JP2003113303A - Polyurethane composition and polyurethane elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane composition and a polyurethane elastic fiber stabilized against discoloration and deterioration with nitrogen oxide (NOX) and having high chlorine resistance. SOLUTION: The polyurethane composition and polyurethane elastic fiber comprise (a) a hindered amine compound, (b) a phenolic antioxidant, (c) a phosphorous ester antioxidant and (d) an inorganic chlorine deterioration inhibitor respectively having a specific structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to nitrogen oxides (NO
The present invention relates to a polyurethane composition which is stabilized against discoloration deterioration due to x) and has high chlorine resistance, and a polyurethane elastic fiber.

[0002]

Polyurethanes made from polyisocyanates, relatively low molecular weight polymeric diols and low molecular weight polyfunctional active hydrogen compounds have been found to have excellent mechanical properties, are easy to process, etc. It is used in a wide range of applications such as elastomers, paints, synthetic leather, and fibers. Among them, 4,4'-as polyisocyanate
A polyurethane obtained by using an aromatic isocyanate such as diphenylmethane diisocyanate is widely used as an elastic fiber because it has particularly excellent mechanical properties. However, polyurethanes obtained from aromatic isocyanates have the drawback that discoloration due to nitrogen oxides (NOx) is particularly significant. NOx is contained in combustion gas and exhaust gas, and even in an extremely small amount, it causes remarkable discoloration of polyurethane.

It is also known that when such elastic fibers mainly composed of segmented polyurethane are exposed to a chlorine water environment such as a detergent containing a chlorine-based bleaching agent, the physical properties of the polyurethane are significantly deteriorated. There is. Further, it is known that a swimsuit in which polyurethane elastic fibers are knitted causes physical properties of the fibers to deteriorate when exposed to water containing an active chlorine concentration of 0.5 to 3 ppm in a swimming pool for a long time.

A number of additives have been investigated to solve such problems of polyurethane. In order to suppress the discoloration deterioration of polyurethane due to NOx, the present applicant has already disclosed JP-A-2000-239519 and JP-A-2000-2.
In Japanese Patent No. 39520, it has been proposed to add a hindered amine compound having a specific structure, a phenolic antioxidant, and a phosphite antioxidant to polyurethane. The polyurethane composition stabilized by these has extremely excellent resistance to discoloration. However, the durability against chlorine water was not sufficient.

As an additive for improving the durability of polyurethane to chlorine, for example, Japanese Patent No. 1316 is used.
No. 267 is zinc oxide, No. 138561 is magnesium oxide and the like, JP-A No. 59-133248 is a hydrotalcite compound and JP-A No. 3-29236.
No. 4 and JP-A No. 5-78569 describe a hydrotalcite compound coated with a higher fatty acid or a silane coupling agent.

As described above, although a large number of stabilizers and additives are disclosed, a polyurethane composition satisfying both discoloration resistance to NOx and embrittlement resistance to chlorine,
Little polyurethane elastic fiber has been proposed.

[0007]

In view of such background of the prior art, the present invention provides a polyurethane composition or polyurethane elastic fiber which is sufficiently stabilized against discoloration deterioration due to NOx and has high chlorine resistance. It is something to do.

[0008]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that (a) a hindered amine compound, (b) a phenol-based antioxidant, and (c) a phosphite-based antioxidant in polyurethane. It was found that, in a polyurethane composition containing (d) an inorganic chlorine deterioration inhibitor, the stabilizing effect is enhanced against discoloration deterioration due to NOx and deterioration due to chlorine. Furthermore, when a specific compound is used as each of the hindered amine compound, the phenol-based antioxidant, the phosphite-based antioxidant, and the inorganic-based chlorine deterioration inhibitor, it has been found that a higher stabilizing effect can be obtained, It was completed. That is, the present invention is
For polyurethane, (a) a hindered amine compound, (b) a phenolic antioxidant, (c) a phosphite antioxidant, and (d) sodium, magnesium, aluminum, silicon, potassium, calcium,
A composition comprising an inorganic chlorine deterioration inhibitor containing at least one selected from zinc and barium, wherein the hindered amine compound has the following general formula (1) in one molecule:

[Chemical 10] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents 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. ]
Monovalent organic group represented by

And the following general formula (2):

[Chemical 11] [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 (D) selected from the group consisting of divalent organic groups represented by
A hindered amine compound having 1 or more of 1), wherein (e) the number of organic groups (D1) per 1 kg of the hindered amine compound is 1.3 mol or more, and (f) the solubility in an acidic solution is 5.0 × 10. ^-3 eq /
A polyurethane composition, which is a hindered amine compound having a l or less,

Further, with respect to polyurethane, (a) a hindered amine compound, (b) a phenol-based antioxidant, (c) a phosphite-based antioxidant, and (d)
A composition comprising an inorganic additive, wherein a hindered amine compound has the following general formula (3) in one molecule:

[Chemical 12] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² represents 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. ]
Monovalent organic group represented by

And the following general formula (4):

[Chemical 13] [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 (D) selected from the group consisting of divalent organic groups represented by
2) and one or more kinds of monovalent and / or divalent organic compounds 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 (F1), which is in the molecule:
The weight fraction of the organic groups (D2) and (F1) is represented by the following formulas (5) and (6); 40 ≦ W _D2 + W _F1 ≦ 70 Formula (5) 0.6 ≦ (W _D2 ÷ W _F1 ) ≦ 3 Formula (6) [In the above formula, W _D2 represents the weight% of the organic group (D2), and W _F1 represents the weight% of the organic group (F1). ] A polyurethane composition which is a hindered amine compound characterized by satisfying:

In addition, with respect to polyurethane, (a) a hindered amine compound, (b) a phenol-based antioxidant, (c) a phosphite-based antioxidant, and (d)
A composition comprising an inorganic chlorine deterioration inhibitor containing at least one selected from sodium, magnesium, aluminum, silicon, potassium, calcium, zinc and barium, wherein the hindered amine compound has the following general formula (5) );

[Chemical 14] [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 a carbon number of 1 to 1
Represents any of the alkoxy groups of 0. X ¹ is an —O— group,
Alternatively, it represents a -NH- group. ] Selected from the group represented by
Radically polymerizable hindered amine derivative monomer component (D3) of one kind or a mixture of two or more kinds, and

The following general formula (6);

