CN102232092A - Process for production of polyurethane, and uses of polyurethane produced thereby - Google Patents

Abstract

Provided is a process for production of a polyurethane urea from a polyether polyol, a polyisocyanate compound, and a chain extender, by which a polyurethane and a polyurethane urea that exhibit low tackiness and high peelability can be produced. Disclosed is a process for production of a polyurethane using (a) a polyhydroxylated hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, which is characterized in that the production is conducted in the presence of an aprotic polar solvent.

Description

The manufacture method of urethane reaches the purposes of the urethane that is obtained by this method

Technical field

The urethane and this purposes that the present invention relates to the manufacture method of urethane, obtain by this manufacture method.

Background technology

Urethanes and urethane urea compounds are applied to various fields.Urethanes is mainly by manufacturings such as the polyol of polyester polyol or polyether glycol etc. and isocyanate compound and the chainextender that adds as required, whipping agent, foam stabilizers, through being commonly used for the polyurethane series spandex fiber or urethane urea is purposes such as spandex fiber.Especially, have the fiber of urethane urea structure, because the soft chain segment composition uses polyether glycol, hard segment uses the high polyamine compounds of cohesive force, so have the character of elastic properties, the restorative excellence that stretches., these polyurethane series spandex fibers, because the adhesivity height between the fiber, so easy zbility worsens when spinning, in addition, because frictional force is big, so break in the machine in the manufacturing procedure of spinning-drawing machine, warper, knitting machine or the guide rail of line contact.Therefore, be easy to generate problems such as broken string takes place in manufacturing procedure.Therefore, for the machine that reduces manufacturing procedure and the frictional force between the line, the method of interpolation as the solid metal soap of finish or oil soluble polymer, higher fatty acid, amino modified polysiloxane etc. arranged, perhaps be dispersed with the method for talcum, silicon-dioxide, colloidal alumina or titanium oxide etc. as smooth agent, (for example, patent documentation 1) such as methods that silicon dibasic alcohol or silicon diamines imported to the part of polyurethane backbone is further arranged.

; even also there is following problem in the method; can not be prevented adherent effect fully; perhaps smooth agent makes spinning-drawing machine, warper, knitting machine or yarn carrier produce great abrasion; perhaps warping, in compiling operation; oligopolymer in the fiber that extracts by the finish composition or the solid in the finish or high viscosity composition become material that solid or pulpous state separate in large quantities attached on the fiber; stained product or make machinery or utensil stops up, thus do not solve problem.Therefore, seek a kind of like this manufacture method of urethane, even do not use such finish or smooth agent, adhesivity also reduces, and the easy zbility when spinning (or the separability between the urethane) height has high separability.

On the other hand, the raw material of urethane uses the example of the poly-hydroxy hydrocarbon system polymkeric substance with hydroxyl, being useful on raising the close-burning of polyolefin material for example is the purposes (patent documentation 2) of the properties-correcting agent of resin as carbamate, perhaps mix with polytetramethylene glycol and make urethane, attempt to improve the Study on durability (patent documentation 3) of polyurethane series spandex fiber as macromolecule polyol., in the method for patent documentation 3 records, the hydrophobicity of macromolecule polyol is too high, and there is gelation when making urethane in the intermiscibility deterioration with polyether glycol, disperses inhomogenous problem when perhaps making yarn or film.In addition, known, the extendible cloth and silk that the fiber that the urethane that the method that adopts patent documentation 3 to put down in writing is made constitutes is made or the resistance to chlorine of swimming suit, hot water resistance, photostabilization excellence etc., but be to use poly-hydroxy hydrocarbon system polymkeric substance as raw material with hydroxyl, the adhesivity of urethane reduces, even the adhesivity of shaping things such as film that is made of urethane or spandex fiber reduces, and is not used in the purpose that improves separability.In addition, the polyurethane series spandex fiber of patent documentation 3 records, though exemplified polyvalent alcohol and polyamine as chainextender, but in fact, it is the spandex fiber that obtains that spin processes obtains that dissolves by with the polyvalent alcohol chainextender, if will obtain using the so-called urethane urea structure of polyamine with this method, gel takes place during the chain extension reaction easily or three-dimensional cross-linkedly wait abnormal response, existence is difficult to be configured as the problem of the fiber or the film of homogeneous.

In addition, on the other hand, having finished following research, is purpose with all rerum naturas that improve polyurethane elastomeric fiber, and the material composition of improvement urethane.For example, as the example that uses polyester polyol, propose by the polyvalent alcohol that has alkyl with side chain serve as glycol constituent that must composition and with the dimeracid serve as must composition the hydrophobicity polyester polyol (patent documentation 4) that forms of carboxylic acid constituent., even when using these polyester polyols, also still can not get showing the urethane of sufficient separability.

The background technology document

Patent documentation

Patent documentation 1: the spy of Japan opens flat 10-259577 communique

Patent documentation 2: the spy of Japan opens flat 6-158016 communique

Patent documentation 3: the spy of Japan opens flat 11-131325 communique

Patent documentation 4: the spy of Japan opens the 2002-212273 communique

Summary of the invention

The problem that invention will solve

The present invention is in view of above-mentioned problem, the object of the present invention is to provide a kind of method of making urethane and urethane urea and to making the useful new polyester polyol of urethane urea, during from polyether glycol, polyisocyanate compounds and chainextender manufacturing urethane, urethane and urethane urea are exceedingly useful to the high function urethane purposes of polyurethane elastomeric fiber or film and dress material etc., and, adhesivity is low, the separability height.

For solving the means of problem

The inventor has carried out conscientious research in order to solve above-mentioned problem, found that, when making urethane, by using polyether glycol and molecular end to have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl, the polyester polyol that preferably has specific structure and certain oxygen level, more preferably mix the pure and mild polyether glycol of this polyester polyols, by under the coexistence of solvent, reacting with polyisocyanate compounds and chainextender, can reduce the adhesivity of resulting urethane and urethane urea, can improve separability and the easy zbility when spinning, thereby finish the present invention.

That is to say, of the present inventionly will be intended to following [1]～[29].

[1] a kind of manufacture method of urethane, it is characterized in that, make (a) molecular end have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) raw material of chainextender carry out polyaddition reaction, when obtaining urethane, (a) to have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl for (a) molecular end be 0.01～50.00 weight % with (b) ratio of the total of polyether glycol to the poly-hydroxy hydrocarbon system polymer phase of molecular end with at least one hydroxyl, is being selected from the acid amides series solvent, N-Methyl pyrrolidone, the coexistence of the solvent of N-ethyl pyrrolidone and methyl-sulphoxide is reaction down.

[2] preferred, the manufacture method of the urethane of above-mentioned [1] record is characterized in that the number-average molecular weight that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is 500～5000.

[3] preferred, the manufacture method of the urethane of above-mentioned [1] or [2] record is characterized in that, the average hydroxyl number of each molecule that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is 1.5～2.7.

[4] preferred, the manufacture method of the urethane of each record is characterized in that in above-mentioned [1]～[3], and described (c) polyisocyanate compounds is an aromatic poly-isocyanate.

[5] preferred, the manufacture method of the urethane of each record is characterized in that in above-mentioned [1]～[4], and described (d) chainextender is a polyamine compounds.

[6] preferred, the manufacture method of the urethane of each record is characterized in that in above-mentioned [1]～[5], and the main framing that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is a hydrogenated butadiene polymer.

