JPS5951633B2 - Dense and supple sheet-like material - Google Patents

Description

[Detailed description of the invention] The present invention relates to a composite sheet-like product.

The present inventors have conventionally proposed artificial leather made of so-called polymer array fibers and a polyurethane elastic body having a specific structure, as described, for example, in Japanese Patent Publication No. 51-33601. The artificial leather obtained by this invention has many excellent features such as its excellent raised appearance, texture, easy care properties, pleochroism and fastness, lightness, and high processing yield, and is different from natural leather. It is known that it is widely popular as a slightly different clothing material. However, when such artificial leather is compared with natural leather, such as curved leather, which is considered to be particularly high-quality, it is still inferior in terms of fine structure and flexibility. From this point of view, in order to have a dense structure like a natural curve and to obtain flexibility, various studies were conducted regarding the constituent fibers and polyurethane elastic bodies, and the structure and interaction of their composites. However, it is extremely difficult to achieve both of these properties, and a dense structure becomes hard and highly repellent.
A supple texture could not be obtained.

On the other hand, those with a supple texture have a coarser structure and are inferior in smoothness, and for this reason, especially when they have naps, it is inevitable that they will be inferior in the appearance of the naps and the elegance of the chiyoke mark. Furthermore, the above-mentioned excellent artificial leather is worn or used for long periods of time as clothing and other secondary products, but during this time it is subjected to various treatments such as dry cleaning, washing, ironing, etc., and is exposed to UV rays, NOx gas, etc. In addition to being affected by chemical changes, such as discoloration and deterioration of strength,
It was inevitable that the initially excellent texture and touch of a secondary product would change over time.

Particularly in the case of high-grade suede, which requires an elegant nap, the appearance of the nap and the elegance of the so-called "york mark" are greatly influenced by the support for the nap, and the elegance changes as the support changes over time. It was inevitable that it would disappear. Of course, it is inevitable that natural or artificial fiber products will sooner or later experience quality changes such as changes in texture and fading.
There is a strong demand for artificial leather to maintain its excellent feel, touch, and in the case of suede-like appearance, to maintain its excellent napped appearance. The present inventors have developed various methods to improve the performance required for such conventional artificial leather (i.e., dense, supple and smooth, and with little change in texture and touch over time). For consideration from this perspective. We have been considering how to achieve this goal.

However, when trying to pursue the precise structure and supple texture and feel of high-quality natural leather,
It often has disadvantages such as poor surface smoothness, local deformation due to wear, and changes in texture and feel, making it unsuitable as a high-quality leather material.

Furthermore, the use of polyurethane elastic material used in conventional artificial leather was unsatisfactory in terms of deformation and change in texture due to wear over time. In other words, it is comparable to high-grade natural leather5
A material suitable for providing such high-quality artificial leather must satisfy these contradictory properties at the same time, and it has not yet been possible to find a material that satisfies these contradictory properties. In order to overcome these problems, the present inventors have considered the interaction between the fibers in artificial leather and the polyurethane elastic body, and the composition, properties, structure and application of the polyurethane elastic body when applied to a fiber sheet. As a result of intensive study on the law, the present invention was arrived at.

That is, an object of the present invention is to provide artificial leather that has a dense structure and a supple texture, and has excellent texture retention so that its suppleness is not lost even after long-term wear and use. It is in.

In addition, when the leather has excellent smoothness and napped appearance, it is an object of the present invention to provide an artificial leather that has an elegant napped appearance and has little change over time in the napped appearance. Another object of the present invention is to provide an artificial leather that exhibits good resistance to discoloration and fading even when exposed to ultraviolet rays, automobile exhaust gas, NOx gas, etc. due to long-term wear and use. The gist of the present invention is as follows.

That is, a polymer diol with a molecular weight of 800 or more is added to the fiber sheet,
A polyurethane elastomer obtained from an organic polyisocyanate, a chain extender, and optionally a terminal stopper, wherein 2 mol% or more of the chain extender and the end stopper have the formula [
A composite sheet material impregnated and/or coated with a polyurethane elastomer which is a hindered amine compound represented by [I]. [However, in the formula, R'' is a hydrogen atom, C, ~C,.

alkyl group, C2-Cl2 alkenyl group, C7-C
12 is an aralkyl group, -(R°O)n-H (where R° is a lower alkylene group and n is an integer of 1 to 50). R'' is a substituent selected from the group consisting of hydrogen and alkyl groups of C, ~Cl2. A substituent selected from the group consisting of a group substituted with one (R゜O)n-H or one (COR4COOR5O)m-H (however, R゜, n are as described above. R" is an organic dicarboxylic acid residue) group, R° is an organic diol residue, m is an integer of 1 to 15), R' is C
,~C,. lower alkyl group, R″, R° are the same or different alkyl groups of C, ~C, 2, or R″ and R° are bonded to C, ~C,. What forms the ring of. ]. The composite sheet obtained by the present invention has both properties of a dense structure and a supple texture, which were difficult to achieve when using conventional polyurethane elastomers, and has excellent smoothness. Moreover, the secondary product has excellent features that cannot be achieved with conventional artificial leather, such as being resistant to hardening or softening of the texture and excellent in texture retention when worn or used for a long period of time.

The above-mentioned excellent properties, which could not be achieved with conventional artificial leather, can only be achieved by combining a specific polyurethane elastomer and a fiber sheet made of specific fibers. This is difficult to predict based solely on the properties of the polyurethane elastic material itself. First, let's talk about the polyurethane elastic body.