[Chemical 15] [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 radical copolymerization with a radically polymerizable monomer component (F2) of one or a mixture of two or more selected from the group represented by: The weight fractions of the component (D3) and the component (F2) are the following formulas (7) and (8); 80 ≦ (W _D3 + W _F2 ) ≦ 100 Formula (7) 0.5 ≦ (W _D3 ÷ W _F2 ). ≤ 2.3 Formula (8) [In the above formula, W _D3 represents the weight% of the component (D3), and W _F2 represents the weight% of the component (F2). ] It is a polyurethane composition which is a hindered amine compound characterized by satisfy | filling, and (a) hindered amine compound and (b) phenolic antioxidant with respect to polyurethane,
A composition comprising (c) a phosphite-based antioxidant and (d) an inorganic additive,

The hindered amine compound has the following general formula (7);

[Chemical 16] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ⁸ represent either a hydrogen atom or a methyl group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. X and Y represent either -O- group or -NH- group. n and m are 0.35 ≦ (n / m) ≦ 1.
It represents a positive number such as 75. ] A polyurethane composition characterized by being a hindered amine compound having a structure represented by:

Further, the phenolic antioxidant in the polyurethane composition is represented by the following formula (8);

[Chemical 17] [In the above general formula, R ¹⁰ represents a group selected from a t-butyl group, a sec-butyl group, and a neopentyl group. ] Is a phenolic antioxidant represented by,

Further, the phosphite type antioxidant is
Formula (9) below;

[Chemical 18] A hydrogenated bisphenol A / pentaerythritol phosphite polymer having a structure represented by

The inorganic chlorine deterioration inhibitor is zeolite, magnesium oxide, calcium oxide, zinc oxide, magnesium oxide / zinc oxide solid solution, magnesium carbonate,
A metal compound containing at least one selected from hydrotalcite compounds, dolomite, and barium thiosulfate,

In addition, the content of (a) the hindered amine compound relative to polyurethane is 0.5 to 5% by weight,
(B) 0.1 to 2% by weight of a phenolic antioxidant, (c) 0.1 to 2% by weight of a phosphite antioxidant, and (d) an inorganic chlorine. A polyurethane composition, characterized in that the content of the deterioration inhibitor is 0.1 to 5% by weight,

In addition, all or part of the hindered amino groups in the hindered amine compound in the polyurethane composition are derived from organic carboxylic acid, carbon dioxide gas, phosphoric acid, phosphoric acid ester compound, phosphorous acid, phosphorous acid ester compound. A polyurethane composition characterized by forming a salt with one or more compounds selected from the group consisting of:

And a polyurethane elastic fiber obtained from the polyurethane composition.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In claim 1 of the present invention, the monovalent and / or divalent organic group (D1) has the general formula (1) above.
And one or more monovalent and / or divalent organic groups selected from the group consisting of monovalent organic groups represented by and divalent organic groups represented by the general formula (2). . Organic group (D
When 1) is a monovalent organic group, it is preferably bonded to another site in the compound at the 4-position of the piperidine ring in the general formula (1). R ¹ in the general formula (1) is either a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and among them, a hydrogen atom or a methyl group has a stabilizing effect. To more preferable. Further, when the organic group (D1) is a divalent organic group, it is preferable that the organic group (D1) is bonded to other sites in the compound at the 1-position and 4-position of the piperidine ring in the general formula (2). Preferred examples of the organic group (2) include the following general formulas (10) to (12);

[0022]

[Chemical 19]

[0023]

[Chemical 20]

[0024]

[Chemical 21] The group represented by can be mentioned. These organic groups may be composed of only one kind of organic group or a mixture of two or more kinds of organic groups as long as they are in the ranges defined 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 (D1) is an organic group represented by the general formula (10). Hindered amine compound 1kg
The number of organic groups (D1) per unit needs to be 1.3 mol or more. If the number of organic groups (D1) is smaller than this, the number of effective sites that contribute to stabilization in the compound decreases, and the stabilization effect is lost. Organic group (D
The smaller the number of 1), the larger the amount of the hindered amine compound added to obtain the same effect, which is economically disadvantageous. Hindered amine compound 1k
As the number of organic groups (D1) per g, 2.0 mol
The above is more preferable in terms of the 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 1 kg of Hindered Amine Compound) 0.0200 g of hindered amine compound is accurately weighed. When the hindered amine compound is in a solution state, it may be weighed after separating the hindered amine compound from the solution, or by weighing the solution amount such that the weight of the hindered amine compound becomes a predetermined amount as a solution. Good. As a method for separating the hindered amine compound, any known method such as reprecipitation, recrystallization, or evaporation of the solvent can be used. The weighed hindered amine compound is dissolved in 100 ml of the solvent. The solvent used is preferably one that dissolves the hindered amine compound well, does not exhibit basicity, and is miscible with water. Examples of such a solvent include lower alcohol solvents such as methanol, ethanol and propanol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and ether solvents such as tetrahydrofuran and dioxane. Can be mentioned. Among these solvents, those in which the hindered amine compound to be measured is soluble can be appropriately selected and used. The hindered amine compound solution was applied to a glass electrode (GE-101 / Hiranuma Sangyo Co., Ltd.) and a reference electrode (R) by using a potentiometric titration device (COMMITTE-980 / Hiranuma Sangyo Co., Ltd.) with a 1/100 N hydrochloric acid aqueous solution.
Neutralization titration using E-101 / Hiranuma Sangyo Co., Ltd.). The end point in the titration curve is the titer. The amount of base per 1 kg of the hindered amine compound is calculated by the following mathematical formula (9).
Can be sought by. B _A = V × F × 10 ⁻² ÷ 0.0200 Formula (9) [In the above formula, B _A is the base amount (eq / kg) per 1 kg of the hindered amine compound, and V is the titer (ml).
And F represents the factor of 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 measuring flask. (Measurement of solubility of hindered amine compound in acidic solution)
From the base amount per 1 kg of the hindered amine compound, the total base amount was 5.0 × 10 ^{−5 based on} the sample weight for the solubility test.
It is calculated by the following mathematical expression (10) so that it becomes mol. W _A = (5 × 10 ⁻² ) / B _A Formula (10) [wherein W _A is the weight of the hindered amine compound (g), B _A is the amount of base per 1 kg of the hindered amine compound (eq / kg), Represent each. ]

The weight of the hindered amine compound determined by the above mathematical formula (10) 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, cooled, and then opened. 3 ml of an ampoule solution filtered through a filter having a pore size of 0.45 μm and 1 ml of a 1/10 N sodium hydroxide aqueous solution are dissolved in 100 ml of a solvent. As the solvent to be used, the same solvent as used in the above-mentioned measurement of the amount of base can be used. The mixed solution is neutralized and titrated with a 1/100 N hydrochloric acid aqueous solution using a potentiometric titrator. As a blank, 3 ml of distilled water containing 3.6 × 10 ⁻³ g of acetic acid and 0.75 × 10 ⁻³ g of anhydrous sodium acetate and 1/10 N
1 ml of an aqueous solution of sodium hydroxide is 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 are all titrated is determined as the end point. The solubility of the hindered amine compound in the acidic solution is determined by the following numerical formula (11) from the titration amount of the sample solution and the blank solution as the amount of the base dissolved per 1 l (1 liter) of the acidic solution. S _A = (V _S −V _B ) / 300 Formula (11) [In the above formula, S _A is the solubility (eq / l) of the hindered amine compound in an acidic solution, and V _S is the sample solution 3 m.
1 represents the titer (ml), and V _B represents the titer (ml) of 3 ml of the blank solution. In the hindered amine compound according to the first aspect of the present invention, it is necessary that the solubility in an acidic solution obtained as described above is 5.0 × 10 ⁻³ eq / l or less.
Lower solubility is preferable, but 2.5 × 10 ^-3 eq / l
The following are more preferable properties.