[7] preferred, the manufacture method of the urethane of each record in above-mentioned [1]～[6], it is characterized in that, the poly-hydroxy hydrocarbon system polymkeric substance that described (a) molecular end has at least one hydroxyl be by (A) poly-hydroxy hydrocarbon polymer with (B) contain the polyester polyol that ester group compound or carboxylated compound form.

[8] preferred, the manufacture method of the urethane of above-mentioned [7] record, it is characterized in that, in the described polyester polyol, described (A) and described (B) form at least one ester bond, and the oxygen level in this polyester polyol is that 2.0 quality % or 2.0 quality % are above, 13.5 quality % or below the 13.5 quality %.

[9] preferred, the manufacture method of the urethane of above-mentioned [7] or [8] record is characterized in that described (B) is polylactone.

[10] preferred, the manufacture method of the urethane of each record is characterized in that in above-mentioned [7]～[9], and described polyester polyol forms (B) (A) segmented copolymer of (B) type by described (A) and described (B).

[11] preferred, the manufacture method of the urethane of above-mentioned [7] or [8] record is characterized in that described (B) is dicarboxylic acid.

[12] preferred, the manufacture method of the urethane of above-mentioned [11] record is characterized in that the carbonatoms of described dicarboxylic acid is more than 2 or 2, below 15 or 15.

[13] preferred, the manufacture method of the urethane of above-mentioned [10] or [11] record is characterized in that described polyester polyol forms (AB) by described (A) and described (B) _nThe segmented copolymer of A type (wherein, n is the integer more than 1 or 1).

[14] a kind of urethane, the manufacture method manufacturing by the urethane of each record in described [1]～[13] obtains.

[15] a kind of urethane, it is characterized in that, contain poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender, the shared part by weight of (b) polyether glycol in the urethane is 54 weight %～99 weight %.

[16] a kind of polyurethane formed body is characterized in that, by the urethane formation of described [14] or [15] record.

[17] a kind of polyurethane formed body, it is characterized in that, by contain poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) urethane of chainextender constitute, it is below 0.22 or 0.22 that the atom on the surface of this polyurethane formed body is formed (Sauerstoffatom/carbon atom).

[18] preferred, the polyurethane formed body of above-mentioned [17] record is characterized in that, the water contact angle on the surface of described polyurethane formed body is more than 80 degree or 80 are spent.

[19] a kind of film is characterized in that, by the urethane formation of described [14] or [15] record.

[20] a kind of fiber is characterized in that, by the urethane formation of described [14] or [15] record.

[21] a kind of polyester polyol, it is characterized in that, by (A) poly-hydroxy hydrocarbon polymer with (B) contain ester group compound or carboxylated compound forms, described (A) and described (B) form at least one ester bond, and the oxygen level in the described polyester polyol is that 2.0 quality % or 2.0 quality % are above, 13.5 quality % or below the 13.5 quality %.

[22] preferred, the polyester polyol of above-mentioned [21] record is characterized in that described (B) is polylactone.

[23] preferred, the polyester polyol of above-mentioned [21] or [22] record is characterized in that described polyester polyol forms (B) (A) segmented copolymer of (B) type by described (A) and described (B).

[24] preferred, the polyester polyol of above-mentioned [21] record is characterized in that described (B) is dicarboxylic acid.

[25] preferred, the polyester polyol of above-mentioned [24] record is characterized in that the carbonatoms of described dicarboxylic acid is more than 2 or 2, below 15 or 15.

[26] preferred, the polyester polyol of above-mentioned [24] or [25] record is characterized in that described polyester polyol forms (AB) by described (A) and described (B) _nThe segmented copolymer of A type (wherein, n is the integer more than 1 or 1).

[27] preferred, the polyester polyol of each record is characterized in that in above-mentioned [21]～[26], and the number-average molecular weight of described polyester polyol is more than 500 or 500, below 5000 or 5000.

[28] preferred, the polyester polyol of each record is characterized in that in above-mentioned [21]～[27], and described (A) poly-hydroxy hydrocarbon polymer is a hydrogenation polydiene polyvalent alcohol.

[29] a kind of polymkeric substance is characterized in that, constitutes the formation amino-formate bond of one at least of the hydroxyl of the polyester polyol of each record in described [21]～[28].

The invention effect

According to the present invention, can simultaneously keep the certain intermiscibility with polyether glycol, one side is made urethane, can reduce the adhesivity of the urethane that obtains.In addition, will obtain polyurethane formed the time, can improve molding separability each other.And, the spandex fiber that use is made of this urethane, when being configured as dress material etc., because the reduction of the usage quantity of finish or smooth agent etc. brings cost cutting, the obstruction frequency of, machinery stained by product or utensil reduces the raising that brings operational stability, frictional force reduces, and can expect to drive electric power reduction etc. thus.

Embodiment

Below the explanation of Ji Zai constitutive requirements is examples (typical example) of embodiments of the present invention, the invention is not restricted to these contents.Below, particular content is described.

＜urethane 〉

Urethane of the present invention can be by (a) of the present invention molecular end being had at least 1 hydroxyl poly-hydroxy hydrocarbon system polymkeric substance with (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender use and obtain.

Urethane among the present invention contains poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least 1 hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender.In addition, the shared part by weight of (b) polyether glycol in the urethane, there is no particular limitation, 54～99 weight % normally, preferred 60～90 weight %, more preferably 70～85 weight %.This ratio is big more, and the flexibility of the urethane that obtains has the tendency of raising more, and on the other hand, this ratio is more little, and the separability of the urethane that obtains has the tendency of raising more.

Include in the urethane of the present invention constitute (a) of the present invention molecular end have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl or (b) one at least of the hydroxyl of polyether glycol form the polymkeric substance of amino-formate bond.Preferably have the polymkeric substance of following part structure, just in polymeric chain, have the polymkeric substance of following such structure, constitute (a) of the present invention molecular end have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl or (b) two or more hydroxyls of polyether glycol form amino-formate bonds.

[changing 1]

(in the formula (I), molecular end that HO-X-OH represents (a) of the present invention has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl or (b) polyether glycol.)

The content or the position of the described polymkeric substance in the urethane of the present invention are not particularly limited, and get final product so long as have the polymkeric substance of said structure in polymeric chain.The compound that contains said structure has for example urethane resin, urethane urea resin or their prepolymer etc. for example.

In addition, in the present invention, " containing the poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least one hydroxyl; (b) polyether glycol; (c) polyisocyanate compounds and (d) urethane of chainextender " is to have amino-formate bond (macromolecular compound NHCOO-) in the repeating unit of main chain, the repeating of its main chain constitutes the unit to be not only from (a) and (b) the two compound, also can be as only from the urethane of the macromolecular compound of (a), as only from the urethane of the macromolecular compound of (b) and the material that they mix and obtain.In addition, also can be unreacted (a) and (b), (c) or (d) and the above-mentioned macromolecular compound material that mixes and obtain.

The so-called urethane of the present invention as long as there is not special restriction, is just represented urethane or urethane urea, and these 2 kinds of resins have roughly the same rerum natura, and this is just known before being.On the other hand, as the difference of structural attitude, urethane is that chainextender uses the manufacturing of short chain polyvalent alcohol to obtain, and urethane urea to be chainextender use the polyamine compounds manufacturing to obtain.