A polyurethane elastomer made of a polymeric diol having a molecular weight of 800 or more, an organic polyisocyanate, and a glycol chain extender is produced, and the polyurethane is woven into fibers 1. It is already known to impregnate and/or coat fiber sheets with
It has been put into practical use with some artificial leathers. However, composite sheets made from such conventional glycol-based polyurethane elastomers tend to have a dense structure, but have a hard texture, lack flexibility, and are difficult to wear as secondary products. The material lost its shape, softened its texture, or hardened during use, and was not suitable for the purpose of the present invention. In addition, composite sheets using diamine-stretched polyurethane were unsatisfactory because they had too high rebound, were soft and lacked flexibility and density. Surprisingly, the present inventors found that a composite sheet made by combining fibers and a polyurethane elastomer made by introducing a specific hindered amine compound into polyurethane has a dense structure and is dense as described above. However, it has a supple texture, has excellent smoothness, and does not lose its suppleness even with long-term wear or use.Furthermore, if it has piloerection, it has an excellent appearance and has a They found that the diurnal variation 3 was small.

This cannot be predicted directly from the properties of the polyurethane elastomer alone, and its quality can only be determined by combining it with a fibrous material. Examples of improving light resistance by bonding a specific hindered amine compound 4 to polyurethane include, for example, JP-A-53-1294, 53-39385, 53-393.
95,5339396, etc., but there is no mention or suggestion of combinations with fiber sheets or sheet-like products as in the present invention, and there is no mention of the density, supple texture, or texture of such composite sheet-like products. The effect of improving retention was unexpected.

The polymeric diol constituting the polyurethane elastomer of the present invention has hydroxyl groups at both ends and has a molecular weight of 800 or more, preferably 800 to 4,000, preferably 7
These include polyester glycol, polyether glycol, polyether ester glycol, polyacetal glycol, polybutadiene glycol, etc., which have a melting point of 0°C or lower. Typical examples include polyethylene adipate, polypropylene adipate, polytetramethylene adipate, and polyhexane. methylene adipate,
Polycaprolactone glycol, poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, etc. or a mixture thereof can be used.

The organic polyisocyanate used in the present invention includes:
Phenyl diisocyanate, toluylene diisocyanate, diphenylmethane-4,4''-diisocyanate, diphenyldimethylmethane-4,4''-diisocyanate, naphthylene diisocyanate, diphenyl diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine Organic diisocyanates consisting of diisocyanate, isoborone diisocyanate, dicyclohexylmethane-4,4''-diisocyanate, synchhexyldimethylmethane-4,4''-diisocyanate, xylylene diisocyanate, etc., and mixtures thereof, and also polyhydroxy compounds with these organic diisocyanates. polyisocyanates containing isocyanate groups, such as those obtained by trimerization of organic diisocyanates, or polyisocyanates containing Biuret groups, such as those obtained by the method of German Patent Specification No. 1 101 394. be.

Preferred are organic diisocyanates, and more preferred are aromatic organic diisocyanates and alicyclic organic diisocyanates. Particularly preferred from the viewpoint of sheet material strength, rebound, and stain resistance are toluylene diisocyanate, diphenylmethane-4,4''-diisocyanate, diphenyldimethylmethane-4,4''-diisocyanate, naphthylene diisocyanate, and dicyclohexylmethane-4. , 4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate: or a mixture thereof. In order to obtain a sheet material having a certain level of strength, appropriate rebound, and sufficient heat resistance and dyeing resistance, the organic diisocyanate should be used in an amount of 1.7 to 6 molar equivalents, more preferably 1.7 to 6 molar equivalents relative to the polymeric diol. 1.8~5
It is necessary to use molar equivalents.

The chain extender used in the present invention is preferably a low molecular weight compound having two functional groups that react with commonly used organic polyisocyanates, such as glycols, diamines, amino alcohols, etc.

Examples of glycol chain extenders used in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, hexanediol, and cyclohexanediol. Sanindiol, 1,4-bis(β-
hydroxyethoxy)benzene, N,N-bis(β-hydroxyethyl)aniline, diethylene glycol, triethylene glycol, etc., or a mixture thereof.

Preferred are ethylene glycol, propylene 2 glycol, 1,4-butanediol, 1,4-bis(β-hydroxyethoxy)benzene, and the like. Specific examples of the organic diamine chain extenders used in the present invention include P-phenylene diamine, m-phenylene diamine, tolylene diamine, naphthylene diamine, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 4
, 4'-diaminodiphenyl sulfone, 4,4'-diamino 5-3,3'-dimethyldiphenylmethane, 4,4
'-diamino-3,3'-dichlorodiphenylmethane,
Aromatic organic diamines such as 4,4'-diaminodiphenyldimethylmethane, ethylenediamine, propylene diamine, menthanediamine, isophorone di4amine, cyclohexylene diamine, 4,4'=diaminodicyclohexylmethane, 4,4'-diamino-3 , 3'-dimethyldicyclohexylmethane, aliphatic organic diamines such as xylylene diamine, hydrazine, hydrazine hydrate, carbodihydrazide, organic dicarboxylic acid dihydrazide (e.g. dihydrazide of adipic acid, sebacic acid, terephthalic acid, isophthalic acid, etc.) , disemicarbazides and dithiosemicarbazides, aminocarboxylic acid hydrazides such as aminoacetic acid hydrazide, α-aminopropionic acid hydrazide, p-aminobenzoic acid hydrazide, etc., or mixtures thereof.

Aromatic organic diamines or alicyclic organic diamines are preferred, among which 4,4'-diaminodiphenylmethane,
Particularly preferred are tolylene diamine, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane. The hindered amine compound used in the present invention is represented by formula [I].