The organic group (D2) of the hindered amine compound in claim 2 of the present invention is a monovalent organic group represented by the general formula (3) and a divalent organic group represented by the general formula (4). 1 or 2 or more 1 selected from the group consisting of groups
It is a valent 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 10 to 10 carbon atoms, of which a hydrogen atom or a methyl group is more preferable from the viewpoint of the stabilizing effect. Further, when the organic group (D2) is a divalent organic group, it is preferable that the organic group (D2) is bonded to other sites in the compound at the 1-position and 4-position of the piperidine ring in the general formula (4). Preferred examples of the organic group (D2) include groups represented by the general formulas (10) to (12). These organic groups may be composed of only one kind of organic group or a mixture of two or more kinds of organic groups as long as they are in the ranges defined 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 (D2) is an organic group represented by the general formula (10).

The organic group (F1) 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. It is one or more selected monovalent and / or divalent organic groups. When the number of carbon atoms in the organic group is small, the effect of each group is small, and when the number of carbon atoms is large, the number of groups is small, and as a result, the effect is small and a sufficient stabilizing effect after processing cannot be obtained. As the organic group (F1), a saturated cycloalkyl group having 5 to 15 carbon atoms is particularly preferable. The cycloalkyl group in the present invention is a group having one or more rings in which a plurality of carbon atoms are covalently bonded to each other and closed, and when two or more rings are present in the same group, each ring is May share some carbon atoms. Further, in the cycloalkyl group, the number of carbon atoms forming a ring may be 3 or more, but 5 or 6 is more preferable. 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 a substituent in the cycloalkyl group is not particularly limited, but it is essential that the total number of carbon atoms is 5 to 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable that all the cycloalkyl groups are composed of covalent bonds and do not contain unsaturated bonds such as double bonds and triple bonds from the viewpoint of the stabilizing effect. The organic groups (F1) may be the same group or may be composed of two or more kinds of groups. As examples of the organic group (F1), the following general formulas (13) to (22);

[0030]

[Chemical formula 22]

[0031]

[Chemical formula 23]

[0032]

[Chemical formula 24]

[0033]

[Chemical 25]

[0034]

[Chemical formula 26]

[0035]

[Chemical 27]

[0036]

[Chemical 28]

[0037]

[Chemical 29]

[0038]

[Chemical 30]

[0039]

[Chemical 31] [In the general formulas (13) to (22), Z is a hydrogen atom, a linear or branched saturated alkyl group having 1 to 5 carbon atoms,
It represents any of the binding sites with other sites in the hindered amine compound. However, the total number of carbon atoms in the above general formula does not exceed 10, and the number of binding sites of Z with other sites in the hindered amine compound is 1 or 2. ] The group etc. which are represented by these can be mentioned. Among them, preferred are cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group and the like, and most preferred are cyclohexyl group and isobornyl group. It is a base.

The hindered amine compound according to claim 2 of the present invention is a compound having one or more organic groups (D2) and (F1) in the molecule. Weight fraction of organic group (D2) and organic group (F1) in the hindered amine compound
It is necessary that the sum of the weight fractions of is in the range of 40 to 70% by weight. If it is less than the above range, the stabilizing effect becomes small and a large amount of stabilizer is required to be added, which is economically disadvantageous. If it is more than this, the stabilizing effect before various processing is relatively improved, but the stabilizing effect after various processing is lost. A more preferable range is 50 to 60% by weight. In addition, the ratio of the weight fraction of the organic group (D2) to the weight fraction of the organic group (F1) 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 processing is lost. A more preferable range is 1.0 to 2.5. The weight fraction of the organic groups (D2) and (F1) is expressed as the 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 repeating unit can be calculated.

The hindered amine compound in claim 3 of the present invention comprises one or more polymerizable hindered amine derivative monomer components (D3) selected from the group represented by the above general formula (5), and the above general compound. A hindered amine compound obtained by copolymerizing, as an essential component, the polymerizable monomer component (F2) of one kind or a mixture of two or more kinds selected from the group represented by the formula (6), and the component (D3 ) And the weight fraction of the component (F2) is between 80 and 100% by weight, and the component (D) relative to the weight fraction of the component (F2).
It is necessary that the ratio of the weight fractions of 3) is between 0.5 and 2.3. The weight fraction of each component is represented by the 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 polymers. Examples of the quantification include, but are not limited to, quantification of each component by ¹ H-NMR and quantification of the hindered amine component by neutralization titration. Further, when it is difficult to quantify from the hindered amine compound, the weight% of the charged various components may be used instead. When the sum of the weight fractions of the component (D3) and the component (F2) is less than 80% by weight, the stability before and after various processing cannot be well expressed in good balance. A more preferred range is 95 to 100% by weight. Further, the component (D3) relative to the weight fraction of the component (F2)
If the ratio of the weight fraction is less than 0.3, the stabilizing effect before processing becomes small, and if the stabilizing effect is to be obtained sufficiently, the compounding amount must be increased, which is economically disadvantageous. Becomes
On the other hand, when it is more than 2.3, the stabilizing effect before processing is sufficiently obtained, but the stabilizing effect after various 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 above 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.
And more preferably a hydrogen atom and a methyl group, and most preferably a hydrogen atom from the viewpoint of the stabilizing effect. X ¹ in the general formula (5) is an —O— group or a —NH— group, and more preferably —O.
-Group. The polymerizable hindered amine derivative monomer component (D3) is one kind or a mixture of two or more kinds selected from the group represented by the general formula (5), and each of R ³ , R ⁴ and X ¹ is Although different groups may be mixed and each may be a single group, it is more preferable that all are a single group. The most preferable combination is that R ³ is a methyl group, R ⁴ is a hydrogen atom, and X ¹
Is a -O- group. As a preferable example of the polymerizable hindered amine derivative monomer component (D3), 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
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 and 1,2,2,6,6-pentamethyl-4-piperidyl acrylate. Most preferred are 2, 2,
It is 6,6-tetramethyl-4-piperidyl methacrylate. As the component (D3), compounds within the range of the compounds defined as above can be mixed at an arbitrary composition ratio and used. Above all, it is preferable to use only 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