Usually, each proportion of composing is with respect to urethane, (a) molecular end is had the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl be set at A with (b) the total mole number of the hydroxyl of polyether glycol, the mole number of the isocyanate group of (c) polyisocyanate compounds is set at B, when the mole number of the active hydrogen substituting group (hydroxyl and amino) of (d) chainextender is set at C, A: B is generally 1: 10～1: 1 scope, preferred 1: 5～1: 1.05, more preferably 1: 3～1: 1.1, more preferably 1: 2.5～1: 1.2, preferred especially 1: 2～1: 1.2, and (B-A): C is generally 1: 0.1～and 1: 5, be preferably 1: 0.8～1: 2, more preferably 1: 0.9～1: 1.5, more preferably 1: 0.95～1: 1.2, preferred especially 1: 0.98～1: 1.1 scope.

＜(a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl 〉

The poly-hydroxy hydrocarbon system polymkeric substance that molecular end among the present invention has at least 1 hydroxyl is meant that hydrocarbon skeleton with representative divinyl, isoprene, chloroprene equiconjugate diene and so on is for repeating unitary polymkeric substance or polyester polyol described later.By they are mixed use with polyether glycol, use them to make urethane, can improve the adhesivity of the urethane that obtains, the separability of polyurethane moulding thing, the easy zbility when spinning.

With hydrocarbon skeleton for repeating unitary polymkeric substance, preferable examples has the following polymkeric substance that obtains, for example by being polymerization starter with the hydrogen peroxide, make 1, the 3-divinyl carries out radical polymerization, directly make end and have the conjugated diene polymer of hydroxyl, perhaps use anionic polymerization catalyst, make reactive polymer terminal and the basic metal bonding, then by making reactions such as mono-epoxy compounds or formaldehyde, make end and have the conjugated diene polymer of hydroxyl, the conjugated diene polymer that obtains is carried out the polymkeric substance that hydrogenation obtains according to well-established law.Also have, at this moment, above-mentioned conjugated diolefine can with vinyl monomer copolymerization such as amount 30 weight % or the vinylbenzene below the 30 weight %, vinyl cyanide, (methyl) methyl acrylate, vinyl-acetic ester.

In addition, give an example useful ozone etc. to iso-butylene or iso-butylene and isoprene, 1, the polymkeric substance oxygenolysis of 3-pentadiene equiconjugate diene is handled, and then, reduces processing with lithium aluminium hydride etc., obtain the isobutylene-based polymer that end has hydroxyl, by well-established law with the polymkeric substance after the polymkeric substance hydrogenation that obtains, and, equally with the multipolymer oxygenolysis of alpha-olefin such as ethene, propylene and diene compound, reduce processing, carry out the polymkeric substance etc. after the hydrogenation.

Molecular end of the present invention has in the poly-hydroxy hydrocarbon system polymkeric substance of 1 hydroxyl at least, preferably, main framing is the poly-hydroxy hydrocarbon system polymkeric substance of hydrogenated butadiene polymer, hydrogenated polyisoprene and polyisobutene, from starting with easily or operating consideration, more preferably main framing is the polymkeric substance of hydrogenated butadiene polymer.

The molecular end that the present invention uses has the ratio of the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl, has the total amount of the poly-hydroxy hydrocarbon system polymkeric substance and the polyether glycol of at least 1 hydroxyl with respect to molecular end, preferably at 0.01 weight % or more than the 0.01 weight %.More preferably 0.03 weight % or more than the 0.03 weight %, further preferred 0.05 weight % or more than the 0.05 weight %, preferred especially 0.07 weight % or more than the 0.07 weight %, most preferably 0.1 weight %.This numerical value is big more, and the resinoid adhesivity of the urethane that obtains has the tendency of decline more.On the other hand, preferred 50.00 weight % of the upper limit or below the 50.00 weight %.More preferably 30.00 weight % or below the 30.00 weight %, further preferred 25.00 weight % or below the 25.00 weight %, preferred especially 15.00 weight % or below the 15.00 weight %, most preferably 10.00 weight % or below the 10.00 weight %.This value is more little, and the resinoid adhesivity of the urethane that then obtains descends, but its elastic properties or the restorative tendency that raising is arranged that stretches.

The number-average molecular weight of described poly-hydroxy hydrocarbon system polymkeric substance is 500～5000, and is preferred 700～4000, more preferably 900～3500, and normal temperature is liquid state or wax shape down.Number-average molecular weight is too high, and following tendency is arranged: the viscosity of polyether glycol or prepolymer, prepolymer solution becomes too high, causes operability or productivity to worsen, and the polyether polyols with reduced unsaturation that perhaps obtains rerum natura at low temperatures worsens.Cross lowly, following tendency is arranged: the polyether polyols with reduced unsaturation hardening that obtains, can't obtain sufficient flexibility, perhaps elastic performance such as intensity or elongation is insufficient, or stretches repeatedly, when recovering, stays the over-drastic residual set.In addition, polyester polyol is meant that intramolecularly has the ester bond more than at least 2 or 2 and the material of the hydroxyl more than 2 or 2, and two ends of preferred polyester polyvalent alcohol main chain are hydroxyl.

Polyester polyol of the present invention is by (A) described later poly-hydroxy hydrocarbon polymer and (B) contain the polyester polyol that ester group compound or carboxylated compound form, is (A) poly-hydroxy hydrocarbon polymer specifically and (B) contains the polymkeric substance that ester group compound or carboxylated compound form at least one ester bond.

The number of ester bond contained, that (A) poly-hydroxy hydrocarbon polymer forms is usually more than 1 or 1 in polyester polyol 1 molecule of the present invention.

Particularly, 1 molecule (A) poly-hydroxy hydrocarbon polymer can form a plurality of ester bonds in molecular end, also can form ester bond by a plurality of poly-hydroxy hydrocarbon polymers (A), and the total number of contained ester bond is more than 2 or 2 in the polyester polyol molecule.

Below, described separately to the important document that constitutes polyester polyol of the present invention.

＜(A) poly-hydroxy hydrocarbon polymer 〉

(A) poly-hydroxy hydrocarbon polymer among the present invention is meant with hydrocarbon skeleton to repeating unitary polymkeric substance, and has the polymkeric substance of at least 2 hydroxyls in the above-mentioned polymkeric substance.

To having no particular limits for repeating unitary polymkeric substance with above-mentioned hydrocarbon skeleton, can be with have beyond the element beyond carbon and the hydrogen element for example the halogen of chlorine, fluorine, bromine etc. as substituent hydrocarbon for repeating unitary polymkeric substance, but preferably with the hydrocarbon of carbon and hydrogen evolution for repeat unitary polymkeric substance (below, sometimes be referred to as hydrocarbon polymer), more preferably aliphatic hydrocarbon polymkeric substance.

It is that the hydrocarbon that repeats unitary polymkeric substance or have side chain with intramolecularly is for repeating unitary polymkeric substance that hydrocarbon polymer among the present invention has for example with straight chain shape hydrocarbon.

Because it is many that intramolecularly has the content of hydrocarbon of side chain, the fusing point of hydrocarbon polymer reduces, and becomes to handle easily, so preferably have the many hydrocarbon polymers of content of the hydrocarbon of side chain.

Above-mentioned hydrocarbon polymer can be 1 repeating unit polymeric self-aggregate, also can be the multipolymer that contains the repeating unit more than 2 or 2.

Carbonatoms to the repeating unit of above-mentioned hydrocarbon is not particularly limited, and is generally more than 2 or 2, is preferably more than 3 or 3, is generally below 9 or 9, is preferably below 6 or 6.