Specific examples of the substituent include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an allyl group, a propenyl group, a butenyl group, an isopropenyl group, a linalyl group, and a geranyl group. , a neryl group, a benzyl group, a benzyl group in which the hydrogen of the benzene nucleus is substituted with a halogen, a lower alkyl group, or a lower alkoxy group, and R'' is hydrogen, a methyl group, an ethyl group, etc., and R' is a methyl group. group, ethyl group, propyl group, butyl group, etc.
Examples of X include a hydroxyl group, an amino group, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and the like. R″ and R° are the same or different methyl group, ethyl group, propyl group, butyl group, etc., or a cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, etc. in which R″ and R° are bonded. Preferably 2,3
, 6-trimethyl-2,6-diethyl-4-hydroxypiperidine, 1,2,3,6-tetramethyl-2,6-
diethyl-4-hydroxypiperidine, 2,3,6-trimethyl-], 2,6-triethyl-4-hydroxypiperidine, l-allyl-2,3,6-trimethyl-
2,6-diethyl-4-hydroxypiperidine, 1-butenyl-2,3,6-trimethyl-2,6-diethyl-
4-hydroxypiperidine, 1-isoprenyl-2,3
, 6-trimethyl-2,6-diethyl-4-hydroxypiperidine, tobenzyl-2,3,6-trimethyl-
2,6-diethyl-4-hydroxypiperidine, 2,3
,6-trimethyl-2,6-diethyl-4-aminopiperidine, 1,2,3,6-tetramethyl2,6-diethyl-4-aminopiperidine, 2,3,6-trimethyl-
1,2,6-triethyl-4-aminopiperidine, 1-
Allyl-2,3,6-trimethyl-2,6-diethyl-
4-aminopiperidine, 1-butenyl-2,3,6-trimethyl-2,6-diethyl-4-aminopiperidine,
1-isopropenyl-2,3,6-trimethyl-2,6
-diethyl-4-aminopiperidine, 1-benzyl-2
, 3,6-trimethyl-2,6-diethyl-4-aminopiperidine, 2,3,6-trimethyl-2,6-diethyl-4-methylaminobiperidine, 1,2,3,6-tetramethyl -2,6-diethyl-4-methylaminobiperidine, 2,3,6-trimethyl-1,2,6-triethyl-4-methylaminopiperidine, 1-alinole-2,
3,6-trimethyl-2,6-diethyl-4-methylaminopiperidine, 1-butenyl-2,3,6-trimethyl-2,6-diethyl-4-methylaminopiperidine,
1-isopropenyl-2,3,6-trimethyl-2,6
-diethynole-4-methylaminopiperidine, 1-penzyl-2,3,6-trimethyl-2,6-diethyl-4
-Methylaminopiperidine, 2,3,6-trimethyl-
2,6-diethyl-4-ethylaminopiperidine, 1,
2,3,6-tetramethyl 2,6-diethyl-4-ethylaminopiperidine, 2,3,6-trimethyl-4,2
, 6-triethyl-4-ethylaminopiperidine, 1
-Allyl-2,3,6-trimethyl-2,6-diethyl-4-ethylaminopiperidine, 1-butenyl-2,3
, 6-trimethyl-2,6-diethyl-4-ethylaminopiperidine, 1-isopropenyl-2,3,6-trimethyl-2,6-diethyl-4-ethylaminopiperidine, 1-benzyl-2,3, 6-trimethyl-2,6-
Diethyl-4ethylaminopiperidine, 2,3,4,6
-tetramethyl-2,6-diethyl-4-hydroxypiperidine, 1,2,3,4,6-pentamethyl-2,6
-diethyl-4-hydroxypiperidine, 2,3,4,
6-tetramethyl-1,2,6-triethyl-4-hydroxypiperidine, 1-allyl-2,3,4,6-tetramethyl-2,6-diethyl-4-hydroxypiperidine, 1-butenyl-2,3, 4,6-tetramethyl-2,
6-diethyl-4-hydroxypiperidine, 1-isopropenyl-2,3,4,6-tetramethyl-2,6-diethyl-4-hydroxypiperidine, 1-benzyl-2,
3,4,6-tetramethyl-2,6-diethyl-4-hydroxypiperidine, 2,3,4,6-tetramethyl-
2,6-diethyl-4-aminopiperidine, 1,2,3
,4,6-pentamethyl-2,6-diethyl-4-aminopiperidine-2,3,4,6-tetramethyl-1,2
, 6-triethyl-4-aminopiperidine, 1-allyl-2,3,4,6-tetramethyl-2,6-diethynole-4-aminopiperidine, 1-butenyl-2,3,4,6-
Tetramethyl-2,6-diethyl-4-aminopiperidine, 1-isopropenyl-2,3,4,6-tetramethyl-2,6-diethynole-4-aminopiperidine, 1-benzyl-2,3,4,6- Tetramethyl-2,6-diethyl-4-aminopiperidine, 2,3,6-trimethyno-2,4,6-triethyl-4-hydroxypiperidine, 1,2,3,6-tetramethyl-2,4, 6-triethynole-4-hydroxypiperidine, 2,3,6-trimethyl-1,2,4,6-tetraethyl-4-hydroxypiperidine, 1-allyl-2,3,6-trimethyl-2,4,6- Triethyl-4-hydroxypiperidine, 1-butenyl-2,3,6-trimethyl-2,4,6
-triethyl-4-hydroxypiperidine, 1-isopropenyl-2,3,6-trimethyl-2,4,6-triethyl-4-hydroxypiperidine, 1--1<2,3,6-trimethyl-2 , 4,6-triethyl-4-hydroxypiperidine, 2,3,6-trimethyl-2,4,6-triethyl-4-aminopiperidine, 1
, 2,3,6-tetramethyl-2,4,6-triethyl-4-aminopiperidine, 2,3,6-trimethyl-1
,2,4,6-tetraethyl-4aminopiperidine, 1
-Allyl-2,3,6-trimethyl-2,4,6-triethyl-4-aminopiperidine, 1-butenyl-2,3,
6-trimethyl-2,4,6-triethyl-4-aminopiperidine, 1-isopropenyl-2,3,6-trimethyl-2,4,6-triethyl-4-aminopiperidine, tobenzyl-2,3,6 -Trimethinole 2,4,
6-triethynole-4-aminopiperidine, 2,6-dimethyl-2,6-dipropyl-3-ethyl-4-hydroxypiperidine, 1,2,6-trimethynole-2,6-
dipropyl-3-ethyl-4-hydroxypiperidine,
2,6-dimethyl-2,6-dipropyl-3-ethyl-
1-Benzyl-4-hydroxypiperidine, 2,6-dimethyl-2,6-dipropyl-3-ethyl-4-aminopiperidine, 1,2,6-trimethyl-2,6-dipropynolyl-3-ethynolyl-4- Aminopiperidine, 1-benzyl-2,6-dimethyl-2,6-dipropylene-3
-ethyl-4-aminopiperidine, etc. or a mixture thereof.

