof such as xylylene diisocyanate can be used. Preferably, 4,4'-diphenylmethane diisocyanate is used. Polymer diol has a molecular weight of 6 having hydroxyl groups at both ends.
Examples of the substantially linear polymer of 00 to 7000 include polyether polyols such as polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol and polypentamethylene ether glycol, and copoly (tetramethylene neopentylene) ether diol. , Two or more carbon atoms such as copoly (tetramethylene / 2,2-dimethylbutylene) etherdiol, copoly (tetramethylene / 2,3-dimethylbutylene) etherdiol, and copoly (tetramethylene / 2,2-dimethylbutylene) etherdiol. Copolyether polyols containing alkylene groups of number 6 or less, adipic acid, sebacic acid, maleic acid, itaconic acid, azelaic acid, malonic acid, succinic acid, glutaric acid,
A mixture of one or more dibasic acids such as suberic acid, dodecanedicarboxylic acid, β-methyladipic acid, hexahydroterephthalic acid and ethylene glycol;
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol, neopentyl glycol, 1,
One of glycols such as 4-dimethylolcyclohexane
Any polyol such as a polyester polyol obtained from a kind or a mixture of two or more kinds, a polyether ester diol, a polylactone diol, and a polycarbonate diol can be used. As low molecular weight polyfunctional active hydrogen compounds, compounds having two or more active hydrogen groups in the molecule that can react with isocyanate groups (chain extenders)
Can be mentioned. Examples of the chain extender include polyamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminopropane, diethylenetriamine and triethylenetetramine, and polyols such as ethylene glycol and butanediol, One or two of hydrazide, polysemicarbazide, polyhydroxylamine, water, hydrazine, etc.
Mixtures of more than one species. In addition, a compound having only one active hydrogen group capable of reacting with an isocyanate group in the molecule can be used as a terminal terminator together with the chain extender. Compounds having only one active hydrogen group in the molecule include dialkylamines such as diethylamine, dimethylamine, dibutylamine, and diethanolamine; ethylamine, n-propylamine, i-propylamine, n-butylamine, t-butylamine, and ethanol. Monoalkylamines such as amines, monools such as n-butanol, ethylenediamine and acetone 1: 1
Dehydration condensates of diamine and ketone such as reactants, N 2, N
-One or a mixture of two or more such as dimethylhydrazine. The polyurethane can be polymerized by a known method. For example, it can be polymerized by any method such as melt polymerization, solution polymerization and the like, and a combination thereof. In addition, an arbitrary method such as a one-shot method in which raw materials are mixed and reacted at once, or a prepolymer method in which a prepolymer is first formed and a chain is extended can be used. In addition, an appropriate amount of an organic acid such as acetic acid or p-toluenesulfonic acid, carbon dioxide, or the like may be added as a reaction rate regulator at an arbitrary stage during the polymerization reaction. These reaction modifiers are preferably added after the completion of the prepolymer reaction and before the completion of the chain extension reaction. These reaction rate regulators may be added as a mixture with a chain extender or a terminal terminator. The polymerized polyurethane can be molded by a known method and used for each purpose.

The compounding time of the hindered amine compound of the present invention is not particularly limited as long as it is up to the spinning step. If it does not affect the polymerization reaction of the resin or the resin to be a fiber, it is added to the raw material. You can also.
It can also be blended after the polymerization of the resin or the resin to be a fiber is completed. It is preferable to mix the resin after the completion of the polymerization of the resin and before the molding. Antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioether antioxidants; and ultraviolet light such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers Metal deactivators such as absorbents, dihydrazide derivative metal deactivators, oxalic acid derivative metal deactivators, magnesium stearate, higher fatty acid amides, higher fatty acid esters, polyorganosiloxanes, polytetrafluoro Anti-adhesives such as ethylene, inorganic fine particles such as titanium dioxide, magnesium oxide, zinc oxide, hydrotalcite, barium sulfate, magnesium silicate, calcium silicate, and other known additions such as flame retardants and fungicides It can also be mixed with an agent and added. In the case of spinning by a melting method when compounding the fibers, the hindered amine compound of the present invention can be compounded by melt-kneading the raw material resin.
When spinning is performed by a wet or dry method, the hindered amine compound of the present invention can be mixed with the spinning dope by mixing it alone or as a solution. The spinning device and spinning conditions used during spinning are not particularly limited,
Any known method can be selected depending on the resin composition, application, purpose, yarn properties, and the like. The hindered amine compounds of the present invention are particularly suitable as stabilizers for fibers, especially polyurethane fibers. Further, among the polyurethane fibers, the polyurethane fiber is particularly suitable for a polyurethane fiber produced from a polyurethane solution by a dry spinning method or a wet spinning method.