Can roll into a ball the end that imports polymkeric substance from easy high-ranking military officer, the control molecular weight is considered easily, poly-hydroxy hydrocarbon polymer among the present invention preferably contains the polymkeric substance of divinyl, iso-butylene, isoprene, chloroprene equiconjugate dienes, more preferably make hydrogenated butadiene polymer, hydrogenated polyisoprene and Parleam etc. make after the independent polymerization of conjugated diene the polymkeric substance that hydrogenation again obtains (below, the hydrogenation polydiene), from easiness or the easiness aspect consideration of processing, the more preferably hydrogenated butadiene polymer of starting with.

Poly-hydroxy hydrocarbon polymer among the present invention is the material that has at least 2 hydroxyls in polymkeric substance.The quantity of above-mentioned hydroxyl is so long as satisfy the scope of following oxygen level, usually without limits, but common more than 2 or 2, below 6 or 6, preferred below 3 or 3.Position to hydroxyl is not particularly limited, and preferably in molecular end hydroxyl is arranged, and more preferably has more than 2 or 2 in molecular end, and more preferably two ends at the main chain of hydrocarbon polymer have hydroxyl.

Poly-hydroxy hydrocarbon polymer (A) by formation polyester polyol of the present invention forms at least 1 ester bond, adjusts the hydrophobicity of polyester polyol, can obtain the polyester polyol with the intermiscibility saturated hydrocarbon ratio polymerization object height of polyether glycol.In addition, the urethane that uses such polyester polyol to obtain demonstrates high separability.

The number-average molecular weight of the poly-hydroxy hydrocarbon polymer among the present invention is usually more than 100 or 100, preferably more than 200 or 200, further more than preferred 300 or 300, usually below 5000 or 5000, preferably below 4000 or 4000, further preferably below 3000 or 3000.Less than above-mentioned lower value, following tendency is arranged: the polyether polyols with reduced unsaturation hardening that obtains, cause flexibility to descend, perhaps cause elastic performances such as intensity or elongation to descend, or stretch repeatedly, when recovering, stay the over-drastic residual set.Surpass above-mentioned higher limit, following tendency is arranged: the viscosity of polyether glycol or prepolymer, prepolymer solution becomes too high, and operability or productivity descend, and the polyether polyols with reduced unsaturation that perhaps obtains rerum natura at low temperatures descends.

Proterties to the poly-hydroxy hydrocarbon polymer among the present invention is not particularly limited, and usually, is liquid state or waxy at normal temperatures.

＜(B) contain ester group compound 〉

As long as the employed ester group compound that contains has ester group among the present invention, just there is no particular limitation, has repeating unit to carry out polymeric compounds by ester bond usually for example, and preferred lactone carries out the polylactone that ring-opening polymerization obtains.

＜polylactone 〉

Polylactone among the present invention can be by being that raw material carries out known polyreaction and obtains with the lactone.

The concrete lactone that uses has 6-caprolactone, 4-methyl caprolactone, 3 for example, 5,5-trimethylammonium caprolactone, 3,3,5-trimethylammonium caprolactone, beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi, γ-Wu Neizhi, oenantholacton etc., they can use separately, also can two or more mix use.Wherein, from start with easily, reactive high aspect considers preferred 6-caprolactone, δ-Wu Neizhi, γ-Wu Neizhi, more preferably 6-caprolactone.

Below, as by poly-hydroxy hydrocarbon polymer and contain the polyester polyol that ester group compound forms, be that example is described with the polyester polyol that forms by poly-hydroxy hydrocarbon polymer and polylactone.

＜the polyester polyol that forms by poly-hydroxy hydrocarbon polymer and polylactone 〉

In the polyester ester polyol of the present invention, one of optimal way is, between above-mentioned poly-hydroxy hydrocarbon polymer and following polylactone, form the ester group more than 1 or 1, in the hydroxyl that preferred poly-hydroxy hydrocarbon polymer 1 molecule has at least 1 forms ester bond, has a plurality of ester bonds in words 1 molecule of total between itself and polylactone; More preferably at least 1 in the terminal hydroxyl that has of poly-hydroxy hydrocarbon polymer 1 molecule forms ester bond between itself and polylactone, has a plurality of ester bonds in words 1 molecule of total.

Copolymerized form to above-mentioned poly-hydroxy hydrocarbon polymer and polylactone is not particularly limited, preferably by (A) poly-hydroxy hydrocarbon polymer part and (B) polylactone partly constitute (B) (A) polyester polyol of the segmented copolymer of (B) type.(B) be the ring-opening polymerization polymer of lactone, (A) He (B) carry out bonding by ester bond.

(A) or the polymerization degree (B) are not particularly limited,, consider that the molecular weight of raw material determines to get final product as long as make oxygen level and molecular weight in the polyester polyol become desired value.

According to the rerum natura of desired urethane resin, described by regulating (A) or the polymerization degree (B) can change the molecular weight or the oxygen level of the polyester polyol that is generated easily.Manufacture method is not particularly limited, can by solvent-free down, in the presence of catalyzer such as titanium isopropylate or tetrabutyl titanate, poly-hydroxy hydrocarbon polymer and lactone are reacted with requirement ratio obtain.

＜(B) carboxylated compound 〉

As long as employed carboxylated compound has carboxyl among the present invention, be not particularly limited, usually, the substituted carboxylic acid compound of monocarboxylic acid compound, dicarboxylic acid compound, alcohol acid or alcoxyl acid etc. etc. is arranged for example, the preferred dicarboxylic compound.

＜dicarboxylic acid 〉

The dicarboxylic acid compound that uses among the present invention can be in aliphatic dicarboxylic acid, the aromatic dicarboxylic acid any, the carbonatoms of aliphatic dicarboxylic acid is usually more than 2 or 2, preferably more than 3 or 3, more preferably more than 4 or 4, usually below 16 or 16, preferably below 15 or 15, more preferably below 14 or 14.Propanedioic acid, succsinic acid, maleic acid, FUMARIC ACID TECH GRADE, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1 are specifically arranged for example, 9-nonane dicarboxylic acid (1, the acid of 9-ノ Na メ チ レ Application ジ カ Le ボ Application), 1,10-decamethylene dicarboxylic acid, 1,11-11 support dicarboxylic acid, 1,12-12 methylene dicarboxylic acid etc.In addition, aromatic dicarboxylic acid has phthalic acid, m-phthalic acid, terephthalic acid, naphthalene diacid, anthracene diacid or luxuriant and rich with fragrance diacid etc. particularly for example.These can a kind ofly use, and the mixture that also can be used as two or more uses.In addition, also can use the halogen substituent etc. of acid anhydrides, alkyl ester or the unsaturated link(age) of these dicarboxylic acid.Wherein, from starting with easily and thermostability is high considers, preferred aliphat dicarboxylic acid, more preferably propanedioic acid, succsinic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, further preferred succsinic acid, hexanodioic acid.

Below, as the polyester polyol that forms by poly-hydroxy hydrocarbon polymer and carboxylated compound, be that example is described with the polyester polyol that forms by poly-hydroxy hydrocarbon polymer and dicarboxylic acid.

＜the polyester polyol that forms by poly-hydroxy hydrocarbon polymer and dicarboxylic acid 〉

The polyester polyol that is formed by poly-hydroxy hydrocarbon polymer and dicarboxylic acid among the present invention normally forms the polyester polyol of ester bond respectively between 2 carboxyls that at least one hydroxyl that 2 molecule poly-hydroxy hydrocarbon polymers have separately and 1 molecule dicarboxylic acid comprise.