R ⁵ in the above 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 of the groups is small, and as a result, the effect becomes small and a sufficient stabilizing effect after processing cannot be obtained. The cycloalkyl group in the present invention is a group having one or more rings in which a plurality of carbon atoms are covalently bonded to each other and closed, and when two or more rings are present in the same group, each ring is May share some carbon atoms. Further, in R ⁶ , the number of carbon atoms forming a ring may be 3 or more, but 5 or 6 is more preferable. 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 a substituent in the cycloalkyl group is not particularly limited, but it is essential that the total number of carbon atoms is 5 to 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable that all the cycloalkyl groups are composed of covalent bonds and do not contain unsaturated bonds such as double bonds and triple bonds from the viewpoint of the stabilizing effect. The bonding site with X ² in R ⁶ may be either a carbon atom on the cycloalkyl group or an alkyl group existing as a substituent of the cycloalkyl group. As specific examples of R ⁶ , the following general formulas (23) to (32);

[0044]

[Chemical 32]

[0045]

[Chemical 33]

[0046]

[Chemical 34]

[0047]

[Chemical 35]

[0048]

[Chemical 36]

[0049]

[Chemical 37]

[0050]

[Chemical 38]

[0051]

[Chemical Formula 39]

[0052]

[Chemical 40]

[0053]

[Chemical 41] [In the general formulas (23) to (32), Z is hydrogen.
Atoms, straight-chain or branched saturated alkyl having 1 to 5 carbon atoms
Kill group, Y¹Represents any of the binding sites for and. However,
The total number of carbon atoms in the above general formula exceeds 10.
Not, Y out of Z¹The number of binding sites for and is one. ]
And the like. Above all
Examples of groups include cyclopentyl, cyclohexyl, and
Cloheptyl group, cyclooctyl group, cyclononyl group,
Cyclodecyl group, decahydronaphthyl group, norbornyl
Group, a bornyl group, an isobornyl group and the like. Most
Also preferred are cyclohexyl group and isobornyl group.
It Y in the general formula (6) ¹Is an -O- group or -NH-
It is a group, More preferably, it is a -O- group. Polymerizable
The monomer component (F2) is a group represented by the above general formula (6).
One or a mixture of two or more selected from R^Five,
R⁶, Y¹Even if each of the
It may be a single group, but it may be a single group.
More preferable. The most preferable combination is R^FiveThe
Is a chill group, R⁶Is a cyclohexyl group, and Y¹But-
This is the case where it is an O-group. With a polymerizable monomer component (F2)
Cyclopentylmethacrylate
G, cyclohexyl methacrylate, cycloheptylmeth
Tacrylate, cyclooctyl methacrylate, cyclo
Nonyl methacrylate, cyclodecyl methacrylate,
Decahydronaphthyl methacrylate, norbornyl meta
Acrylate, bornyl methacrylate, isobornyl methacrylate
Tacrylate, cyclopentyl acrylate, cyclohexyl
Xyl acrylate, cycloheptyl acrylate,
Crooctyl acrylate, cyclononyl acrylate
Todo, cyclodecyl acrylate, decahydronaphthyla
Acrylate, norbornyl acrylate, bornylac
Relate, isobornyl acrylate, N-cyclopen
Cyl-methacrylamide, N-cyclohexyl-methac
Rylamide, N-cycloheptyl-methacrylamide,
N-cyclooctyl-methacrylamide, N-cyclono
Nyl-methacrylamide, N-cyclodecyl-methacrylate
Lamide, N-decahydronaphthyl-methacrylamide
De N-norbornyl-methacrylamide, N-bornyl
L-methacrylamido, N-isobornyl-methacryl
Amide, N-cyclopentyl-acrylamide, N-si
Chlohexyl-acrylamide, N-cycloheptyl-
Acrylamide, N-cyclooctyl-acrylic acid
De, norbornyl methacrylate, norbornyl acryl
Rate, N-norbornyl-methacrylamide, N-no
Rubornyl-acrylamide, N-cyclononyl-ac
Rylamide, N-cyclodecyl-acrylamide, N-
Decahydronaphthyl-acrylamide, N-norborni
L-acrylamide, N-bornyl-acrylamide,
N-isobornyl-acrylamide is mentioned. In particular
Preferred examples include cyclohexyl methacrylate,
Cyclohexyl acrylate, isobornyl methacrylate
And isobornyl acrylate, among which
A good example is cyclohexyl methacrylate.

In claim 3 of the present invention, the most preferable combination of the polymerizable hindered amine compound monomer component (D3) and the polymerizable monomer component (F2) is
2,2,6,6-tetramethylmethacrylate and cyclohexylmethacrylate.

General formula (7) in claim 4 of the present invention
R ⁷ and R ^{8 each} represent a hydrogen atom or a methyl group. Both are preferably the same group, and particularly preferably all are methyl groups. R ⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
Represents any of the 10 alkoxy groups. A hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. X and Y are -O- groups, or -NH
Represents any of the groups. Both X and Y are preferably the same group, and more preferably both are -O- groups. n and m represent the composition ratio of the respective constituent units in the hindered amine compound.
Is preferably a positive number such that 0.35 ≦ (n / m) ≦ 1.75, and further 0.70 ≦ (n / m).
It is more preferable that ≦ 1.40. The hindered amine compound represented by the general formula (7) can be synthesized from any known compound by any method. Examples of the hindered amine compound in the present invention 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 and the like, and one or more mixtures thereof, and cyclohexyl methacrylate, cyclohexyl acrylate, N-cyclohexyl-methacrylamide, N-cyclohexyl-acrylamide, N-cycloheptyl-acrylamide, N-cyclooctyl-acrylamide. It can be synthesized by using as a raw material a compound consisting of one kind or a mixture of two or more kinds selected from the group consisting of: As a raw material, 2, among others
2,6,6-Tetramethyl-4-piperidyl methacrylate and cyclohexyl methacrylate are preferred.