Particularly preferably, 2,3,6,6-tetramethyl-2-
Ethyl-4-hydroxypiperidine, 1,2,3,6,
6-pentamethyl-2-ethyl-4-hydroxypiperidine, 2,3,6,6-tetramethyl-4,2-diethyl-4-hydroxypiperidine, 1-allyl-2,3
, 6,6-tetramethyl-2-ethyl-4-hydroxypiperidine, 1-butenyl-2,3,6,6-tetramethyl-2-ethyl-4-hydroxypiperidine,
1-isopropenyl-2,3,6,6-tetramethyl-2-ethyl-4-hydroxypiperidine, 1-benzyl-2,3,6,6-tetramethyl-2-ethyl-4-
Hydroxypiperidine, 2,3,6,6-tetramethyl-2-ethynole-4-aminopiperidine, 1,2,3,
6,6-pentamethyl-2-ethyl-4-aminopiperidine, 2,3,6,6-tetramethyl-4,2-diethyl-4-aminopiperidine, 1-allyl-2,3,6
, 6-tetramethyl-2-ethynole-4-anopiperidine, 1-butenyl-2,3,6,6-tet3. lamethyl-2-ethyl-4-aminopiperidine, 1-isopropenyl-2,3,6,6-tetramethyl-2-ethynole-4-aminopiperidine, 1-benzyl-2,3,6,
6-tetramethyl-2-ethynole-A-aminopiperidine, 2,6,6-4ιlymethyl-3-ethyl-2-propyl-4-hydrocoxypiperidine, 1,2,6,6-
Tetramethynole-3-ethyl-2-propyl-4-hydroxypiperidine, 2,6,6-trimethyl-4,3-
diethyl-2-propyl-4-hydroxypiperidine,
1-allyl-2,6,6-trimethyl-3-ethyl-2-propyl-4-hydroxypiperidine, tobenzine-2,6,6-trimethyl-3-ethyl-2-propyl-4-hydroxypiperidine, 2, 6,6-trimethyl-3-ethyl-2-propyl-4-aminopiperidine, 1,2,6,6-tetramethyl-3-ethynole-2
-Propynolyl-4-aminopiperidine, 2,6,6-trimethyl-4,3-diethyl-2-propyl-4-aminopiperidine, 1-alinolyl-2,6,6-trimethyl-3-ethyl-2 -propyl-4-aminopiperidine, tobenzyl-2,6,6-trimethynole-3-ethyl-2-propyl-4-aminopiperidine, 2,3-dimethyl-2,6,6-triethynole-4-hydroxypiperidine, 1,2,3-trimethyl-2,6,6-triethyno-4-hydroxypiperidine, 2,3-dimethyl-1,2,6,6-tetraethyl-4-hydroxypiperidine, l-allyl-2,3- dimethyl-2,6,
6-triethyl-4-hydroxypiperidine, tobenzyl-2,3-dimethyl-2,6,6-triethyl-4
-Hydroxypiperidine, 2,3-dimethyno-2,6
, 6-triethyl-4-aminopiperidine, 1,2,3
-Trimethyl-2,6,6-triethyl-4-aminopiperidine, 2,3-dimethyl-4,2,6,6-tetraethyl-4-aminopiperidine, 1-allyl-2,3
-dimethyl-2,6,6-triethyno-4-aminopiperidine, tobenzyl-2,3-dimethyl-2,6,
6-triethyl-4-aminopiperidine, 7,8-dimethynole J me[ethynolyl-91-hydroxy-6-azaspiro [4,5]decane, 6,7,8-trimethynole J
Me[ethinole-9-hydroxy-6-azaspiro [4]
,5]decane, 7,8-dimethyl-6,7-diethyl-
9-hydroxy-6-azaspiro [4,5]decane,
6-alinole 7,8-dimethyl-Jmethynole-19-
hydrocoxy-6-azaspiro [4,5]decane, 6-
Benzinole 7,8-dimethynole J meethyl-9-hydroxy-6-azaspiro [4,5]decane, 7,8
-dimethyl-J-meth[ethyl-9-amino-6-azaspiro [4,5]decane, 6,7,8-trimethynole
[Ethyl-9-amino-6-azaspiro[4,5]decane, 7,8-dimethyl-6,7-diethyl-9-amino-3-azaspiro[4,5]decane, 6-aryl7,
8-Dimethyl-J-ethyl-9-amino-6-azaspiro[4,5]decane, 6-benzyl-7,8-dimethyl-J-[ethyl-9-amino-6-azaspiro[4]
,5] Decane, 2,3-dimethyno-2-ethyl-4-
Hydroxy-1-azaspiro [5,5]undecane,
1,2,3-trimethyno2-ethyl-4-hydroxy-1-azaspiro[5,5L undecane, 2,3-dimethyno-1,2-diethyl-4-hydroxy-1-azaspiro[5,5]undecane, 1-allyl-2,3-dimethyl-2-ethyl-4-hydroxy-1-azaspiro[5,5]undecane, 1-benzyl-2,3-dimethyl-2-ethynole-4-hydroxy-1-azaspiro[
5,5]Undecane, 2,3-dimethyl-2-ethyl-
4-amino-1-azaspiro[5,5]undecane, 1
,2,3-trimethyl-2-ethyl-4-amino-1-
Azaspiro[5,5]undecane, 2,3-dimethyl-
1,2-diethyl-4-amino-1-azaspiro [5,
5] Undecane, 1-alinoto-2,3-dimethyl-2-
Ethyl-4-amino-1-azaspiro[5,5]undecane, 1-<. 2,3-dimethyl-2-ethyl-4-amino-1-azaspiro[5,5]undecane, 2,3-dimethyl-2-ethyl-4-hydroxy-
1-Azaspiro[5,11)heptadecane, 1,2,3
-trimethynoto2-ethyl-4-hydroxy-1-azaspiro[5,11)heptadecane, 2,3-dimethynolyl-1,2-diethynolyl-4-hydroxy-1-azaspiro[5,11)heptadecane, 1-allyl -2,3-dimethyl-2-ethinoto4-hydroxy-1-azaspiro[5,11)heptadecane, 1-<. Njinore 1 2,3
-dimethynole-2-ethyl-4-hydroxy-1-azaspiro[5,11)heptadecane, 2,3-dimethyl-
2-ethyl-4-amino-1-azaspiro [5,11]
Heptadecane, 2,3-dimethyl-1,2-diethyl-4-amino-1-azaspiro[5,11] Heptadecane, 1-allyl-2,3-dimethyl-2-ethynole-4
-amino-1-azaspiro[5,11)heptadecane,
1-benzyl-2,3-dimethynolyl-2-ethynolyl-4
amino-1-azaspiro[5,11)heptadecane, etc., or a mixture thereof.