Preferred (AB) that forms by poly-hydroxy hydrocarbon polymer (A) and dicarboxylic acid (B) _nThe polyester polyol of A type.(A) and (B) carry out bonding and get final product, also can be by the carboxylic acid derivative manufacturing of carboxylic acid diesters etc. by ester bond.

Usually, n is that the integer more than 1 or 1 gets final product, more preferably be equivalent to said n=1 o'clock, dicarboxylic acid two terminal each with the polyester polyol of the ABA type of a part poly-hydroxy hydrocarbon polymer bonding.

The molecular weight of the poly-hydroxy hydrocarbon polymer that can obtain usually is bigger, and is minimum also more than 1500 or 1500, two terminal reactions with the poly-hydroxy hydrocarbon polymer and the generation polyester polyol of dicarboxylic acid, and molecular weight is more than 3000 or 3000.This be because, when the n value became big, the molecular weight of polyester polyol becomes excessive, has following tendency: the viscosity of prepolymer or prepolymer solution was too high, operability when making urethane or productivity descend, and the rerum natura of the polyether polyols with reduced unsaturation that perhaps obtains in low temperature descends.

The intramolecularly of polyester polyol of the present invention can have the structure beyond the said structure, but does not preferably contain the polyester polyol of other structures except that above-mentioned part.

In addition, the formation thing (A) that is used to form ester bond has been described in detail in detail in the above-mentioned record has reached (B), but polyester polyol of the present invention is not limited to this, as long as the molecular structure that obtains is identical, it can be the material that obtains by any raw material, reaction method.

＜oxygen level 〉

Oxygen level in the polyester polyol of the present invention is meant the oxygen level in the 1 molecule polyester polyol, typically refers to the ratio of the molecular weight of Sauerstoffatom contained in the molecule and 1 molecule polyester polyol.For example, when having 10 Sauerstoffatoms in the polyester polyol of molecular weight 2000, be (10 * 16/2000) * 100=8.0 quality %.

The oxygen level of polyester polyol of the present invention is 2.0 quality % or more than the 2.0 quality %, 13.5 the scope that quality % or 13.5 quality % are following, preferred 2.2 quality % or more than the 2.2 quality %, more preferably 2.5 quality % or more than the 2.5 quality %, further preferred 3.0 quality % or more than the 3.0 quality %, preferred 13 quality % or below the 13 quality %, more preferably 12 quality % or below the 12 quality %, further preferred 11.0 quality %.Deficiency is above-mentioned down in limited time, and is insufficient with the intermiscibility of polyether glycol or the solvability in solvent, surpasses above-mentioned going up and prescribes a time limit, and the resinoid adhesivity of the urethane that obtains increases, thereby undesirable.

Ratio to the poly-hydroxy hydrocarbon polymer in the polyester polyol of the present invention is not particularly limited, usually, mass ratio is 10.0 quality % or more than the 10.0 quality %, preferred 20.0 quality % or more than the 20.0 quality %, more preferably 30.0 quality % or more than the 30.0 quality %, further preferred 40.0 quality % or more than the 40.0 quality %, preferred especially 45.0 quality %.The mass ratio of the poly-hydroxy hydrocarbon polymer in the polyester polyol of the present invention is big more, and the adhesivity of the urethane that obtains has the tendency of decline more.On the other hand, the upper limit is not particularly limited, be 99.5 quality % or below the 99.5 quality %, preferred 99.0 quality % or below the 99.0 quality %, more preferably 98.5 quality % or below the 98.5 quality %, further preferred 98.2 quality % or below the 98.2 quality %, preferred especially 98.0 quality % or below the 98.0 quality %.Above-mentioned mass ratio is more little, with the intermiscibility of polyether glycol or the solvability in polar solvent the tendency of raising is arranged more.

The rerum natura of＜polyester polyol 〉

The number-average molecular weight of polyester polyol of the present invention can be adjusted by (A) that use or kind (B) or amount.Number-average molecular weight is generally more than 500 or 500, more than preferred 600 or 600, further more than preferred 800 or 800, is generally below 10000 or 10000, is preferably below 7000 or 70000, further below preferred 5000 or 5000.Number-average molecular weight is represented the molecular-weight average of each molecule.Number-average molecular weight surpasses above-mentioned higher limit, and following tendency is arranged: the viscosity of prepolymer, prepolymer solution becomes too high, and operability or productivity descend, and the polyether polyols with reduced unsaturation that perhaps obtains rerum natura at low temperatures descends.Less than above-mentioned lower limit, following tendency is arranged: the polyether polyols with reduced unsaturation hardening that obtains sometimes, can't obtain sufficient flexibility, perhaps elastic performance such as intensity or elongation is insufficient sometimes, stretches repeatedly, when recovering, stays the over-drastic residual set.

＜(b) polyether glycol 〉

Polyether glycol among the present invention is the oxy-compound that has at least one or more than one ehter bond in the intramolecular main framing, repeating unit in the main framing can be any of stable hydrocarbon or unsaturated hydrocarbons, for example have for example, 1,4-butyleneglycol unit, the 2-methyl isophthalic acid, 4-butyleneglycol unit, the 3-methyl isophthalic acid, 4-butyleneglycol unit, 1, the ammediol unit, 1,2-propylene glycol unit, the 2-methyl isophthalic acid, the ammediol unit, the 2 unit, the 3-methyl isophthalic acid, 5-pentanediol unit, 1,2-ethylene glycol unit, 1,6-hexylene glycol unit, 1,7-heptanediol unit, 1,8-ethohexadiol unit, 1,9-nonanediol unit, the decamethylene-glycol unit, 1,4 cyclohexane dimethanol unit etc.

Wherein, constitute in the polyol unit of polyether glycol the copolyether dibasic alcohol of the 3-methyltetrahydrofuran of preferred polytetramethylene ether diol or polytrimethylene ether glycol, 1～20 mole of % and the copolyether polyvalent alcohol of tetrahydrofuran (THF) (for example, " PTG-L1000 ", " PTG-L2000 " of the production of the native ケ paddy chemistry of guarantor society, " PTG-L3500 " etc.) or neopentyl glycol and tetrahydrofuran (THF) etc.

＜(c) polyisocyanate compounds 〉

Among the present invention for example there be for example employed polyisocyanate compounds, 2,4-or 2,6-benzylidene vulcabond, the xylylene vulcabond, 4,4 '-diphenylmethanediisocyanate (MDI), 2,4 '-MDI, to phenylene vulcabond, 1, the 5-naphthalene diisocyanate, the aromatic diisocyanate of tolidine vulcabond etc., α, α, α ', the aliphatic diisocyanate with aromatic nucleus of α '-tetramethyl-benzene dimethyl vulcabond etc., methylene diisocyanate, trimethylene diisocyanate, lysinediisocyanate, 2,2,4-or 2,4, the 4-trimethyl hexamethylene diisocyanate, 1, the aliphatic diisocyanate of 6-hexamethylene diisocyanate etc., 1, the 4-cyclohexyl diisocyanate, methylcyclohexane diisocyanate (hydrogenation TDI), 1-isocyanic ester-3-isocyanic ester methyl-3,5,5-trimethyl-cyclohexane (IPDI), 4,4 ' double-hexyl methane vulcabond, isopropylidene dicyclohexyl-4,4 '-alicyclic diisocyanate of vulcabond etc. etc.They can use separately, also can more than 2 kinds or 2 kinds and use.

