| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | December 31, 2002 |
| PATENT TITLE |
Polyester diol and derived polyurethane and acrylic copolymer |
| PATENT ABSTRACT | The invention provides polyester dials suitable for preparation of polyurethanes, and provides polyurethanes derived therefrom. The invention also provides spandex filaments prepared from these polyurethanes, which exhibit improved elasticity, tensile strength, and resistance to hydrolysis. The present invention also provides dialkyl amino group-containing polyol additives having a high solubility in dimethylacetamide solvent, which when incorporated into a polyurethane protect the polyurethane and derived spandex filaments from deterioration or discoloration, and confer an improved modulus of elasticity. The polyurethanes and spandex filaments of the invention provide fabrics having a soft feeling, excellent hydrolysis resistance, wrinkle resistance, and adhesive properties, and which are particularly suitable for preparation of an artificial leather |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | March 8, 2001 |
| PATENT CT FILE DATE | May 22, 2000 |
| PATENT CT NUMBER | This data is not available for free |
| PATENT CT PUB NUMBER | This data is not available for free |
| PATENT CT PUB DATE | November 30, 2000 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED | International Search Report for Application No. PCT/JP00/03265, Aug., 2000 |
| PATENT CLAIMS |
What is claimed is: 1. A polyurethane which is a copolymer of: (i) a polyester polyol composition (X) which is a copolymer of a polyol (Al) having an ultraviolet absorbing group and/or a lactone-modified polyol (A2) derived therefrom, optionally one or more other polyol components (A3), and adipic acid; and (ii) an organic diisocyanate (Y). 2. The polyurethane according to claim 1, wherein the polyol (A1) is the compound represented by formula (1): ##STR6## 3. The polyurethane according to claim 1, wherein said lactone is .epsilon.-caprolactone. 4. The polyurethane according to claim 2, wherein said lactone is .epsilon.-caprolactone. 5. The polyurethane according to any one of claims 1-4, wherein the number average molecular weight of the polyester diol ranges from 500 to 5,000. 6. The polyurethane according to any one of claims 3-4, wherein the proportion of .epsilon.-caprolactone is between 20% and 95% by weight of the polyester. 7. The polyurethane according to any one of claims 3-4, wherein the proportion of .epsilon.-caprolactone is between 20% and 95% by weigh of the polyester, and wherein the number average molecular weight of the polyester diol ranges from 500 to 5,000. 8. The polyurethane according to any one of claims 1-4, wherein the molar ratio {(A1)+(A2)}/{(A1)+(A2)+(A3)} of polyols in said polyol composition is from 0.01 to 1.0. 9. The polyurethane according to claim 5, wherein the molar ratio {(A1)+(A2)}/{(A1)+(A2)+(A3)} of polyols in said polyol composition is from 0.01 to 1.0. 10. A spandex filament which comprises a polyurethane according to any one of claims 1-4. 11. A spandex filament which comprises a polyurethane according to claim 5. 12. A spandex filament which comprises a polyurethane according to claim 6. 13. A spandex filament which comprises a polyurethane according to claim 7. 14. A spandex filament which comprises a polyurethane according to claim 8. 15. A spandex filament which comprises a polyurethane according to claim 9. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
TECHNICAL FIELD The present inventions No. 1 and No. 2 relate to a spandex filament (a polyurethane elastic fiber) which is excellent in view of a recovering ability of elasticity, high tensile strength and, further, hydrolysis resistance, and relate to a polyurethane which can provide thereof and, further, relate to a polyester diol. The present invention No. 3 relates to a spandex filament which is excellent in view of hydrolysis resistance and a novel polyurethane which can provide thereof. The present invention No. 4 relates to a polyurethane which is excellent in weatherability. In more detail, it relates to a polyurethane having a (washing resistance) property in which the weatherability does not almost lower even though being repeatedly washed, and relates to a spandex filament comprising the polyurethane. The present invention No. 5 relates to a dialkyl amino group-contained acrylic-based copolymer which is useful as a high molecular-state amine stabilizer for a polyurethane. In more detail, the present invention relates to an improvement of the amine stabilizer for, particularly, a polyurethane/spandex filament and a film. It is to be noted that