The hindered amine compound of the present invention can be added in an amount sufficient to exert a stabilizing action, depending on the type and use of the resin or fiber. Although not particularly limited, it is preferably 0.05 to 10% by weight based on the weight of the fiber. In the case of polyurethane fibers, it is particularly preferred that it is between 1 and 5% by weight.

It is more preferable to use a phosphite compound in addition to the hindered amine compound of the present invention since the yellowing resistance of the resin can be further improved. As the phosphite compound, any known compound can be used. As a specific example, tetrakis (2,4-di-t-butylphenyl)-
4,4'-biphenylenephosphonite, tris (nonylphenyl) phosphite, tris (2,4-di-t
-Butylphenyl) phosphite, distearylpentaerythritol diphosphite, di (2,4-di-t
-Butylphenyl) -pentaerythryl diphosphite, di (2,6-di-t-butyl-4-methylphenyl) -pentaerythryl diphosphite, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-ditridecyl) phosphite, cyclic neopentanetetrayl (octadecyl phosphite), tris (mono and / or dinonyl phenyl) phosphite , Diisodecylpentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythrite Diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl diphosphite And tetraphenyl dipropylene glycol diphosphite. Of these, hydrogenated bisphenol A / pentaerythritol phosphite polymer and hydrogenated bisphenol A phosphite polymer are preferred. The amount of the phosphite compound is preferably in the range of 0.1 to 2% by weight. Also,
The amount of the phosphite compound is more preferably in the range of 20 to 300% based on the amount of the hindered amine compound.

[0066]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to the scope of these examples. Parts and% in the examples represent parts by weight and% by weight, respectively. (Dyeing Model Processing Method) The tubular knitted fabric for evaluation is treated in hot water at 95 ° C. for 1 minute, and then treated in air at 190 ° C. for 60 seconds. Thereafter, about 7 g of the tubular knitted fabric was put together with a 20-fold dye model solution in a sealed container at 98 ° C. for 30 times by weight.
Process for a minute. The dyeing model solution was 0.5 g of New Pont TS100 (Nichika Chemical) as a dyeing aid in 1 liter of pure water,
A solution prepared by dissolving 0.5 g of acetic acid and 0.25 g of sodium acetate is used. Thereafter, the tubular knitted fabric is washed with water, dried, and treated in air at 180 ° C. for 60 seconds. The (NO _x discoloration test) Evaluation for cylindrical knitted fabric of approximately 1g, permeator PD-1-B The dried air containing NO ₂ of 200ppm generated using (manufactured Gastec) of 500 ml / min Exposure is for 1.5 hours in a closed container which is continuously run at a flow rate. After exposure, JIS-L08
Thoroughly washed with the buffered urea solution described in 55, then with pure water,
Dry under a nitrogen stream for 24 hours.
Hu using 500MC-88 (Tokyo Denshoku Co., Ltd.)
The b value in the Lab color system of nter is measured for eight knitted tubular knitted fabrics. The greater the b value, the greater the discoloration. (Chlorine embrittlement test) The tenacity (g) of the polyurethane fiber obtained by knitting the sample tubular knitted fabric before chlorination is measured. An effective chlorine concentration of 3 ppm having a pH of 7.5 was prepared using a commercially available aqueous sodium hypochlorite solution.
And then continuously treated with chlorine water at 25 ° C. for 10 hours, washed with pure water, and dried under a nitrogen stream for 24 hours. The tenacity (g) of the polyurethane fiber obtained by unknitting the tubular knitted fabric after the chlorination treatment was measured, and the strength retention ratio with respect to the strength of the polyurethane fiber obtained by unknitting the tubular knitted fabric before the chlorination treatment ( %).