The hindered amine compound according to claim 3 or 4 of the present invention can be synthesized by using the above-mentioned compounds as raw materials. 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. Further, a known chain regulator may be added during the polymerization reaction, if necessary. The polymerization reaction can be carried out by any known method, but among them, the radical polymerization method is preferable, and moreover, since the reaction is simple and the reaction can be easily controlled, the raw material in a solvent in the presence of a radical polymerization initiator is used. A solution polymerization method of reacting is preferable. The polymerization solvent used is, for example, a hydrocarbon solvent such as toluene, benzene, or xylene, an ester solvent such as ethyl acetate or butyl acetate, a ketone solvent such as acetone or methyl ethyl ketone, methanol, ethanol, isopropanol, n-butanol, or the like. Alcohol solvents, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphonamide, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc. Any solvent can be used as long as it is a solvent that does not react with a radical and dissolves a monomer and a copolymer such as the ether 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),
2,2'-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-imidazolin-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'-azobisisobutyramide dihydrate, 2,2'-azobis [2- (hydroxymethyl)
Propionitrile], 2,2'-azobis [N- (2-
Propenyl) -2-methylpropionamide], 2,
Azo-based polymerization initiators such as 2'-azobis (2,4,4-trimethylpentane) are preferable. The monomer concentration during polymerization is not particularly limited, but is 20 to 70% by weight.
Is preferably between A solvent can be added at any time as the reaction progresses. The amount of the polymerization initiator added can be freely changed according to the desired degree of polymerization.
Although not particularly limited, the range of 0.01 to 2% by weight with respect to the monomer is suitable. The polymerization initiator may be added to the system as it is, or may be dissolved in a polymerization solvent and added. Also, it may be added at once or divided into several times. If necessary, a known chain regulator may be added. The reaction temperature is not particularly limited, but is preferably 50 to 100 ° C. The reaction time is not particularly limited, but is preferably 1 to 24 hours. The amount of unreacted monomer in the polymer composition is not particularly limited, but is 20% by weight based on the weight of the polymer.
The following is desirable. If the amount of unreacted monomer in the hindered amine compound is too large, the 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 an arbitrary method such as reprecipitation, evaporation of a solvent, or column chromatography. The molecular weight of the hindered amine compound in the present invention is not particularly limited, but 10
It is preferably between 00 and 500,000. 100
If it is less than 0, the mobility in the resin is increased and bleeding 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 as compared with the case where the molecular weight is small. A more preferable molecular weight range is 2000 to 200.
It is between 000. An appropriate molecular weight can be used depending on the use and purpose.

The hindered amine compound in the present invention is a group in which all or part of the hindered amino group is composed of organic carboxylic acid, carbon dioxide gas, phosphoric acid compound, phosphoric acid ester compound, phosphorous acid compound, phosphorous acid ester compound. A salt may be formed with one or more compounds selected from the above. By forming a salt with all or part of the hindered amine group of the hindered amine compound, a salt is formed with the compound to adjust the basicity and solubility of the hindered amine compound without impairing the stabilizing effect originally possessed by the hindered amine compound. be able to.

The organic carboxylic acid has 1 to 10 carbon atoms.
The organic carboxylic acid of 1 is preferable, and a saturated carboxylic acid is preferable. Also, 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 etc. can be mentioned.

The phosphoric acid compound refers to phosphoric acid and salts of phosphoric acid with basic compounds such as amines and metal ions. The phosphorous acid compound represents phosphorous acid or a salt of phosphorous acid and a basic compound such as an amine or a metal ion. The phosphoric acid ester compound is preferably a phosphoric acid monoester compound or a diester compound, but may be a polymer compound which is partially a phosphoric acid monoester or diester structure. As the phosphite compound, a phosphite monoester compound or a diester compound is preferable, but even a compound having a phosphite monoester or diester structure as a polymer compound Good. The phosphoric acid ester compound and the phosphorous acid ester compound may partially be a salt with a basic compound such as an amine or a metal ion.

As the hindered amine compound in the present invention, two or more kinds can be used at the same time as long as they are included in the above range. The content of the hindered amine is preferably 0.5 to 5% by weight with respect to polyurethane. If it is less than 0.5% by weight, the stabilizing effect cannot be obtained. If it is more than 5% by weight, the stabilizing effect does not improve so much, and rather it has a bad influence on the properties of polyurethane such as mechanical properties.

As the phenolic antioxidant, any known phenolic antioxidant can be used. Considering the solubility in solvent and the compatibility with polyurethane,
Appropriate compounds can be selected. Examples of phenolic antioxidants are pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5).
-Di-t-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-
Tris (4-t-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-tris (4-s
ec-Butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-tris (4-neopentyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 2,2′-methylenebis (4 -Methyl-6-t-butylphenol), 4,4'-butylidenebis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-) t-butyl-4-hydroxybenzyl) benzene, tris- (3,3
5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl] -2,4
8,10-tetraoxaspiro [5,5] undecane,
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di- t-Butyl-4-hydroxybenzylphosphonate-diethyl ester, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
-Isocyanurate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyl] hydrazine,
Examples thereof include polycondensates of p-chloromethylstyrene and p-cresol, polycondensates of p-chloromethylstyrene and divinylbenzene, and isobutylene reaction products of p-cresol and divinylbenzene polycondensates. Among them 1,
3,5-tris (4-t-butyl-3-hydroxy-
2,6-Dimethyl) isocyanuric acid, 1,3,5-Tris (4-sec-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-Tris (4-neopentyl-3- Hydroxy-2,6-dimethyl) isocyanuric acid is particularly preferred, and 1,3,5-tris (4-
Most preferred is t-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid. The phenolic antioxidant can be used by blending it with polyurethane in an amount such that deterioration can be sufficiently suppressed in actual use. Moreover, you may use together 2 or more types of phenolic antioxidants. The blending amount of the phenolic antioxidant is preferably 0.1 to 2% by weight with respect to the polyurethane.

As the phosphite type antioxidant,
Any known compound can be used. A suitable compound can be selected in consideration of solubility in a solvent, compatibility with polyurethane and the like. Examples of the phosphite-based antioxidant include 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) -pentaerythril diphosphite, di (2,6-di-t-butyl-
4-Methylphenyl) -pentaerythril diphosphite, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-t)
-Butylphenyl-ditridecyl) phosphite, cyclic neopentanetetrayl (octadecylphosphite), tris (mono and / or dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 2,2-methylenebis (4,6) -The-
t-butylphenyl) octylphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, hydrogenated bisphenol A / pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyl tetra (Tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4′-isopropylidene diphenyl diphosphite, tetraphenyl dipropylene glycol diphosphite and the like. Among them, hydrogenated bisphenol A / pentaerythritol phosphite polymer and hydrogenated bisphenol A phosphite polymer are preferable. The phosphite-based antioxidant can be used by blending with polyurethane in an amount such that deterioration can be sufficiently suppressed in actual use. Further, two or more kinds of phosphite type antioxidants may be used in combination. The blending amount of the phosphite-based antioxidant is preferably 0.1 to 2% by weight with respect to the polyurethane.