More preferably, 2,3,6-trimethinoto2,6-
Diethyl-4-hydroxypiperidine, 1,2,3,6
-tetramethyl-2,6-diethyl-4-hydroxypiperidine, 1-benzyl-2,3,6-trimethyno-2,6-diethyl-4-hydroxypiperidine, 2,
3,6-trimethyl-2,6-diethyl-4-aminopiperidine, 1,2,3,6-tetramethyl-2,6-diethyl-4-aminopiperidine, 1-benzyl-2,3
, 6-trimethyl-2,6-diethyl-4-aminopiperidine, etc. or a mixture thereof.

More preferably, 2,3,6,6-tetramethyl-2-ethyl-4-hydroxypiperidine, 1,2,3
, 6,6-pentamethyl-2-ethinoto-4-hydroxypiperidine, 1--1<<2,3,6,6-tetramethyl-2-ethynoto-4-hydroxypiperidine, 2
, 3,6,6-tetramethyl-2-ethyl-4-aminopiperidine, 1,2,3,6,6-1<ntamethyl-2
-ethyl-4-aminopiperidine, 1-benzyl-2,
3,6,6-tetramethyl-2-ethyl-4-aminopiperidine, 2,3-dimethyl-2,6,6-triethyl-4-hydroxypiperidine, 1,2,3-trimethyl-2,6,6 -triethyl-4-hydroxypiperidine, tobenzyl-2,3-dimethyl-2,6,6-triethyl-4-hydroxypiperidine, 2,3-dimethyl-2,6,6-triethyl-4-aminopiperidine, 1,
2,3,1-trimethyl-2,6,6-triethyl-4-
Aminopiperidine, 1-<2,3-dimethyl-2,6,6-triethyl-4-aminopiperidine, 2,
3-dimethynole-2-ethyl-4-hydroxy-1-azaspiro[5,5]undecane, 1,2,3-trimethynole-2-ethyl-4-hydroxy-1-azaspiro[
5,5]Undecane, 1-benzinole-2,3-dimethyl-2-ethyl-4-hydroxy-1-azaspiro[5
, 5] undecane, 2,3-dimethyno-2-ethyl-4
-amino-1-azaspiro[5,5]undecane, 1,
2,3-trimethylethyl-2-ethyl-4-amino-1-
Azaspiro[5,5]undecane, 1-benzyl-2,
3-dimethyl-2-ethyl-4-amino-1-azaspiro [5,5]undecane, etc. or a mixture thereof. In addition to the above-mentioned compounds, the hindered amine compound of the present invention has hydrogen bonded to the oxygen atom or nitrogen atom of the amino group, hydroxyl group, and monoalkylamino group of the substituent represented by R and/or X. (R゜O)n
-H or one (COR4COOR5O)m-H may be substituted.

In the former case, R° represents a lower alkylene group, and n represents an integer of 1 to 50.

The lower alkylene group usually refers to one having about 2 to 14 carbon atoms, and includes those in which one hydrogen is replaced with a phenyl group or the like. The compound is the original hindered amine compound and R
Obtained by reacting "R" O (alkylene oxide). Specific examples of R"O (alkylene oxide) include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, etc., and mixtures thereof. . In the latter case, R'' represents an organic dicarboxylic acid residue, R° represents an organic diol residue, and m represents an integer from 1 to 15.

The organic dicarboxylic acid preferably has 2 to 12 carbon atoms, and specific examples include succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, anhydrides thereof, and mixtures thereof. . The organic diol preferably has 2 to 8 carbon atoms, and specific examples include ethylene glycol, propylene glycol, butylene glycol, hexane glycol, octane glycol J, diethylene glycol, triethylene glycol, and mixtures thereof. The above-mentioned hindered amine compound is synthesized, for example, according to the method described in JP-A-53-1294 and its cited documents.
5. When the above-mentioned hindered amine compound is a monofunctional compound, if it is used in a certain amount or more, the molecular weight of the polyurethane elastomer becomes small, and the amount to be used is naturally limited.

The amount used is 2 mol % or more, preferably 2 to 20 mol %, more preferably 2 to 15 mol %, more preferably 12 to 15 mol %, based on the total weight of the chain extender and terminal stopper.
It is in the range of 2 mol%.