Among the present invention, the special high aromatic poly-isocyanate of preferred reactive, preferred especially benzylidene vulcabond (TDI), diphenylmethanediisocyanate (MDI).In addition, it can be the material that the part of the NCO base of polymeric polyisocyanate is changed into carbamate, urea, biuret, allophanate, carbodiimide, oxazolidone, acid amides, imines etc., further, in polykaryon, also comprise isomer except that above-mentioned.

The usage quantity of these polyisocyanate compounds, have the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl and (b) hydroxyl and amino total 1 equivalent of the total of the hydroxyl of polyether glycol and chainextender with respect to (a) molecular end, be generally 0.1 equivalent～5 equivalents, preferred 0.8 equivalent～2 equivalents, more preferably 0.9 equivalent～1.5 equivalents, further preferred 0.95 equivalent～1.2 equivalents, 0.98 equivalent～1.1 equivalents most preferably.

The words that the usage quantity of polymeric polyisocyanate is too much, unreacted isocyanate group is carried out unfavorable reaction, and the tendency that is difficult to obtain desired rerum natura is arranged, very few words, the molecular weight of urethane and urethane urea is insufficiently big, the tendency that has desired performance not manifest.

＜(d) chainextender 〉

The chainextender of indication mainly is divided into the compound with the hydroxyl more than 2 or 2, the compound with the amino more than 2 or 2, water among the present invention.Wherein, the preferred short chain polyvalent alcohol of urethane purposes is specially the compound with the hydroxyl more than 2 or 2, the preferred polyamine compounds of urethane urea purposes, the concrete compound that preferably has the amino more than 2 or 2.Wherein, carry out, preferably reduce water as far as possible in order to make stable reaction ground.

In addition, urethane resin of the present invention and with molecular weight (number-average molecular weight) be compound below 500 or 500 as chainextender, the caoutchouc elasticity of polyurethane elastomer is improved, thus on rerum natura more preferably.

Compound with the hydroxyl more than 2 or 2 for example has for example, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 2, the 3-butyleneglycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, the 2-methyl isophthalic acid, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 2-methyl-2, the 4-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 2-ethyl-1, the 3-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 2-butyl-2-hexyl-1, ammediol, 1, the 8-ethohexadiol, the 2-methyl isophthalic acid, the 8-ethohexadiol, 1, the aliphatic diol of 9-nonanediol etc., the alicyclic diol of two hydroxymethyl hexanaphthenes etc., xylyl alcohol, the glycol with aromatic nucleus of two hydroxyl-oxethyl benzene etc. etc.

Compound with the amino more than 2 or 2 for example has for example, and 2,4-or 2, the 6-tolylene diamine, the xylylene diamines, 4,4 '-aromatic diamine of ditan diamines etc., quadrol, 1, the 2-propylene diamine, 1, the 6-hexanediamine, 2,2-dimethyl-1, the 3-propylene diamine, the 2-methyl isophthalic acid, the 5-pentamethylene diamine, 1,3-diamino pentane, 2,2,4-or 2,4,4-trimethylammonium hexanediamine, 2-butyl-2-ethyl-1, the 5-pentamethylene diamine, 1, the 8-octamethylenediamine, 1, the 9-nonamethylene diamine, the aliphatie diamine of 1 etc., 1-amino-3-amino methyl-3,5,5-trimethyl-cyclohexane (IPDA), 4,4 '-double-hexyl methane diamines (hydrogenation MDA), isopropylidene cyclohexyl-4,4 '-diamines, 1, the 4-diamino-cyclohexane, 1, the alicyclic diamine of the two amino methyl hexanaphthenes of 3-etc. etc.These chainextenders can use separately, also can more than 2 kinds or 2 and use.Wherein, preferred quadrol, propylene diamine, 1 among the present invention, 3-diamino pentane, 2-methyl isophthalic acid, the 5-pentamethylene diamine, wherein, more preferably quadrol, propylene diamine.

There is no particular limitation to the usage quantity of these chainextenders, will deduct the equivalent that the equivalent of polyisocyanate compounds obtains from the hydroxyl equivalent of (a) and total (b) and be used as at 1 o'clock, is generally 0.1 equivalent or more than 0.1 equivalent, 5.0 equivalents or below 5.0 equivalents.Preferred 0.8 equivalent or 0.8 equivalent are above, 2.0 equivalents or below 2.0 equivalents, more preferably above, 1.5 equivalents of 0.9 equivalent or 0.9 equivalent or below 1.5 equivalents.The words that usage quantity is too much, following tendency is arranged: urethane that obtains and urethane urea become really up to the mark, can not get desired characteristic, perhaps be difficult to be dissolved in solvent, it is difficult, very few that processing becomes, and following tendency is arranged: too soft, can not get full intensity, elastic recovery properties or elasticity and keep performance, perhaps hot properties worsens.

In the time of will being used for the high-performance polyurethane elastomer purposes of polyurethane elastomeric fiber or synthetic leather etc. as the urethane of the target among the present invention and urethane urea, raw material combination has following example for example.

In addition, for the purpose of the molecular weight of controlling urethane, can use chain terminator as required with 1 active hydrogen base.These chain terminators have for example ethanol with hydroxyl, propyl alcohol, butanols, hexanol etc. aliphat single-alcohol, have the aliphatics monoamine of amino diethylamine, dibutylamine, n-Butyl Amine 99, monoethanolamine, diethanolamine etc.They can use separately, also can more than 2 kinds or 2 kinds and use.

＜other additives 〉

Except above-mentioned, can also add other additives as required in the urethane of the present invention.These additives have " CYANOX1790 " (manufacturing of CYANAMID society) for example, " IRGANOX245 ", " IRGANOX1010 " (above) by the manufacturing of チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ society, " Sumilizer GA-80 " (manufacturing of Sumitomo Chemical society) or 2, the antioxidant of 6-dibutyl-4-methylphenol (BHT) etc., " TINUVIN622LD ", " TINUVIN765 " (above) by the manufacturing of チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ society, " SANOL LS-2626 ", " SANOL LS-765 " (more than, three Gong She System) etc. photostabilizer, " TINUVIN328 ", the ultraviolet Line absorption agent of " TINUVIN234 " (above) etc. by the manufacturing of チ バ ス ペ シ ヤ リ テ イ one ケ ミ カ Le ズ society, the silicon compound of dimethyl siloxane polyoxyalkylene copolymers etc., red phosphorus, organo phosphorous compounds, the organic compound that contains phosphorus and halogen, the organic compound of brominated or chlorine, ammonium polyphosphate, aluminium hydroxide, the interpolation of weisspiessglanz etc. and reactive flame retardant, the pigment of titanium dioxide etc., dyestuff, the tinting material of carbon black etc., the hydrolysis of carbodiimide compound etc. prevents agent, staple glass fibre, carbon fiber, aluminum oxide, talcum, graphite, melamine, the filler of terra alba etc., lubricant, finish, tensio-active agent, other inorganic sweetening agents, organic solvent etc.

The manufacture method of＜urethane 〉

Below, the manufacture method of polyester polyol of the present invention and urethane is described in detail.