the terminology "spandex" employed in the No. 5 means a synthesized elastomeric composition having a long chain which contains at least 85% by weight of a segment-state polyurethane. The present invention No. 6 relates to a polyurethane having properties which are excellent in a soft feeling, hydrolysis resistance, wrinkle resistance, and an adhesive property and, particularly, it is excellent as an artificial leather. TECHNICAL BACKGROUND In the present inventions No. 1 and No. 2, a polyurethane having a linear-state structure is obtained by allowing to react a long chain diol having hydroxyl groups at both terminals with an organic diisocyanate and a diol or a diamine, etc. which is named a relatively low molecular weight chain extender having two active hydrogens. Concerning a recovering ability of elasticity and hydrolysis resistance in thus-obtained polyurethane, various attempts for an improvement have been proposed. As described in JP-A-58059212 Official Gazette, although a polyurethane using a polyethylene glycol adipate polyester is excellent in a recovering ability of elasticity, it is poor in hydrolysis resistance. Further, although a 1,4-butylene glycol adipate polyester has a certain extent of hydrolysis resistance, a recovering ability of elasticity is poor in a polyurethane therefrom. Still further, although a polyurethane prepared from a polycaprolactone polyol is excellent in hydrolysis resistance, weatherability, and heat resistance, it is poor in a recovering ability of elasticity. In the JP-A-58059212 Official Gazette, there is described a technology using a specified polycaprolactone polyester polyol obtained by an esterification reaction of a polyester polyol synthesized by a dehydration esterification of neopentylglycol with adipic acid with .epsilon.-caprolactone as a method for solving a drawback of a polycaprolactone-based polyurethane. Further, in the JP-A-11001822 Official Gazette, there are disclosed polyurethane elastic fibers which are excellent in alkali-hydrolysis resistance in which there are employed 2-n-butyl-2-ethyl-1,3-propane diol and 2,2-diethyl-1,3-propane diol as a diol component which constructs a polyester polyol. In relation to the present invention No. 2, in JP-A-63097617 Official Gazette, there is described a spandex filament, etc. which is improved in bacteria resistance, and which is prepared from a poly(2,2-dimethyl-1,3-propane dodecanedioate). However, since the recovering ability of elasticity and hydrolysis resistance are not always sufficient in the polyurethane described in the JP-A-58059212 Official Gazette, there is desired a polyurethane in which those are improved. Further, although the polyurethane elastic fibers in the JP-A-11001822 Official Gazette are excellent in hydrolysis resistance, it is desired to further improve a recovering ability of elasticity and strength. Still further, in the spandex filaments described in the JP-A-630978617 Official Gazette, there is desired a further improved strength. In relation to the present invention No. 3, a polyurethane having a linear structure is obtained by allowing to react a long chain diol having hydroxyl groups at both terminals with an organic diisocyanate and a relatively low molecular weight diol or diamine which is named a chain extender having two active hydrogens. For improvement of characteristics of thus-obtained polyurethane, various proposes have been made. For example, in the JP-A-11001822 Official Gazette, there are disclosed polyurethane elastic fibers which are excellent in alkali hydrolysis resistance in which there are employed 2-n-butyl-2-ethyl-1,3-propane diol and 2,2-diethyl-1,3-propane diol as a diol component which constructs a polyester polyol. Further, in JP-A-63097617 Official Gazette, there is described a spandex filament, etc. which is improved in bacteria resistance, and which is prepared from a poly(2,2-dimethyl-1,3-propane dodecanedioate). However, although the polyurethane described in the JP-A-11001822 Official Gazette is excellent in a certain extent of hydrolysis resistance, there is further desired an improvement. Also in the spandex filament described in the JP-A-63097617 Official Gazette, it is in the same situation. The polyurethane having a linear structure in relation to the present invention No. 4 is prepared by allowing to react a long chain diol having hydroxyl groups at both terminals with an organic diisocyanate and a relatively low molecular weight diol or diamine which is named a chain extender having two active hydrogens. Thus-obtained polyurethanes are employed for a variety of uses, for example, a thermoplastic elastomer, a hard or soft urethane