Of course, a monofunctional terminal capping agent made of other monoamines or monoalcohol compounds may also be used in combination. In addition, when the hindered amine compound is a difunctional compound, the amount used is preferably 2 to 3 of the chain extenders.
It is preferably used in a range of 0 mol%, more preferably 2 to 20 mol%, and even more preferably 12 to 2 mol%.

Furthermore, when it comes to trifunctional compounds, if they are used in too large an amount, the viscosity becomes too high and may even cause gelation, so they should be used in an amount of 2 to 10 mol% or less of the total chain extender. is preferable.

Of course, each type of hindered amine compound may be used in combination. The solvent for the polyurethane of the present invention is not particularly limited as long as it dissolves the polyurethane and does not react with isocyanate groups.

Preferred are dimethylformamide, diethylformamide, dimethylacetamide, hexamethylvos, phoramide, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, dioxane, etc., or mixtures thereof. When producing the polyurethane elastomer of the present invention, in addition to the above-mentioned monovalent hindered amine compounds, commonly used monofunctional compounds having one amino group or hydroxyl group can be used to adjust the degree of polymerization to a desired degree. .

The polyurethane elastomer of the present invention can be obtained by adding and reacting a polymeric diol, an organic polyisocyanate, a chain extender, and, if necessary, a terminal capping agent, all at once, as is generally practiced.

It is also possible to use a so-called prepolymer method in which a so-called prepolymer is synthesized by reacting a polymeric diol organic polyisocyanate in advance and then extended with a chain extender. The hindered amine compound, which is a feature of the present invention, may be added at any stage in the above reaction process.

When using a hindered amine compound having a hydroxyl group that has low reactivity with isocyanate groups, it is desirable to add it at an early stage of the reaction to ensure intramolecular introduction. In order to accelerate the reaction rate when synthesizing the polyurethane of the present invention, for example, S. L. ReegenandK. C
．． Frisch, “Advances in Uretha.
neScience and Technology,''
1, (1971) TechnOmic. , Pub. C.O.
Jnc. It is of course possible to add a tertiary amine such as triethylene diamine as described in , or an organometallic compound such as dilauryl dibutyltin.

Of course, according to the above method, a prepolymer is synthesized, and chain extension is performed in an aqueous solvent using an appropriate emulsifier as necessary with a chain extender containing the aforementioned hindered amine compound to synthesize an aqueous emulsion of polyurethane. Methods used for impregnation may also be employed.

Although it is not as good as the solution type polyurethane in terms of mechanical properties, etc., it is very advantageous in producing fiber sheets, as will be described later. In the solution of the polyurethane elastomer of the present invention,
As is already known, additives such as weathering agents such as various antioxidants and ultraviolet absorbers, organic and inorganic pigments, carbon black, titanium oxide, and coagulation regulators may be added.

Next, the fiber sheet used in the present invention will be described.

The fiber sheet used in the present invention has a fineness of 1
．． Two or more ultrafine fibers of 5 deniers or less, preferably 5
Non-woven fabrics, woven fabrics, and knitted fabrics mainly composed of bundles of ultrafine fibers having a collection of one or more fibers are particularly preferred in order to obtain a supple texture. The fibers are not particularly limited, but those made of polyamide or polyester are preferably used. Do you prefer it? Alternatively, it is a fiber made of 6-nylon, 6,6-nylon, polyethylene terephthalate, or a copolymer thereof. In the present invention, ultrafine fibers are generated, for example, when at least one component is removed, ultrafine fibers composed of other components are produced. It is preferable to use composite fibers that can be obtained in bundles of 1 to 2. Particularly preferred fibers are ultrafine fiber bundles obtained by removing the sea component of polymer array fibers as shown in Japanese Patent Publication No. 46-3817, for example. .

In addition, we also use fibers produced by the known mixed yarn protection method, and peelable type fibers, that is, fibers made of two or more components that are peeled off from the interface by means such as applying an external force to generate ultrafine fibers. can. In some cases, ultrafine fibers obtained by the method of Spadro 1 etc. may also be used. The thickness of each fiber is 1.5d or less, preferably 0.
．． It is preferably 0.2 d or less than 8 d or less.

The fiber sheet of the present invention can be produced by, for example, forming fibers mainly composed of composite fibers such as polymer array fibers into a sheet by needle punching, weaving/knitting techniques, etc., and removing the components to be removed with a solvent. It can be obtained by making the composite fiber ultra-fine by applying mechanical action or the like.

There are various methods for producing the composite sheet-like object of the present invention from a fiber sheet and the polyurethane elastic body.
A typical manufacturing method using polymer array fibers is as follows.

A web is formed from the above-mentioned polymer array fibers, entangled by a method such as needle punching, and the sea component is extracted with a solvent to form a nonwoven fabric consisting of ultrafine fiber bundles of polyethylene terephthalate. The raised sheet is impregnated with a polyurethane solution, wet-coagulated in water, desolventized, dried, and then the surface is hubbed.The resulting raised sheet is preferably passed repeatedly through a nozzle in a liquid stream to give a kneading effect while being heated at high temperature. How to dye. More preferable methods include a method in which a nonwoven fabric made of polymer array fibers is impregnated with the polyurethane of the present invention, and after coagulation, the sea component of the fibers is removed to generate ultrafine fibers, and a similar raised dyeing process is performed. A nonwoven fabric made of molecular array fibers is treated with an aqueous solution of a water-soluble polymer such as polyvinyl alcohol, starch, or carboxymethyl cellulose, and after drying, the sea component is extracted with a solvent to form a microfiber bundle sheet, and then the polyurethane solution of the present invention is applied. There is a method in which the material is impregnated, wet-coagulated and solvent removed in water, and the water-soluble polymer is extracted in warm water, followed by a similar nap dyeing treatment. A slicing or pressing step may be added at an appropriate stage to adjust the thickness. Further, a step such as applying silicone may be added to adjust the pils-up state. In addition, when using a water-based polyurethane emulsion,
For example, a fabric made of the above-mentioned polymer array fibers is impregnated with an aqueous emulsion of polyurethane, dried, the sea component is removed using perchloren to generate ultrafine fibers, and the surface is then hubbed. A method of dyeing the raised sheet is adopted.