The manufacture method of＜polyester polyol 〉

Polyester polyol of the present invention uses the poly-hydroxy hydrocarbon polymer to make.The poly-hydroxy hydrocarbon polymer itself is a compound known, can make according to common employed method.In addition, also can adopt these commercially available compounds to use.Representational have the following polymkeric substance that obtains for example, by being polymerization starter with the hydrogen peroxide, make divinyl, isoprene, chloroprene equiconjugate diene, preferred 1, the 3-divinyl carries out radical polymerization, directly make the conjugated diolefin polymer that end has hydroxyl thus, perhaps use anionic polymerization catalyst, make reactive polymer terminal and the basic metal bonding, then by making reactions such as mono-epoxy compounds or formaldehyde, make end and have the conjugated diolefin polymer of hydroxyl, the conjugated diene polymer that obtains is carried out the polymkeric substance that hydrogenation obtains according to well-established law.Also have, at this moment, above-mentioned conjugated diolefine can with amount in vinyl monomer copolymerization such as 30 quality % or the vinylbenzene below the 30 quality %, vinyl cyanide, (methyl) methyl acrylate, vinyl-acetic esters.

In addition, polymkeric substance or iso-butylene and the isoprene, 1 to iso-butylene such as useful ozone of giving an example, the polymkeric substance oxygenolysis of 3-pentadiene equiconjugate diene is handled, then, reduce processing, obtain the isobutylene-based polymer that end has hydroxyl with lithium aluminium hydride etc., by well-established law with the polymkeric substance after the polymkeric substance hydrogenation that obtains and, equally with the multipolymer oxygenolysis of alpha-olefin such as ethene, propylene and diene compound, reduce processings, carry out hydrogenation polymkeric substance afterwards etc.

Known esterification techniques before the manufacturing of polyester polyol of the present invention can be adopted.For example, following method is arranged: make method that polyvalent alcohol and lactone or dicarboxylic acid react under normal pressure, under reduced pressure esterification method, after carrying out esterification in the presence of the inert solvent of toluene and so on, condensation water or condensation alcohol and solvent azeotropic are removed, made it the outer method of reaction system etc.

The temperature of reaction of esterification is 100～250 ℃ scope normally.Preferred 120～240 ℃, further preferred 140～230 ℃, preferred especially 150～220 ℃ scope.Reaction temperature is spent low, and esterification is insufficient carries out, too high, and the painted of resultant might become big.

Reaction is preferably carried out under the inert gas atmosphere of nitrogen or argon gas etc.Reaction pressure is any, can implement under normal pressure or decompression according to purpose.Reaction as polyvalent alcohol and dicarboxylic acid or dicarboxylic ester is because generate water or alcohol, so in order to promote them to break away from from reaction system, rare gas element is circulated in reaction system in the reaction.

＜catalyzer 〉

The form of described esterification is not had special restriction, can in the system that catalyst-free exists, carry out esterification, usually yet, successfully carry out in order to make esterification, can use the whole catalyzer that in esterification usefulness and transesterify usefulness, uses usually, for example, mineral acid or organic acid; The fatty acid salt of the muriate of metals such as Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Sn, Sb or Pb, oxide compound, oxyhydroxide or acetate, oxalic acid, sad, lauric acid or naphthenic acid etc.; The alcohols of sodium methylate, sodium ethylate, aluminum isopropylate, isopropyl titanate or metatitanic acid n-butyl etc.; The phenols of sodium phenylate etc.; Perhaps other organometallic compounds of the metal of Al, Ti, Zn, Sn, Zr or Pb etc. etc. and so on.From starting with easily, toxicity is also low, is widely used in esterification and considers, most preferably the Titanium series catalyst of metatitanic acid isopropyl esters or tetrabutyl titanate etc.All raw material total amounts that the usage quantity of the catalyzer of this moment is used with respect to the described polyester diol of preparation, preferred 0.00001～5.0 quality %, preferred further 0.0001～2.0 quality %, most preferably 0.001～1.0 quality %.This amount is very few, and forming polyester polyol needs the extremely long time, and resultant is painted easily.On the other hand, the catalyzer usage quantity is too much, might show the reaction promoter action to the surplus of polyurethane-reinforcement reaction.

Described esterification is preferably carried out under the inert gas atmosphere of nitrogen or argon etc.Reaction pressure is any, can implement under normal pressure or decompression according to purpose.Reaction as polyvalent alcohol and dicarboxylic acid or dicarboxylic ester is because generate water or alcohol, so in order to promote them to break away from from reaction system, rare gas element is circulated in reaction system in the reaction.

Described reaction time of esterification is according to the matrix of the usage quantity of catalyzer, temperature of reaction, reaction, to the difference of the desired rerum natura of the polyester polyol that generates etc. and difference, lower limit is generally 0.5 hour, preferred 1 hour, the upper limit was generally 30 hours, preferred 20 hours.

When using catalyzer during described esterification, residual (titanium system) catalyzer that responds and use in the polyester polyol resultant that obtains.Because removing of above-mentioned catalyzer is accompanied by complicated step usually, so the polyester polyol that generates does not generally separate (titanium system) catalyzer, great majority are directly used in the manufacturing of urethane like this.

Just, the content of catalyzer preferably makes the titanium catalyst inactivation in the polyester polyol more for a long time or according to the urethane purposes.The method that can for example have (1) that polyester polyol is contacted with water under heating for example as the method for deactivating of the Titanium series catalyst in the polyester polyol; (2) method of polyester polyol being handled with the phosphorus compound of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester etc. etc.And when adopting the method for described (1) contact with water, for example, interpolation 1 quality % or the water more than the 1 quality % in polyester polyol under 70～150 ℃, preferred 90～130 ℃ temperature, heat and got final product in about 1～3 hour.At this moment, the inactivation that is undertaken by heating is handled and can be carried out under normal pressure, also can carry out adding to depress, and inactivation is handled the back system is reduced pressure, and can successfully the employed moisture of inactivation be removed from polyester polyol.

The manufacture method of＜urethane 〉

Among the present invention, when making urethane, poly-hydroxy hydrocarbon system polymkeric substance, (b) polyether glycol, (c) polyisocyanate compounds that main production of raw material for use uses (a) molecular end to have at least 1 hydroxyl reach (d) chainextender.

When making above-mentioned urethane, generally can under the condition of solvent coexistence, make urethane.Among the present invention, preferably under the coexistence of non-proton property polar solvent, make urethane.

Also have, the usage quantity of each compound is not had special restriction, use the amount of above-mentioned record to get final product.Below, show an example of the manufacture method under the coexistence of non-proton property polar solvent, but so long as under the coexistence of non-proton property polar solvent, just be not particularly limited.

There is no particular limitation to the non-proton property polar solvent among the present invention, considers the preferred solvent that is selected from acid amides series solvent, N-Methyl pyrrolidone, N-ethyl pyrrolidone and methyl-sulphoxide that uses in the non-proton property polar solvent from deliquescent viewpoint.The concrete example of acid amides series solvent is N,N-dimethylacetamide, N, dinethylformamide and their mixture more than 2 kinds or 2 kinds, preferred especially dimethyl formamide or N,N-DIMETHYLACETAMIDE.

Example as manufacture method, (a) and (b), (c) and (d) method that reacts (single stage method) or at first mix (a) and (b) of making arranged for example, make this mixture and (c) reaction, preparation two ends are the prepolymer of isocyanate group, then, make this prepolymer and (d) reaction method (two-step approach), make after (b) and (c) reaction, mixes with (a), with the method for (d) reaction, make (b) (c) (d) reaction back and (a) blended method.Wherein, two-step approach is through such operation, promptly by making polyether glycol react the intermediate that preparation uses two terminal isocyanates of the soft chain segment that is equivalent to urethane to seal in advance with 1 equivalent or the polymeric polyisocyanate more than 1 equivalent.By preparing prepolymer for the time being, make it then and the chainextender reaction, the molecular weight of soft chain segment part is adjusted easily, and being separated of soft chain segment and hard segment becomes fully easily, and the feature that demonstrates easily as elastomeric properties is arranged.Especially, when chainextender is diamines, compare, bigger difference is arranged, so more preferably adopt two-step approach (prepolymer method) to implement urethane ureaization with the speed of response of isocyanate group with the hydroxyl of polyether glycol.