(Synthesis Example 1): Synthesis of Hindered Amine Compound 2,2,6,6
60 parts of tetramethyl-4-piperidyl methacrylate (ADEKA STAB LA-87 / Asahi Denka Kogyo Co., Ltd.), 40 parts of cyclohexyl methacrylate, and 213 parts of N, N-dimethylacetamide were taken and dissolved by stirring.
The flask was heated in an oil bath with stirring to 60 ° C. while bubbling nitrogen through. After reaching 60 ° C,
2,2'-azobis (isobutyronitrile) (AIB
N) 0.8 part was added. The reaction was maintained at 60 ° C. while stirring as it was. Five hours after the initial addition of AIBN, an additional 0.2 parts of AIBN was added. 6 more reactions
After continuing at 0 ° C. for 15 hours, the reaction was terminated by cooling to room temperature to obtain a hindered amine compound solution. The solution viscosity measured with an E-type viscometer at 30 ° C. using a rotor having a cone angle of 3 ° and a radius of 14 mm was 15 poise. The unreacted polymerizable monomer in the solution was quantified by gas chromatography and found to be 4% by weight based on the weight of the charged polymerizable monomer. The number average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent and a refractometer as a detector is 2700.
Met. The resulting hindered amine compound ¹ H-
When the NMR spectrum was measured at 50 ° C. using a 1: 1 mixture of DMSO-d ₆ and CDCl ₃ as a solvent, the proton of the methine carbon of the piperidyl group and the proton of the methine carbon of the cyclohexyl group were 5.0, 4,. 6
ppm, and the integration ratio was 52:48. This integral ratio is 2,2,2 in the hindered amine compound.
Since it is considered to be the molar ratio of the unit derived from 6,6-tetramethyl-4-piperidyl methacrylate to the unit derived from cyclohexyl methacrylate, the weight fraction of each was calculated to be 60,40% by weight. It was consistent with the value obtained from the quantity.

(Synthesis Example 2) As the polymerizable monomer,
65 parts of 2,6,6-tetramethyl-4-piperidyl methacrylate and 35 parts of cyclohexyl methacrylate
A hindered amine compound was obtained in the same manner as in Synthesis Example 1 except that all parts were used.

(Synthesis Example 3) As the polymerizable monomer, 2,
45 parts of 2,6,6-tetramethyl-4-piperidyl methacrylate and 55 parts of cyclohexyl methacrylate
A hindered amine compound was obtained in the same manner as in Synthesis Example 1 except that all parts were used.

(Synthesis Example 4) As the polymerizable monomer,
40 parts of 2,6,6-tetramethyl-4-piperidyl methacrylate and 45 parts of cyclohexyl methacrylate
Parts, and 15 parts of hydroxyethyl methacrylate were used in the same manner as in Synthesis Example 1 to obtain a hindered amine compound.

(Synthesis Example 5) As the polymerizable monomer,
Except that 60 parts of 2,6,6-tetramethyl-4-piperidyl methacrylate and 40 parts of stearyl methacrylate were used, respectively,
A hindered amine compound was obtained.

(Synthesis Example 6) After polymerizing a hindered amine compound in the same manner as in Synthesis Example 1, 5.3 parts of acetic acid was added and mixed well to obtain a hindered amine compound.

(Comparative Synthesis Example 1) As a polymerizable monomer,
A hindered amine compound was obtained in the same manner as in Synthesis Example 1, except that 80 parts of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 20 parts of cyclohexyl methacrylate were used.

(Comparative Synthesis Example 2) As a polymerizable monomer,
A hindered amine compound was obtained in the same manner as in Synthesis Example 1, except that 20 parts of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 80 parts of cyclohexyl methacrylate were used.