The composite dowel-shaped article of the present invention thus obtained has excellent properties such as being dense and at the same time supple in texture and touch, and having little change over time.

Furthermore, it has excellent properties such as a smooth surface, an elegant chiyoke mark, and little change over time. As is clear from the above explanation, the effects of the present invention are particularly preferably exhibited when the sheet has raised naps. Of course, it is also possible to make artificial leather.

The present invention will be specifically explained below using examples.

The following measuring method was used to evaluate the sheet-like products in the examples. Flexibility: Bending stress (grams) when a 2 x 5 cm sample is lifted 2 cm from the horizontal position between fulcrums spaced at 1 cm intervals
It is shown with.

Sheets with a value of 100 g or less feel particularly flexible. Repulsion elasticity. A sample of 2 × 10 cn1 is folded into four, and the force when it recovers is 25 at a distance of 50 cn1 from the fulcrum.
It is indicated by the length of the arc when an arc is drawn on the object g (0.5 to 1.0 cm for natural suede leather).

Smoothness and surface appearance. The unevenness of the surface and the elegance of the nap surface were visually judged and divided into five grades.

5 means the best.

Weather meter 1 irradiation: Weather meter 1 [WEL-5S manufactured by Suga Test Instruments Co., Ltd.
Using UN-HMO (hereinafter abbreviated as WM), at a temperature of 60 to 6
Irradiation was performed under conditions of 6° C. and 70% humidity.

Discoloration after irradiation was evaluated visually and divided into 5 grades. 5 shows the least discoloration.

Tensile test: A sample of 20 x 100 mm was prepared and measured using a Tensilon UTM-111-100 tensile tester manufactured by Toyo Port Win Co., Ltd.

Surface appearance after being worn for 2 months: The surface appearance was determined and graded after sewing jumpers and wearing them for 2 months, dry cleaning once, and washing with water an average of 3 times. .

Note that the following abbreviations are used in the examples.

Example 1 A clip consisting of 50 parts of polyethylene terephthalate as the island component and 50 parts of polystyrene as the sea component, 16 islands/flyment stretched 2 to 3 times, thickness 3.4 denier, length 51 mm. Using 15/inch polymer array fibers, the apparent density was 0.170 g/cm3 through each process of carding, cross-punching, and needle punching.
A nonwoven fabric was obtained.

The nonwoven fabric was impregnated with a 20% aqueous solution of polyvinyl alcohol, and after drying, it was immersed in perchloroethylene to dissolve the polystyrene to obtain a nonwoven fabric in which bundles of ultrafine fibers were entangled. PCL with a molecular weight of 2060 was reacted with 3 times the molar equivalent of MDI to obtain a prepolymer, and then DMF2
Dilute EG, BEHP and IPA to 50% with 93:6
A mixed solution containing a molar ratio of :1 was added in an amount of 0.97 molar equivalent based on the remaining isocyanate groups, and the mixture was reacted at 30° C. for 20 hours.

The mixture was then diluted to 30% with DMF and reacted at 30°C for 8 hours. After standing for a day and night, it was diluted with DMF to obtain a 13% DMF solution of the polyurethane elastomer of the present invention. The nonwoven fabric was impregnated into the obtained polyurethane solution, squeezed with a roll to remove excess solution, wet-coagulated in water for 1 hour, raised the water temperature to 80°C, removed the solvent and polyvinyl alcohol, and dried. did.

The obtained sheet was sliced to a thickness of 1.1 mm, and the surface was roughened with sandpaper. The thickness of the sheet after the hub was 0.85 mm. The sheet was dyed with Kayalon Polyester Gray NG (disperse dye) 2%0. w. 1 at 125℃ using the dye solution of f.
Time stained. The resulting sheet is brushed and
A raised sheet of the present invention having an apparent density of 0.269 g/CTff was obtained. Separately, for comparison, chain elongation reactions were performed with EG and IPA.
A raised sheet was produced in the same manner as in the above invention example except that the molar ratio was 96:4 (Comparative Example 1).

In Examples 2 to 6 and Comparative Examples 2 to 4, napped sheets were produced in the same manner as in Example 1, except that polyurethane having the composition shown in Table 1 was used. Example 7 A DMF solution containing PCL (molecular weight 2060), MDI, EG, and MEHP in a molar ratio of 1:3:1.8:0.11 was heated to 50°C, and a 25% polyurethane solution (250 poise) was added. Obtained.

In the same manner as in Example 1 except that the polyurethane was used,
A raised sheet was produced. Example 8 Two molar equivalents of MDI was added to PTHF with a molecular weight of 2004 and reacted to obtain a prepolymer, then diluted to 50% with DMF, and then MBA, MEHP, and DBA were added equally to the remaining isocyanate groups. A DMF solution containing a molar ratio of 0.85:0.1:0.05 was added to obtain a 13% polyurethane elastomer.

A raised sheet material of the present invention was obtained in the same manner as in Example 1 except that the above binder was used.

For comparison, the chain elongation reaction was performed with MBAI::. A polyurethane solution was prepared in the same manner as in the inventive example except that DBA (molar ratio (0.85:0.15) was used), and a napped sheet was prepared using it (Comparative Example 5).

In Examples 9 to 14 and Comparative Examples 6 and 7, raised sheets were produced in the same manner as in Example 1, except that polyurethane having the composition shown in Table 1 was used.

Table 1 shows the evaluation results of the obtained sheet-like material.