As the inorganic chlorine deterioration inhibitor in the present invention, a metal oxide containing at least one selected from sodium, magnesium, aluminum, silicon, potassium, calcium, zinc and barium, for example, zeolite, magnesium oxide, calcium oxide, Zinc oxide, magnesium oxide / zinc oxide solid solution, magnesium carbonate,
Examples thereof include hydrotalcite compounds, dolomite, barium thiosulfate, and the like. Among them, II in the periodic table
It is preferable to contain elements of the group, namely magnesium, calcium and zinc. These inorganic chlorine deterioration inhibitors may be used alone or in combination of two or more. The blending amount of the inorganic chlorine deterioration inhibitor is 0.
It is preferably between 1 and 5% by weight. Excessive compounding is not preferable because it adversely affects the physical properties of polyurethane.

The polyurethane composition of the present invention includes
Other additives may be added depending on the purpose. For example, UV absorbers such as benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, magnesium stearate, calcium stearate, higher fatty acid amides, higher fatty acid esters, higher alcohols, polyorganosiloxanes, and polyorganosiloxanes. Anti-adhesion agents such as tetrafluoroethylene, metal deactivators such as dihydrazide derivative-based metal deactivators, oxalic acid derivative-based metal deactivators, titanium dioxide, barium sulfate, magnesium silicate, calcium silicate Inorganic fine particles such as, a flame retardant, a fungicide, and a known additive such as a bluing agent may be blended in arbitrary amounts according to the purpose. These additives can also be added to the raw materials or during the polymerization reaction as long as they do not adversely affect the polymerization reaction of polyurethane.

Polyurethanes used in the present invention include polyether type, polyester type, polycarbonate type, etc.
Known polyurethane can be mentioned. Such polyurethanes include polyisocyanates, polymer diols,
If desired, it can be obtained by reacting a low-molecular polyfunctional active hydrogen compound.

As the polyisocyanate, for example, 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,
One or a mixture of 4'-dicyclohexylmethane diisocyanate and xylylene diisocyanate can be used. Preferred is 4,4'-diphenylmethane diisocyanate.

The polymer diol is a substantially linear polymer having hydroxyl groups at both ends and having a molecular weight of 600 to 7,000, and examples thereof include polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol and polypentamethylene ether glycol. Such as polyether polyol, copoly (tetramethylene neopentylene) ether diol, copoly (tetramethylene-2-methylbutylene) ether diol, copoly (tetramethylene / 2,3-dimethylbutylene) ether diol, copoly (tetramethylene. 2,2-dimethylbutylene) ether diol and other copolyether polyols containing two or more alkylene groups having 6 or less carbon atoms, adipic acid, sebacic acid,
One or a mixture of two or more dibasic acids such as maleic acid, itaconic acid, azelaic acid, malonic acid, succinic acid, glutaric acid, suberic acid, dodecanedicarboxylic acid, β-methyladipic acid and hexahydroterephthalic acid; Ethylene glycol, 1,2-propylene glycol, 1,4-
Polyester polyol obtained from one or a mixture of two or more glycols such as butanediol, 1,6-hexanediol, neopentyl glycol and 1,4-dimethylolcyclohexane, polyether ester diol, polylactone diol, polycarbonate Any polyol such as a diol can be used.

Examples of the low molecular weight polyfunctional active hydrogen compound include compounds having two or more active hydrogen groups capable of reacting with an isocyanate group in the molecule (chain extender).
As the chain extender, for example, ethylenediamine, 1,2-
Diaminopropane, 1,3-diaminopropane, 1,4
-Polyamines such as diaminopropane, diethylenetriamine and triethylenetetramine, polyols such as ethylene glycol and butanediol, polyhydrazides, polysemicarbazides, polyhydroxylamine,
One or a mixture of two or more of water, hydrazine and the like can be mentioned. Also, as a chain terminator together with a chain extender, only one active hydrogen group capable of reacting with an isocyanate group is present in the molecule.
It is also possible to use a compound having two compounds together. Examples of the compound 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. One or more of monoalkylamines such as amines, monools such as n-butanol, dehydration condensation products of diamines and ketones such as 1: 1 reaction products of ethylenediamine and acetone, N, N-dimethylhydrazine and the like. Mention may be made of mixtures.

Polyurethane can be polymerized by a known method. For example, it can be polymerized by any method such as melt polymerization and solution polymerization, and a combination thereof. In addition, any method such as a one-shot method in which the raw materials are mixed and reacted at once, or a prepolymer method in which a prepolymer is first formed and chain extension is performed can be employed. Further, as a reaction rate adjusting agent, an organic acid such as acetic acid or p-toluenesulfonic acid, carbon dioxide gas, or the like can be added in an appropriate amount at any 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. Further, 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.

A hindered amine compound in the present invention,
The method of blending the phenolic antioxidant, the phosphite ester antioxidant, and the inorganic chlorine deterioration inhibitor with the polyurethane is not particularly limited, and any known method can be used. Each may be blended alone, or may be blended with a mixture of several kinds of stabilizers including other additives in advance. Further, a part or all of the additives may be blended in the raw material in advance and polymerized, or may be blended during the polymerization reaction, as long as the polymerization reaction of the polyurethane is not affected. It may also be added after the polymerization of polyurethane. It is preferable to add various additives after the completion of the polymerization reaction of the polyurethane. Various additives can be blended with polyurethane by melt-kneading or by dissolving or dispersing in a solvent and adding. When the polyurethane is polymerized in a solution, it is preferable to add the additives in advance as a solution or dispersion. The method for producing a polyurethane elastic fiber of the present invention is particularly suitable for a dry spinning method or a wet spinning method using a polyurethane solution as a raw material.

[0071]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the scope of these examples. In addition, part and% in an Example represent a weight part and weight%, respectively.

(Dyeing Model Processing Method) The sample for evaluation is treated in hot water of 95 ° C. for 1 minute and then in air of 190 ° C. for 60 seconds. Then, about 7 g of the sample was weighed, and the dyeing model solution of 20 times was added to the sample in a closed container.
Treat for 30 minutes at 8 ° C. The dyeing model liquid is 1 liter of pure water and Newbon TS100 (Nichika Kagaku) as a dyeing aid.
What melt | dissolved 0.5 g, 0.5 g of acetic acid, and 0.25 g of sodium acetate is used. Then, the sample is washed with water and dried,
Treat in air at 0 ° C. for 60 seconds.

(NOx discoloration test) About 1 g of an evaluation sample was dried with 500 ml / min of dry air containing 200 ppm of NO ₂ generated by using a permeator PD-1-B (Gastech Co., Ltd.). Expose for 1.5 hours in a closed container with continuous flow. After exposure, J
The buffered urea solution described in IS-L0855, followed by thorough washing with pure water, drying under a nitrogen stream for 24 hours, and using a color meter TC1500MC-88 (Tokyo Denshoku Co., Ltd.) in Hunter's Lab color system. b value is 8
Measurement is performed on a pile of tubular knitted fabrics. The color change property (Δb) was determined by the following mathematical formula (12). Δb = b value after NOx treatment−b value before NOx treatment Equation (12) The smaller the Δb value, the smaller the discoloration and the better.