(Comparative Synthesis Example 3) As a polymerizable monomer,
A hindered amine compound was obtained in the same manner as in Synthesis Example 1 except that 50 parts of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 50 parts of methyl methacrylate were used.

(Comparative Synthesis Example 4) As a polymerizable monomer,
40 parts of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and 2 parts of cyclohexyl methacrylate
A hindered amine compound was obtained in the same manner as in Synthesis Example 1 except that 0 parts and 30 parts of hydroxyethyl methacrylate were used.

(Measurement of solubility of hindered amine compound in acidic solution) The hindered amine compound solutions obtained in the above Synthesis Examples 1 to 5 and Comparative Examples 1 to 4 were dropped into pure water to reprecipitate the hindered amine compound. The precipitate was filtered and dried under vacuum at 80 ° C. for 12 hours to obtain a hindered amine compound. The solubility of each of the obtained hindered amine compounds in an acidic solution was measured according to the method described in the text. Methanol was used as the solvent for the titration.

(Example 1) (Production of polyurethane solution) 175.37 parts of polytetramethylene ether glycol having a number average molecular weight of 1800 and 4,4'-diphenylmethane diisocyanate 38.9
Two parts of the mixture were reacted at 80 ° C. for 3 hours under a stream of N 2 to obtain a prepolymer having isocyanate groups at both ends. After cooling the prepolymer to 40 ° C., 308.36 parts of N, N-dimethylacetamide was added and dissolved, and further cooled to 10 ° C. 3.58 parts of ethylenediamine and 0.46 parts of diethylamine were combined with N, N-dimethylacetamide.
The solution dissolved in 86 parts was added at a time to the prepolymer solution with high speed stirring and mixed to complete the reaction. The viscosity at 30 ° C. of this solution was 2000 poise.
To this solution, 13.42 parts of the hindered amine compound solution obtained in Synthesis Example 1 above, and 1,3,5 as an antioxidant
-Tris (4-tert-butyl-3-hydroxy-2,6-
2.15 parts of dimethylbenzyl isocyanurate) (Cyanox 1790 / Nippon Cyanamid), and 2-[(2-hydroxy-3,5-di-t-amyl) phenyl] benzotriazole (KEMISOR) as an ultraviolet absorber
(B74 / Chempro Chemical Co., Ltd.) (1.08 parts) and 0.69 part of magnesium stearate as an antiadhesive were added and mixed by stirring to obtain a polyurethane solution. (Production of polyurethane fiber and preparation of sample for evaluation) After defoaming the polyurethane solution, the polyurethane solution was extruded from a die having a hole diameter of 0.3 mm and 4 holes into a spinning cylinder in which air heated to 230 ° C. was flowed, and the oil agent was removed. 5% by weight
Winding was performed at 00 m / min to obtain a polyurethane fiber of 44 dtex. Course 108 / i consisting of polyurethane fiber only, using a single mouth knitting machine (manufactured by Koike Seisakusho)
n, a 178 / in wale cylindrical knitted fabric was prepared and used as a sample for evaluation.

(Examples 2 to 5) Instead of 13.42 parts of the hindered amine compound solution obtained in Synthesis Example 1, 13.42 parts of the hindered amine compound solution obtained in Synthesis Examples 2 to 5 were used as the hindered amine compound. Except for using it, a tubular knitted fabric for evaluation was prepared in the same manner as in Example 1. Examples using the hindered amine compounds obtained in Synthesis Examples 2 to 5 are Examples 2 to 5, respectively.

(Example 6) As the hindered amine compound, the hindered amine compound solution 1 obtained in Synthesis Example 1 was used.
A tubular knitted fabric for evaluation was prepared in the same manner as in Example 1 except that 14.13 parts of the hindered amine compound solution obtained in Synthesis Example 6 was used instead of 3.42 parts.

Example 7 1,3,5-Tris (4-t
-Butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate) instead of 2.15 parts, hydrogenated bisphenol A / pentaerythritol phosphite polymer (JPH-3800 / Johoku Chemical Co., Ltd.)
A knitted fabric for evaluation was prepared in the same manner as in Example 1 except that 15 parts were used.