foam, an adhesive, an artificial leather, a synthetic leather, a coating, and an elastic fiber (a spandex filament), etc. The polyurethanes are naturally excellent in weatherability (including a light resistance) and durability and, in order to further give weatherability, there are employed publicly-known ultraviolet ray absorbents, for example, benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 5-chloro-2-(2'-hydroxy-3', 5'-di-t-butylphenyl)benzotriazole, and benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone. However, since the conventional ultraviolet ray absorbents are a low molecular weight compound having a low boiling point, the addition thereof to a polyurethane causes various inconveniences. For example, the addition of a large amount of the ultraviolet ray absorbents causes a phase separation, resulting in that whiteness and mechanical strength are lowered in the polyurethane. Therefore, although the ultraviolet ray absorbent is added as a small amount as possible and, in the case, light resistance is not elevated until a satisfying extent in the polyurethane. Further, since the ultraviolet ray absorbent is lost by evaporation or decomposed during processing or molding, or it oozes out on the surface of a molded article, it becomes impossible to give a stable light resistance over a long time of period. Still further, when a spandex filament product is repeatedly washed, the ultraviolet ray absorbent is removed from the product, and an effect is gradually reduced. By the way, an object is not limited to the polyurethane, in order to solve the above-described drawbacks, there is tried an attempt (JP-A-60038411 Official Gazette, JP-A-62181360 Official Gazette, and JP-A-03281685 Official Gazette, etc.) for giving a polymerizable double bond such as vinyl group to the above-described ultraviolet ray absorbent, for highly-polymerizing the absorbent to improve a compatibility with a variety of resins, and for preventing evaporation, thermal decomposition, and bleeding, etc. of the ultraviolet ray absorbent. However, these ultraviolet ray absorbable polymers also have a drawbacks as described below, and room for an improvement remains. That is, although thermoplastic resins such as thermoplastic polyurethane resins have an exceedingly high mechanical strength and those are widely employed as a various molding materials, since the thermoplastic polyurethane resins have a drawback of a decline in the mechanical strength by decomposition due to alkali components, and there has been desired an improvement of chemical resistance such as an alkali resistance and solvent resistance. It is to be noted that JP-A-10265557 Official Gazette describes a lactone-modified polyol made from a polyol having an ultraviolet ray absorbable group. However, it does not describe the use thereof as a constructing component for a polyester diol which is a raw material for a polyurethane. In relation to the present invention No. 5, a segment-state polyurethane is well known, which is prepared by forming an isocyanate-terminated polymer through allowing to react a high molecular weight diol (most of those are a polyether glycol or a polyester glycol) with an organic diisocyanate, and by chain-extending through allowing to react thereof with a diamine or a diol. The terminology "fiber" includes staple fibers and continuous filaments. U.S. Pat. No. 3,428,711 by Hunt discloses the use of a high molecular weight tertiary aminoalkyl acrylate and methacrylate for stabilizing a segment-state polyurethane, and a large commercial use is found out as fibers for spandex. Hunt discloses a large amount of such additives. A preferred stabilizer disclosed by Hunt is a copolymer of diisopropyl amino ethylmethacrylate (hereinafter, named "DIPAM") which has a steric hindrance with n-decylmethacrylate (hereinafter, named "DM"). The copolymer (hereinafter, named "poly(DIPAM/DM)") provides a polymer for a spandex which has a large resistance to deterioration by exposure to chlorine than a similar amine which does not have a steric hindrance. Additives containing a tertiary amino group having a high molecular weight and a steric hindrance are useful for preventing deterioration and discoloration of for a spandex polymer. However, the additives are occasionally cause a problem in the preparation and/or a change to worse of properties in a fiber prepared from the spandex polymer. For example, the use of the poly(DIPAM/DM) additives causes a certain kind of a problem in the case of dry-spinning a filament from a spandex polymer solution. Dimethyl acetoamide (hereinafter, named "DMAc") is a solvent to be most preferably employed