(Chlorine resistance evaluation test method) The evaluation sample was immersed in a water tank kept at an active chlorine concentration of 3 ppm, a pH of 7.5 and a water temperature of 30 ° C. for 72 hours. After the treated sample was washed with distilled water and air-dried, the knitted fabric was unknitted, and the tensile strength of the single yarn was measured using a tensile tester (RTM-250 manufactured by Orientec). The chlorine resistance (strength retention) was calculated by the following mathematical formula (13). Strength retention = (Strength after chlorination / Strength before chlorination) × 100 Formula (13) The higher the strength retention, the smaller the deterioration and the better.

[0075]

EXAMPLES (Synthesis Example 1) Synthesis of hindered amine compound In a 500 cc side-armed flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser, 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 with stirring in an oil bath to 60 ° C. with nitrogen bubbling. After reaching 60 ℃,
2,2'-Azobis (isobutyronitrile) (AIB
N) 0.8 part was added. While stirring as it was, the temperature was maintained at 60 ° C. for reaction. Five hours after the first addition of AIBN, 0.2 parts of AIBN was further 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 by 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. When the residual monomer in the solution was quantified by gas chromatography, it was 4% by weight based on the weight of the charged monomers. The polystyrene-reduced number average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent was 2,700. The ¹ H-NMR spectrum of the hindered amine compound obtained was analyzed by DMSO-d ₆ and CDC.
When a 1: 1 mixture of l ₃ was used as a solvent at 50 ° C., the proton of the methine carbon of the piperidyl group and the proton of the methine carbon of the cyclohexyl group were 5.0,
It was detected at 4.6 ppm and the integration ratio was 52:48.
This integral ratio is 2, in the hindered amine compound.
Since it is considered that it is the mol ratio of the units derived from 2,6,6-tetramethyl-4-piperidyl methacrylate and the units derived from cyclohexyl methacrylate, the weight fraction of each is calculated to be 60,40% by weight. , And was in agreement with the value obtained from the charged amount.

(Synthesis Example 2) A hindered amine compound solution was obtained by polymerizing a hindered amine compound in the same manner as in Synthesis Example 1 and then adding 5.3 parts of acetic acid and mixing them well.

(Comparative Synthesis Example 1) The amount of 2,2,6,6-tetramethyl-4-piperidyl methacrylate was 80 parts,
A hindered amine compound solution was obtained in the same manner as in (Synthesis Example 1) except that the amount of cyclohexyl methacrylate was changed to 20 parts.

(Comparative Synthesis Example 2) The amount of 2,2,6,6-tetramethyl-4-piperidyl methacrylate was 20 parts,
A hindered amine compound solution was obtained in the same manner as in (Synthesis Example 1) except that the amount of cyclohexyl methacrylate was changed to 80 parts.

(Measurement of Solubility of Hindered Amine Compound in Acidic Solution) The hindered amine compound solutions obtained in the above Synthesis Example 1 and Comparative Synthesis Examples 1 and 2 were dropped into pure water to reprecipitate the hindered amine compound. The precipitate was filtered and vacuum dried 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 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 were reacted at 80 ° C. for 3 hours under a N 2 stream 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 added to N, N-dimethylacetamide 146.
The solution dissolved in 86 parts was added all at once to the prepolymer solution that was being stirred at high speed, and mixed to complete the reaction. The viscosity of this solution at 30 ° C. 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-
Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate) (Cyanox 1
790 / Nippon cyanamide) 2.15 parts, 2- [2-hydroxy-3,5-di-t-amyl) phenyl] benzotriazole (KEMISORB) as an ultraviolet absorber
74 / Chemipro Kasei Co., Ltd.) 1.08 parts, hydrogenated bisphenol A / pentaerythritol phosphite polymer (JPH-3 as a phosphite type antioxidant.
800 / Johoku Chemical Industry Co., Ltd.) 2.15 parts, as a chlorine deterioration inhibitor, a hydrotalcite compound (Mg ₆ Al ₂ (OH))
₁₆ CO ₃ .4H ₂ O) 6.55 parts and magnesium stearate 0.69 parts as an anti-tacking agent were added and mixed with stirring to obtain a polyurethane solution. (Production of Polyurethane Elastic Fiber and Preparation of Sample for Evaluation) After defoaming the polyurethane solution, it is extruded from a spinneret having a hole diameter of 0.3 mm and a number of holes of 4 into a spinning cylinder in which air heated at 230 ° C. While adding 5% by weight to the fiber, 5
It was wound at 00 m / min to obtain a polyurethane elastic fiber of 44 decitex. This polyurethane elastic fiber is made of polyurethane elastic fiber only, using a single knitting machine (manufactured by Koike Seisakusho), course 108 / in, wale 178
A tubular knitted fabric of / in was prepared and used as a sample for evaluation.

Example 2 An evaluation sample was obtained in the same manner as in Example 1 except that 2.15 parts of a polycondensate of p-chloromethylstyrene and p-cresol was used as a phenolic antioxidant. It was

Example 3 All of the examples except that 2.15 parts of di (2,4-di-t-butylphenyl) -pentaerythril diphosphite were used as the phosphite type antioxidant. A sample for evaluation was obtained in the same manner as in 1.

Example 4 An evaluation sample was obtained in the same manner as in Example 1 except that 6.55 parts of magnesium oxide was used as a chlorine deterioration inhibitor.

Example 5 An evaluation sample was obtained in the same manner as in Example 1 except that 6.55 parts of magnesium carbonate was used as a chlorine deterioration inhibitor.

Example 6 5Mg as a chlorine deterioration inhibitor
Except for using _{O · 2Al 2 O 3 · 4H} 2 O6.55 parts, a sample for evaluation was obtained in the same manner as in Example 1.

Comparative Example 1 A sample for evaluation was obtained in the same manner as in Example 1 except that 13.42 parts of the hindered amine compound solution obtained in Comparative Synthesis Example 1 was added as a hindered amine compound.

Comparative Example 2 An evaluation sample was obtained in the same manner as in Example 1 except that 13.42 parts of the hindered amine compound solution obtained in Comparative Synthesis Example 2 was added as a hindered amine compound.

Comparative Example 3 An evaluation sample was obtained in the same manner as in Example 1 except that no chlorine deterioration inhibitor was added.

