Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From reactant having at least one -n=c=x group as well as...
Reexamination Certificate
2001-03-08
2002-12-31
Gorr, Rachel (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From reactant having at least one -n=c=x group as well as...
C528S906000, C428S364000
Reexamination Certificate
active
06500911
ABSTRACT:
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 &egr;-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, al
Endo Toshio
Miho Takuya
Daicel Chemical Industries Ltd.
Gorr Rachel
Morgan & Finnegan , LLP
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