(Comparative Examples 1 to 4) As the hindered amine compound, 13.42 parts of the hindered amine compound solution obtained in Comparative Synthesis Examples 1 to 4 was replaced with 13.42 parts of the hindered amine compound solution obtained in Synthesis Example 1. Except for using each, a tubular knitted fabric for evaluation was prepared in the same manner as in Example 1. Comparative Examples using each hindered amine compound obtained in Comparative Synthesis Examples 1 to 4 are Comparative Examples 1 to 4, respectively.
It is.

(Comparative Example 5) As the hindered amine compound, the hindered amine compound solution 1 obtained in Synthesis Example 1 was used.
Instead of 3.42 parts, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3 ,
9- (2,4,8,10-tetraoxaspiro [5,
5] Undecane) A tubular knitted fabric for evaluation was prepared in the same manner as in Example 1 except that 4.30 parts of a condensate with diethanol (ADK STAB LA-68LD / Asahi Denka Kogyo Co., Ltd.) was added.

Comparative Example 6 The hindered amine compound solution 1 obtained in Synthesis Example 1 was used as the hindered amine compound.
Instead of 3.42 parts, a condensate of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol (ADK STAB LA-57 / Asahi Denka Kogyo Co., Ltd.) A tubular knitted fabric for evaluation was prepared in the same manner as in Example 1 except that 4.30 parts were added.

(Comparative Example 7) Instead of the hindered amine compound, a known discoloration inhibitor, 4-ethyl-2,6-
Dimethyl-azaheptanediol and methylene-bis (4
Polyaddition products of -cyclohexyl isocyanate) 4.
Except for adding 30 parts, a tubular knitted fabric for evaluation was prepared in the same manner as in Examples 1 to 5. A part of the created tubular knitted fabric for evaluation was subjected to a dyeing model process as an example of a secondary process. Various tests were performed on the untreated and treated tubular knitted fabrics to evaluate the stabilizing effect. Table 1 shows the structural parameters obtained from the chemical structure and the results of various tests before and after the dyeing processing model processing as an example of processing for the polyurethane fiber tubular knitted fabrics obtained in the examples and comparative examples. Polyurethane fibers blended with a hindered amine compound within the scope of the present invention have a smaller NO _x discoloration property after dyeing model processing than polyurethane fibers blended with a hindered amine compound other than the present invention, and even after processing. Stabilized and excellent. Further, the polyurethane fiber containing a hindered amine compound within the scope of the present invention has a smaller NO _x discoloration property especially before and after processing than the polyurethane fiber containing a tertiary amine derivative which is a known stabilizer. In addition, the decrease in strength due to chlorine water is extremely small, and it can be said that this is an excellent fiber which has never been seen before.

[0086]

[Table 1]

[0087]

The resin or fiber containing the hindered amine compound according to the present invention may lose the stabilizing effect after secondary processing such as dyeing, like the resin or fiber containing the hindered amine compound outside the present invention. No, it is fully stabilized. Further, the hindered amine compound of the present invention exhibits a higher stabilizing effect than other known stabilizers. The hindered amine compound of the present invention is suitable as a stabilizer for fibers, films, molding resins, etc., and is particularly suitable for fibers, and among them,
Most suitable as stabilizer for polyurethane fibers.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/3432 C08K 5/3432 C08L 75/04 C08L 75/04 101/00 101/00 D01F 6/70 D01F 6/70 Z 6/94 6/94 A

Claims (12)