for the preparation of the spandex polymer solution. The poly(DIPAM/DM), an antioxidant, and other additives such as pigments are usually changed to a slurry together with the DMAc, followed by being mixed with the spandex polymer solution prior to spinning. However, such the slurry usually prepared at room temperatures occasionally causes a phase-separation in the case that a high molecular weight amine lacks a solubility to the DMAc solvent. The phase-separation has a possibility of causing aggregation of the additives, a problem during spinning and/or an uniform distribution of the additives into a solution for spinning and filaments spun therefrom. That is, the polymer for spandex containing the poly(DIPAM/DM) or the (DPAM) additives adversely affects to a preparation step because of inferiority of solubility to solvent when being spun, and it causes a certain kind of drawback to elasticity in filaments prepared from the spandex polymer, that is, an undesired decline (that is, permanent extension (set)) of elasticity in the spandex filaments made by dry-spinning. A great parts of high molecular weight tertiary aminoalkyl(meth)acrylate additives have any one of or both drawbacks. On the other hand, JP-A-02086655 by Roden et al suggests the DIPAM and a hydroxybutyl acrylate- or methacrylate-based copolymer in order to provide an additive containing a high molecular weight tertiary amine having a steric hindrance which is employed for a spandex polymer. However, in the copolymer described in the JP-A-02086655, although it suppresses a manifestation of the decline (that is, permanent extension (set)) in elasticity related to the use of already known additives containing a high molecular weight tertiary amino group having a steric hindrance to a certain extent, it is not always sufficient in solubility to the DMAc solvent, and it still has a possibility of a manifestation of the decline in elasticity. In relation to the present invention No. 6, it is usually and widely known that an artificial leather is obtained by processing of adding a variety of polymer compounds to a nonwoven sheet-like material primarily composed of an ultra-fine fiber. As the polymer compounds in the case, there are employed many elastic polymer compounds such as a polyurethane, etc. in order to obtain physical properties such as a soft and elastic feeling as an artificial leather, durability, and dimensional stability. And, the elastic polymer compounds are coated on a nonwoven sheet-like material as a solution dissolved in an organic solvent, and then, very often moisture-solidified. On the other hand, since the organic solvent employed in the case is often a substance which is very inflammable and highly toxic, many attention must be paid when recollecting the solvent for preventing a fire and a danger by toxicity. Further, there is a drawback that the solvent is expensive and many costs are required for recollecting it from a diluted aqueous solution. Because of the various drawbacks, a variety of investigations are made for shifting from an organic solvent type to a water-based emulsion in the elastic polymer compound for coating on the nonwoven sheet-like material. However, it is the existing state that there is not still obtained an artificial leather having a satisfying a feeling and physical properties using a water-based emulsion. In general, a polyurethane having a linear structure is obtained by allowing to react a long chain diol having hydroxyl groups at both terminals with an organic diisocyanate and a relatively low molecular weight diol or diamine which is named a chain extender having two active hydrogens, and a technical background relating to the polyurethane is as described in technical background relating to the present inventions No. 1 and No. 2. DISCLOSURE OF THE INVENTION Accordingly, purpose of the present inventions No. 1 and No. 2 is to provide a spandex filament which is excellent in recovering ability of elasticity, strength, and hydrolysis resistance, a polyurethane which provides it, and a polyester diol which provides thereof. The present inventors found out that the above-described problems can be solved by the use of a polyester diol obtained from a specified branched aliphatic diol, e-caprolactone, and adipic acid, which is a raw material for a polyurethane, and the present invention No. 1 has been completed. Further, the present inventors found out that the above-described problems can be solved by the use of a polyester diol obtained from a specified branched aliphatic diol, .epsilon.