Of course, the characteristic values of the sheet-like material vary depending on the type of polyurethane, but the examples of the present invention using a hindered amine compound have a dense structure as shown by the higher apparent density compared to the comparative example that does not use a hindered amine compound. Despite this, it has low flexibility and repulsion, and is excellent in so-called suppleness. Moreover, it has excellent smoothness and surface appearance. Furthermore, it is clear from Table 1 that it has excellent properties such as the elegance of the fluff on the surface and small changes in characteristic values (strength and abrasion properties) due to weather 1/0 meter irradiation and wearing. Example 15 Example 1
The sheet before slicing described in 1. has a thickness of 1.5 mm and is used as a base material for leather production.

Also, 25% D of the same polyurethane used in Example 1
Paint containing 3% carbon black in MF solution,
A reverse roll coater is applied to the above substrate to a thickness of 0.
It was coated to a thickness of 5 mm and wet coagulated with water. After 30 minutes, the product was washed with hot water for 30 minutes to remove the solvent, and dried at 100° C. for 1 hour to obtain the artificial leather of the present invention.

Separately, a similar paint was made using the polyurethane of Comparative Example 1, and comparative artificial leather was obtained in the same manner using the above-mentioned base material (Comparative Example 8).

The resulting artificial leather was pushed in all directions with the silver side up using a hemispherical plasticity tester to evaluate the unevenness that occurs on the silver surface (evaluation of roughness during shoe making), depending on the smoothness of the base material. As shown in Table 2, the examples of the present invention are excellent, perhaps because of this.

Furthermore, a treatment was carried out for 50 hours with weather meter irradiation, and the surface cracking condition measured with a flexometer (JIS K6545-1970) was compared, and the results shown in Table 3 were obtained. It is clear that the durability is also significantly improved when using the polyurethane of the present invention. Example 16,
17 A raised sheet was produced in the same manner as in Example 1 except that the hindered amine compound and polymer diol shown in Table 1 were used.

Examples 18 and 19 A raised sheet material was produced in the same manner as in Example 8, except that the hindered amine compound and polymer diol shown in Table 1 were used.

Example 20 PTHF with a molecular weight of 2040 was added with 2 times the mole of MDI, O. O
After adding 9 mol of HEHP to obtain a prepolymer, it was diluted with DMF to 50%, and then MBA. ! A DMF solution containing -DBA in an equimolar molar ratio of 0.96:0.04 to the remaining isocyanate was added to obtain a 14% polyurethane elastomer solution.

A sheet-like product was produced in the same manner as in Example 1 using the solution. Example 21 2,3,6-trimethyl-2,6-diethyl-4-(N
-Methylamino)piperidine and 2 times the mole of ethylene oxide were reacted for 2 hours at 80°C without solvent in an autotale to obtain a mixture containing the compound of the following formula as the main component.

A raised sheet was obtained in the same manner as in Example 20, except that the mixture was used as it was in the prepolymer reaction without being purified. Example 22 A raised sheet material was obtained in the same manner as in Example 21, except that ethylene oxide was used in an equimolar amount as MEAP, and a mixture containing the compound of the following formula as the main component was used.

Example 23 10.5 wt% MM for PEA with molecular weight 2020
HP was added, and the ethylene glycol produced and unreacted MMHP were removed under reduced pressure while stirring for 10 hours in a molten state at 100°C without a solvent. A mixture (modified PEA) containing the compound as a main component was obtained.

The modified PEA6O part, unmodified PEA2O part, PTHF2
With respect to 40 parts, 3 times the mole of MDI and 1.93 times the mole of EG were dissolved in DMF to give a concentration of 60%, and a polyurethane polymerization reaction was carried out by the so-called "one shot method" while stirring at 50.degree. As the viscosity increased, the reaction product was diluted with DMF to finally reach 30%, and 0.07 times the mole of IPA was added. The viscosity of the solution is 830p0ise
It was hot. The solution was further diluted with DMF to 13%, and then a raised sheet was produced in the same manner as in Example 1. Example 24 A raised sheet material was obtained in the same manner as in Example 23, except that PEA was modified with MEAP and a mixture containing the following compounds as main components was used.

Example 25 A raised sheet material was obtained in the same manner as in Example 23, except that PEA was modified with MMAP and a mixture containing the following compounds as main components was used.

Table 1 shows the evaluation results of the sheet-like materials obtained in Examples 16 to 25.

Claims (1)

[Scope of Claims] 1. A polyurethane elastomer obtained from a fiber sheet, a polymeric diol having a molecular weight of 800 or more, an organic polyisocyanate, a chain extender, and optionally a terminal stopper, which A composite sheet material impregnated and/or coated with a polyurethane elastomer in which 2 mol% or more of the agent and terminal stopper is a hindered amine compound represented by the formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...
・・・・・・・・・〔I〕〔However, in the formula, R^1 is a hydrogen atom,
Alkyl group of C_1 to C_1_2, C_2 to C_1_2
alkenyl group, C_7 to C_1_2 aralkyl group,
-(R^3O)_n-H (where R^3 is a lower alkylene group, n is an integer from 1 to 50). R^2 is a substituent selected from the group consisting of hydrogen and an alkyl group of C_1 to C_1_2. X is a hydroxyl group, an amino group, a monoalkylamino group of C_1 to C_1_2, and the hydrogen bonded to these nitrogen or oxygen atoms is -(
R^3O)_n-H or -(COR^4COOR^5O
)_m-H substituent selected from the group consisting of a group substituted with H (however, R^3, n are as described above, R^4 is an organic dicarboxylic acid residue, R^5 is an organic diol residue, m is 1-1
Represents an integer of 5. ) R^6 is a lower alkyl group of C_1 to C_1_2, R^7 and R^8 are the same or different C_
An alkyl group of 1_ to _1_2 or R^7 and R^8 bonded together to form a ring of C_5_ to _1_2. ].
2. The composite sheet-like article according to claim 1, wherein the fiber sheet is mainly composed of bundles of ultrafine fibers having a fineness of 1.5 denier or less. 3. A composite sheet-like article according to claim 1, which has napped hair on at least one side.