[Claims] 1. A molecule represented by the following general formula (1): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]
And a monovalent organic group represented by the following general formula (2): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or more monovalent and / or divalent organic groups (A) selected from the group consisting of divalent organic groups represented by
1) a hindered amine compound having at least one compound, wherein (a) the number of organic groups (A1) per kg of the hindered amine compound is at least 1.3 mol, and (b) the solubility in an acidic solution is 5.0 × 10 5 ^-3 eq /
hindered amine compound. 2. A compound represented by the following general formula (3) in one molecule: [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]
And a monovalent organic group represented by the following general formula (4): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or more monovalent and / or divalent organic groups (A) selected from the group consisting of divalent organic groups represented by
2) and one or more monovalent and / or divalent organics selected from the group consisting of a saturated cycloalkyl group having 5 to 10 carbon atoms and a saturated cycloalkylene group having 5 to 10 carbon atoms A compound having a group (C1), wherein
Weight fraction of the organic group (A2) and (C1) is the following formula (1) and _{(2); 40 ≦ W A2} + W C1 ≦ 70 Equation _{(1) 0.6 ≦ (W A2} ÷ W C1) ≦ 3 Formula (2) [In the above formula, W _A2 represents the weight percent of the organic group (A2), and W _C1 represents the weight percent of the organic group (C1). ] Hindered amine compound. 3. The following general formula (5): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom or a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
Represents any one of 0 alkoxy groups. X ¹ is a —O— group,
Or a -NH- group. 1 selected from the group represented by
A polymerizable hindered amine compound monomer component (A3) of a kind or a mixture of two or more kinds, and the following general formula (6): [In the above general formula, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a saturated cycloalkyl group having 5 to 10 carbon atoms. Y ¹ represents a —O— group or a —NH— group. ]
A hindered amine compound obtained by copolymerizing as an essential component one or a mixture of two or more polymerizable monomer components (C2) selected from the group represented by the following components: The weight fraction of A3) and the component (C2) is expressed by the following formulas (3) and (4): 80 ≦ (W _A3 + W _C2 ) ≦ 100 Formula (3) 0.5 ≦ (W _A3 ÷ W _C2 ) ≦ 2 0.3 Formula (4) [In the above formula, W _A3 is the weight% of the component (A3),
W _C2 represents the weight percentage of component (C2). ] Hindered amine compound. 4. The following general formula (7): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ represents a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
Represents any one of 0 alkoxy groups. X ² is a —O— group,
Or a -NH- group. 1 selected from the group represented by
A polymerizable hindered amine compound monomer component (A4) of a kind or a mixture of two or more kinds, and the following general formula (8): [In the above general formula, R ⁹ represents a hydrogen atom or a methyl group. R ¹⁰ represents a linear or branched saturated alkyl group having 10 to 30 carbon atoms. Y ² represents a —O— group or a —NH— group. A hindered amine compound obtained by copolymerizing, as an essential component, one or a mixture of two or more polymerizable monomer components (D1) selected from the group represented by:
The weight fraction of the component (A4) and the component (D1) in the hindered amine compound is expressed by the following formulas (5) and (6); 80 ≦ W _A4 + W _D1 ≦ 100 Formula (5) 0.3 ≦ (W _A4 ÷) W _D1 ) ≦ 2.3 Expression (6) [wherein W _A4 is the weight% of the component (A4),
W _D1 represents the weight percentage of component (D1). ] Hindered amine compound. 5. A method according to claim 1, wherein all or a part of the hindered amino groups in the hindered amine compound is selected from the group consisting of organic carboxylic acids, carbon dioxide, phosphoric acid, phosphoric ester compounds, phosphorous acid, and phosphite compounds. Seed or 2
The hindered amine compound according to any one of claims 1 to 4, which forms a salt with at least one kind of compound. 6. A resin composition comprising the hindered amine compound according to claim 1. 7. The resin composition according to claim 6, wherein the resin is a polyurethane. 8. The resin composition according to claim 6, comprising a phosphite compound. 9. A polyurethane fiber comprising the hindered amine compound according to claim 1. 10. The polyurethane fiber according to claim 9, further comprising a phosphite-based antioxidant. 11. A method for producing a polyurethane fiber, comprising blending the hindered amine compound according to any one of claims 1 to 5 with polyurethane and spinning. 12. A method for producing a polyurethane fiber, comprising blending the hindered amine compound and a phosphite compound according to claim 1 and spinning the mixture. .