-caprolactone, and an aliphatic dicarboxylic acid having a carbon number of 10-12, and the present invention No. 2 has been completed. That is, according to the present invention No. 1, as (1), there is provided a polyester diol containing at least one diol selected from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol, .epsilon.-caprolactone, and adipic acid as constructing components. Further, as (2), there is provided a polyester diol as described in the (1), in which a number average molecular weight ranges in 500-5,000. Still further, as (3), there is provided a polyester diol as described in the (1) or (2), in which (the content of a constructing unit polyester)/(the content of constructing unit of .epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and the polyester is composed of at least one diol selected from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol, and adipic acid. Also, as (4), there is provided a polyurethane obtained from a polyester diols as described in any one of the (1)-(3) and an organic diisocyanate. And also, as a (5), there is provided a spandex filament which comprises the polyurethane in the (4). Further, according to the present invention No. 2, as (1), there is provided a polyester diol containing a branched aliphatic diol, .epsilon.-caprolactone, and an aliphatic dicarboxylic acid having a carbon number of 10-12 as constructing components. Further, as a (2), there is provided a polyester diol as described in the (1), in which a number average molecular weight ranges in 500-5,000. Still further, as a (3), there is provided a polyester diol as described in the (1) or (2), in which (the content of a constructing unit polyester)/(the content of constructing unit of .epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and the polyester is composed of a branched diol and an aliphatic dicarboxylic acid having a carbon number of 10-12. Also, as (4), there is provided a polyurethane obtained from a polyester diols as described in any one of the (1)-(3) and an organic diisocyanate. And also, as a (5), there is provided a spandex filament which comprises the polyurethane described in the (4). Purpose of the present invention No. 3 is to provide a spandex filament which is particularly excellent in view of hydrolysis resistance, and a polyurethane which provides thereof. The present inventors found out that the above-described problems in the present invention No. 3 can be solved by the use of a polyester diol containing a specified diol as a raw material for the polyurethane, and the present invention has been completed. That is, according to the present invention No. 3, as (1), there is provided a polyurethane obtained by allowing to react a polyester diol containing 2,4-diethyl-1,5-pentanediol as a constructing component with an organic diisocyanate. Further, as (2), there is provided a polyurethane described in the (1), in which a number average molecular weight ranges in 500-5,000. Still further, as (3), there is provided a spandex filament which comprises the polyurethane described in the (1) and (2). Purpose of the present invention No. 4 is to provide a spandex filament in which there is improved washing resistance as a weatherability, and to provide a polyurethane which provides thereof. The present inventors found out that the above-described problems can be solved by the use of a polyester diol in which a polyol component (A) is composed of a polyol (A1) having an ultraviolet ray-absorbable group or a lactone-modified polyol (A2) therefrom and other polyol (A3) as a raw material for the polyurethane, and the present invention has been completed. That is, according to the present invention No. 4, as (1), there is provided a polyurethane obtained from a polyetherpolyol (X) containing a polyol component (A) composed of a polyol (A1) having an ultraviolet ray-absorbable group or a lactone-modified polyol (A2) therefrom and other polyol components (A3), adipic acid (B), and an organic diisocyanate (Y). Further, as (2), there is provided a polyurethane described in the (1), in which the polyol (A1) having an ultraviolet ray-absorbable group is a compound represented by formula (1). ##STR1## Still further, as (3), there is provided a polyurethane described in the (1) or (2), in which the lactone is .epsilon.