Comparative Example 4 An evaluation sample was obtained in the same manner as in Example 1 except that the hindered amine compound, the phosphite type antioxidant and the chlorine deterioration inhibitor were not added at all.

Table 1 shows the NOx discoloration resistance and chlorine resistance of the knitted fabrics not treated with the dyeing model and the knitted fabrics after the dyeing model processing for the evaluation samples obtained in the examples and the comparative examples. In addition, Table 2 shows the characteristics of the hindered amine compound of the present invention. It can be seen that the polyurethane fiber of the present invention is unlikely to be discolored and deteriorated by NOx and is not easily deteriorated by chlorine. Also, it is understood that these effects are not easily lost even after dyeing. On the other hand, when a hindered amine compound other than the present invention is used, the stabilizing effect before and after the dyeing process is small, or even if the hindered amine compound is well stabilized before the dyeing process, the stable process is lost after the dyeing process. You can see that they have been broken. Therefore,
The polyurethane composition and polyurethane fiber of the present invention,
It is excellent in that it shows good resistance to NOx discoloration and chlorine resistance, and that the stabilizing effect is retained even after post-processing such as dyeing.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

INDUSTRIAL APPLICABILITY The polyurethane composition of the present invention and the polyurethane fiber obtained from the polyurethane composition have nitrogen oxides (NOx).
It is sufficiently stabilized against discoloration and deterioration due to discoloration and has high stability against deterioration in a chlorine water environment.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D01F 6/94 D01F 6/94 A // D01F 6/70 6/70 ZF term (reference) 4J002 BG072 CK021 CK031 CK041 DE05 DE06 DE07 DE08 DE10 EJ017 EJ047 EN016 EU006 EU016 EU036 EW068 FD01 FD05 FD077 FD078 FD34 GK00 GK01 4L035 BB02 BB11 DD14 FF10 GG04 HK01 JJ05 JJ07 JJ08 JJ21 JJ21 JJ16 JJ16 JJ16 JJ16 JJ16 JJ16 JJ16 JJ20

Claims (8)

[Claims] 1. A polyurethane comprising (a) a hindered amine compound, (b) a phenolic antioxidant, and (c).
A phosphite type antioxidant and (d) sodium,
A composition comprising an inorganic chlorine deterioration inhibitor containing at least one selected from magnesium, aluminum, silicon, potassium, calcium, zinc and barium, wherein the hindered amine compound has the following general formula in one molecule: (1); [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents 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. ]
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 (D) selected from the group consisting of divalent organic groups represented by
A hindered amine compound having 1 or more of 1), wherein (e) the number of organic groups (D1) is 1.3 mol or more per 1 kg of the hindered amine compound, and (f) the solubility in an acidic solution is 5.0 × 10 5. ^-3 eq /
A polyurethane composition, which is a hindered amine compound having a ratio of 1 or less. 2. A polyurethane comprising: (a) a hindered amine compound; and (b) a phenolic antioxidant.
(C) A phosphite-based antioxidant and (d) an inorganic chlorine deterioration inhibitor containing at least one selected from sodium, magnesium, aluminum, silicon, potassium, calcium, zinc and barium. A hindered amine compound having 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 one 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 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 (D) selected from the group consisting of divalent organic groups represented by
2) and one or more monovalent and / or divalent organic compounds 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 (F1), which is in the molecule:
The weight fraction of the organic groups (D2) and (F1) is represented by the following formulas (1) and (2); 40 ≦ W _D2 + W _F1 ≦ 70 Formula (1) 0.6 ≦ (W _D2 ÷ W _F1 ) ≦ 3 Formula (2) [In the above formula, W _D2 represents the weight% of the organic group (D2), and W _F1 represents the weight% of the organic group (F1). ] The polyurethane composition characterized by being a hindered amine compound which satisfy | fills these. 3. A polyurethane containing (a) a hindered amine compound, and (b) a phenolic antioxidant.
(C) A phosphite-based antioxidant and (d) an inorganic chlorine deterioration inhibitor containing at least one selected from sodium, magnesium, aluminum, silicon, potassium, calcium, zinc and barium. A composition comprising a hindered amine compound represented by 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 a carbon number of 1 to 1
Represents any of the alkoxy groups of 0. X ¹ is an —O— group,
Alternatively, it represents a -NH- group. ] Selected from the group represented by
Radical polymerizable hindered amine derivative monomer component (D3) of one 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 radical copolymerization with a radical-polymerizable monomer component (F2) of a mixture of one kind or two or more kinds selected from the group represented by: component (D3) and the weight fraction of component (F2) is the following formula (3) and (4); 80 ≦ (W D3 + W F2) ≦ 100 equation _{(3) 0.5 ≦ (W D3} ÷ W F2) ≤ 2.3 Formula (4) [W _D3 represents the weight% of the component (D3), and W _F2 represents the weight% of the component (F2) in the above formula. ] The polyurethane composition characterized by being a hindered amine compound which satisfy | fills these. 4. A hindered amine compound has the following general formula (7): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ⁸ represent either a hydrogen atom or a methyl group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. X and Y represent either -O- group or -NH- group. n and m are 0.35 ≦ (n / m) ≦ 1.
It represents a positive number such as 75. ] The polyurethane composition of Claim 2 which is a structure represented by these. 5. A phenolic antioxidant is represented by the following general formula (8); [In the above general formula, R ¹⁰ represents a group selected from a t-butyl group, a sec-butyl group, and a neopentyl group. ] And a phosphite type antioxidant represented by the following formula (9); Is a hydrogenated bisphenol A / pentaerythritol phosphite polymer having a structure represented by, and the inorganic chlorine deterioration inhibitor is zeolite, magnesium oxide,
The metal compound containing at least one selected from calcium oxide, zinc oxide, magnesium oxide / zinc oxide solid solution, magnesium carbonate, hydrotalcite compounds, dolomite, and barium thiosulfate. Polyurethane composition. 6. A blending amount of (a) the hindered amine compound with respect to polyurethane is 0.5 to 5% by weight, and (b)
The amount of the phenolic antioxidant blended is 0.1 to 2% by weight,
(C) The compounding amount of the phosphite antioxidant is 0.1.
The polyurethane composition according to any one of claims 1 to 5, wherein the content of the inorganic chlorine deterioration inhibitor (d) is 0.1 to 5% by weight. 7. A hindered amino group in a hindered amine compound is wholly or partially selected from the group consisting of organic carboxylic acids, carbon dioxide, phosphoric acid, phosphoric acid ester compounds, phosphorous acid and phosphorous acid ester compounds. Seed or 2
The polyurethane composition according to any one of claims 1 to 6, which forms a salt with one or more compounds. 8. A polyurethane elastic fiber obtained from the polyurethane composition according to any one of claims 1 to 7.