Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2001-10-11
2003-07-15
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C428S423100, C524S590000, C528S044000
Reexamination Certificate
active
06593419
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for producing a polyurethane resin which forms a sheet-form article such as a synthetic leather, an artificial leather, a film, a sheet form article such as a sheet for molding, or a surface of the sheet-form article excellent in dry touch property and oleic acid-resistance. The present invention also relates to a sheet-form article.
BACKGROUND OF THE INVENTION
Heretofore, polyurethane resins have been widely used for sheet-form articles such as synthetic leathers, artificial leathers, films, or sheets for molding or surface treatment of the sheet-form articles. In theses field, various feel is required for the sheet-form articles when they are touched, together with higher durability. Particularly, in the uses for wheeled vehicles and the like in which a high performance is required, a polyurethane resin having both of dry touch property and oleic acid-resistance has been desired.
Dry touch property means a feel free from so-called wet touch when a sheet-form article is touched. Hitherto, for example, a method of blending a polyurethane resin with a hard polymer or a technique for enhancing crystallinity of a polyurethane resin have been employed but these method and technique result in a defect that flexural resistance and a soft feel of a sheet-form article thereof are deteriorated.
Moreover, oleic acid-resistance is a substitute property for the durability against human sweat which comes into contact with a sheet-form article. Hitherto, so-called yellowing or hardly yellowing polyurethane resins wherein aromatic isocyanates are used have exhibited relatively satisfactory oleic acid-resistance but there is a problem of poor discoloring resistance. On the other hand, so-called yellowing-free polyurethane resins wherein aliphatic isocyanates are used are excellent in discoloring resistance but it is difficult to attain satisfactory oleic acid-resistance.
SUMMARY OF THE INVENTION
An object of the invention is to provide a method for producing a polyurethane resin excellent in discoloring resistance and also having both of dry touch property and oleic acid-resistance, which is hitherto difficult to obtain.
Another object of the present invention is to provide a resin composition comprising the polyurethane resin.
A still other object of the present invention is to provide a sheet-form article comprising the polyurethane resin.
Other objects and effects of the present invention will become apparent from the following description.
As a result of extensive studies, the present inventors have found that the above problem can be solved by using, as components of a compound having an active hydrogen-containing group, (A
1
) a compound having one spiro ring and active hydrogen-containing groups at both ends and (A
2
) an aliphatic polycarbonate polyol, and thus, have accomplished the invention.
Namely, the invention provides a method for producing a polyurethane resin which comprises reacting: (A) a compound having an active hydrogen-containing group, containing (A
1
) a compound having one spiro ring and active hydrogen-containing groups at both ends and (A
2
) an aliphatic polycarbonate polyol; (B) a polyisocyanate; and (C) a chain-extending agent, preferably a diamine compound.
The present invention also provides a polyurethane resin composition comprising the polyurethane resin.
Furthermore, the present invention also provides a sheet-form article comprising the resin or the resin composition.
In a preferred embodiment, the content of said compound (A
1
) is from 0.2 to 40% by weight relative to the polyurethane resin.
In another preferred embodiment, said compound is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane.
DETAILED DESCRIPTION OF THE INVENTION
As the compound (A
1
) having one spiro ring and active hydrogen-containing groups at both ends, a glycol, a diamine, or the like represented by the following formula (1) is mentioned.
(wherein R represents an active hydrogen-containing alkyl group)
Specific examples of the glycol include 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-methyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-1-methyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(2-hydroxyethyl-2-methyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-methyl-2-hydroxy-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-2-hydroxy-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1,1-dimethyl-2-hydroxy-2-methoxylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-1-methyl-2-hydroxy-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, and 3,9-bis(2-hydroxypropyl)-2,4,8,10-tetraoxaspriro[5.5]undecane.
Examples of the diamine include 3,9-bis(1,1-dimethyl-2-aminoethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(2-aminoethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-methyl-2-aminoethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-2-aminoethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-1-methyl-2-aminoethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(2-aminoethyl-2-methyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-methyl-2-amino-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-2-amino-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1,1-dimethyl-2-amino-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9-bis(1-ethyl-1-methyl-2-amino-2-methylethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane, 3,9bis(2-aminopropyl)-2,4,8,10-tetraoxaspriro[5.5]undecane and the like. Among these active hydrogen-containing group-having compounds, preferred is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspriro[5.5]undecane.
The content of the compound (A
1
) having a spiro ring and active hydrogen-containing groups at both ends, in the polyurethane resin is preferably from 0.2 to 40% by weight, and the content of such a range can result in excellent dry tough property and solution stability. The most preferred content is from 0.5 to 35% by weight.
The aliphatic polycarbonate polyol (A
2
) for use in the invention has a constituting unit represented by the following formula (2).
(wherein R represents an aliphatic alkylene group, preferably an aliphatic alkylene group having 4 to 20 carbon atoms, more preferably an aliphatic alkylene group having 4 to 9 atoms. Particularly preferred carbon number of the R groups in the aliphatic alkylene groups is 4 alone or a combination of 4 and 6.
For the production of the aliphatic polycarbonate polyol for use in the invention, a glycol is used as a starting material. Examples of the glycol having an aliphatic alkylene group which satisfies the requirement of the aliphatic alkylene group (R) in the constituting unit (formula (2)) of the aliphatic polycarbonate polyol (A
2
) in the active hydrogen-containing group-having compound of the invention include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, 1,3-cyclohexanediol, 2,2′-bis(4-hydroxycyclohexyl)propane, 1,4-dimethylolcyclohexane, dipropylene glycol, polytetramethylene glycol, 2,6′-dihydroxyethyl hexyl ether, 2,4′-dihydroxyethyl butyl ether, 2,5′-dihydroxyethyl pentyl ether, 2,3′-dihydroxy-2,2′-dimethylpropyl ether, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propnaediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular w
Nishino Shigetoki
Takeuchi Hideyuki
Tanaka Hiroki
Armstrong Westerman & Hattori, LLP
Dainippon Ink and Chemicals Inc.
Niland Patrick D.
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