-caprolactone. Also, as (4), there is provided a polyurethane described in any one of the (1)-(3), in which a number average molecular weight of the polyester polyol ranges in 500-5,000. And also, as (5), there is provided a polyurethane described in any one of the (1)-(4), in which (a constructing unit content of the polyester)/(the content of constructing unit of a lactone) is 5/95-80/20 (weight ratio), and the polyester is composed of the polyol compound (A) and adipic acid. And also, as the present invention (6), there is provided a polyurethane as described in any one of embodiments (1)-(5), in which a molar ratio of constructing unit content in the polyol {(A1)+(A2)}/{(A1)+(A2)+(A3)} ranges from 0.01 to 1.0. And also, as the present invention (7), there is provided a spandex filament which comprises the polyurethane described in any one of the (1)-(6). Purpose of the present invention No. 5 is to provide a tertiary amino group-contained additive which is employed for a spandex polymer, in which solubility into DMAc which is a solvent is higher, by which the spandex polymer is protected from deterioration and discoloration, and in which a decrease of elasticity (permanent extension (set)) is further improved in relation to the use of an already-known tertiary amino group-contained additive having a high molecular weight and steric hindrance, to provide a polyurethane composition and a spandex composition containing the additives. The present inventors, as an intensive investigation for solving the above-described problems, found out that an acrylic-based copolymer has a high solubility into DMAc which is a solvent and has an exact effect, and the above-described problems can be solved, which contains a novel tertiary amino group formed by a dialkylaminomethyl(meth)acrylate and a reactive monomer having a specified structure which are an essential copolymerizable component, and the present invention No.5 has been completed. That is, according to the present invention No. 5, as (1), there is provided a dialkylamino group-contained acrylic-based copolymer formed by an essential copolymer component which includes a dialkylaminoethyl(meth)acrylate represented by a general formula (1) described below and a reactive monomer represented by a general formula (2) described below. CH.sub.2.dbd.CRCOOCH.sub.2 CH.sub.2 NR.sup.0 R.sup.0 (1) (in the formula, R is a hydrogen atom or a methyl group, R.sup.0 is an alkyl group having a carbon atom number of 1-4) CH.sub.2.dbd.CRCOOCH.sub.2 CH.sub.2 O[--C(.dbd.O)(CR.sup.1 R.sup.2).sup.2x --O--].sub.n --H (2) (in the formula, R is a hydrogen atom or a methyl group, x pieces of R.sup.1 and R.sup.2 are independently a hydrogen atom or an alkyl group having a carbon atom number of 1-12, respectively, and n pieces of ring-opened lactone chains may be identical or different from each other. x is an integer of 4-7, and an average value of n is 1-5) Further, as (2), there is provided a polyurethane composition characterized by containing a dialkylamino group-contained acrylic-based copolymer described in the present invention (1). Still further, as (3), there is provided a polyurethane composition as described in the invention (3), in which the content of the dialkylamino group-contained acrylic-based copolymer is 0.5-10% by weight. Also, as (4), there is provided a spandex composition containing a dialkylamino group-contained acrylic-based copolymer as described in the invention (1). Also, as (5), there is provided a spandex composition as described in the invention (4), in which the content of the dialkylamino group-contained copolymer is 0.5-10% by weight. Purpose of the present invention No. 6 is to provide a polyurethane which provides an artificial leather which is excellent in a recovering ability of elasticity, strength, and hydrolysis resistance, that is, which satisfies hydrolysis resistance, wrinkle resistance, an adhesive property, and a feeling. The present inventors, as a result of an intensive investigation for solving the purpose in the present invention No. 6, have attained to the present invention. That is, according to the present invention No. 6, as (1), there is provided a polyester diol containing at least an aliphatic dicarboxylic acid, an aliphatic diol, and e-caprolactone as constructing component units. Further, as (2), there is provided a polyester diol as described in the (1), in which a number average molecular weight of the polyester polyol ranges in 500-5,000. Still further, as (3), there is provided a polyester diol as described in the (1) or (2), in which (the content of a polyester constructing unit composed of an aliphatic diol and an aliphatic dicarboxylic acid having a carbon number of 9-12)/(the content of .epsilon.-caprolactone constructing unit) ranges in 5/95-80/20 (weight ratio). Also, as (4), there is provided a polyurethane obtained from a polyester diol as described in any one of the (1)-(3) and an organic diisocyanate. And also, as (5), there is provided a polyurethane described in the (4) for an artificial leather |
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