＜single stage method 〉

Single stage method is also referred to as one step foaming (one-shot), is by (a) and (b), (c) being reached the method for reacting that (d) drops into together.The usage quantity of each compound uses the amount of above-mentioned record to get final product.

Reaction makes each composition 0～250 ℃ of down reaction usually, and its temperature is according to the difference of the amount of solvent, the reactivity of using raw material, conversion unit etc. and difference.Temperature is low excessively, and the carrying out of reaction is slow excessively, and perhaps because the solvability of raw material or polymkeric substance is low, productivity worsens, and is too high again, the decomposition of side reaction or urethane resin takes place and not preferred.A reaction under reduced pressure froth breaking (deaeration) one side is carried out.In addition, reaction also can be added catalyzer, stablizer etc. as required.Catalyzer has for example triethylamine, Tributylamine, dibutyl tin dilaurate, stannous octoate, acetate, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid etc.; stablizer for example has 2 for example, 6-dibutyl-4-methylphenol, thio-2 acid two (octadecanoyl) ester, two betanaphthyl phenylenediamines, three (dinonyl phenyl) phosphide etc.

＜two-step approach 〉

Two-step approach is also referred to as the prepolymer method, usually, also can make it to react in two stages, polymeric polyisocyanate composition and polyhydroxy reactant are reacted with reaction equivalence ratio=1.0～10.00, make prepolymer, then, toward wherein adding polymeric polyisocyanate composition or polyvalent alcohol, amine compound isoreactivity hydrogen compound composition.Especially, following method is useful, makes with respect to the polyisocyanate compounds reaction of polyhydroxy reactant more than equivalent, prepares two terminal NCO prepolymers, then, short chain dibasic alcohol or diamines as chainextender is played a role, and obtains urethane.

Among the present invention, two-step approach can be implemented under the solvent coexistence, but preferably under the non-protonic solvent coexistence, carry out, acid amides series solvent or N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethylsulfoxide solvent and their mixture more than 2 kinds or 2 kinds are specifically arranged for example.

Among the present invention, when making urethane, consider preferred non-proton property polar solvent in these solvents from deliquescent viewpoint.Further, in the non-proton property polar solvent, preferred amide series solvent or N-Methyl pyrrolidone, N-ethyl pyrrolidone, methyl-sulphoxide, the acid amides series solvent will exemplify concrete example, more preferably N,N-dimethylacetamide, N, dinethylformamide, preferred especially N, dinethylformamide or N,N-dimethylacetamide.

When synthesizing prepolymer, (1) can at first, not use solvent like this, makes polyisocyanate compounds and polyether glycol direct reaction, and synthetic prepolymer directly uses like this; (2) can be dissolved in the solvent then and using with the synthetic prepolymer of the method for (1); (3) can use solvent to make polymeric polyisocyanate and polyether Glycols reaction from the beginning.(1) situation among the present invention, importantly, makes it to do the time spent with chainextender, is dissolved in the solvent by making chainextender, perhaps simultaneously prepolymer and chainextender is imported the medium method of solvent, obtains the urethane with the form of solvent coexistence.

The lower limit of the scope of the reaction equivalence ratio of NCO/ active hydrogen base (polyvalent alcohol) is generally 1, and is preferred 1.05, and the upper limit is generally 10, preferred 5, and more preferably 3.This is than too small, because the molecular weight of the prepolymer that obtains becomes excessive, the quantitative change of hard segment described later is low, and the tendency that can not get sufficient retractility is arranged, and excessive, the quantitative change height of hard segment described later has the tendency that can not get sufficient flexibility.

Usage quantity to chainextender is not particularly limited, but the equivalent of the NCO base contained with respect to prepolymer, and the lower limit of the scope of usage quantity is generally 0.1, and is preferred 0.8, and the upper limit is generally 5.0, and preferred 2.0.

In addition, also can make the organic amine or the alcohol coexistence of simple function during reaction.

Chain extension reaction makes each composition 0～250 ℃ of reaction down usually, and its temperature is according to the difference of the amount of solvent, the reactivity of using raw material, conversion unit etc. and difference.Temperature is low excessively, and the carrying out of reaction is slow excessively, and perhaps because the solvability of raw material or polymkeric substance is low, so productivity worsens, and is too high again, takes place that side reaction or urethane resin decompose and not preferred.A reaction under reduced pressure froth breaking is simultaneously carried out.

In addition, reaction also can be added catalyzer, stablizer etc. as required.Catalyzer has for example triethylamine, Tributylamine, dibutyl tin dilaurate, stannous octoate, acetate, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid etc.; stablizer for example has 2 for example, 6-dibutyl-4-methylphenol, thio-2 acid two (octadecanoyl) ester, two betanaphthyl phenylenediamines, three (dinonyl phenyl) phosphide etc.Yet, when chainextender is the reactive high compound of short-chain fat family amine etc., does not preferably add catalyzer and implement.

The rerum natura of＜urethane 〉

The urethane that obtains with above-mentioned manufacture method is owing to react in the presence of solvent, thus generally obtain with the state that is dissolved in the solution, but physics value is to state without limits, and solution state, solid state are not had special restriction.

The weight-average molecular weight of urethane is according to the difference of purposes and difference as urethane polymerization solution, is generally 10,000～1,000,000, and is preferred 50,000～500,000, and more preferably 100,000～400,000, preferred especially 100,000～300,000.As molecular weight distribution, Mw/Mn=1.5～3.5, preferred 1.7～3, more preferably 1.8～3.As fiber, film, water vapour permeability resin molded body, the weight-average molecular weight of urethane is generally 10,000～1,000,000, and is preferred 50,000～500,000, and more preferably 100,000～400,000, preferred especially 150,000～400,000.As molecular weight distribution, Mw/Mn=1.5～3.5, preferred 1.7～3, more preferably 1.8～3.

In addition, the amount of the hard segment that the urethane that above-mentioned manufacture method obtains preferably contains is 1～20 weight % with respect to the gross weight of polyether polyols with reduced unsaturation, more preferably 3～15 weight %, further preferred 4～12 weight %, preferred especially 5～10 weight %.This hard segment amount is too much, and the polyether polyols with reduced unsaturation that obtains has following tendency: do not show sufficient flexibility or elastic performance, be difficult for dissolving when using solvent, processing becomes difficulty.Very few, following tendency is arranged: urethane polymer is too soft, and it is difficult that processing becomes, and perhaps can not obtain full intensity or elastic performance.

In addition, so-called hard segment is with P.J.Flory, Journal of American Chemical Society among the present invention, and 58,1877～1885 (1936) is the basis, according to following formula, calculates the weight with respect to the isocyanic ester and the amine bonding part of gross weight.

Hard segment (%)=[(R-1) (Mdi+Mda)/Mp+R+Mdi+ (R-1) Mda}] * 100

Here,

The mole number of R=isocyanic ester/(mole number+molecular end of the hydroxyl of polyether glycol has the mole number of hydroxyl of the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl)

The number-average molecular weight of Mdi=vulcabond

The number-average molecular weight of Mda=chainextender

The number-average molecular weight of Mp=polyether glycol and molecular end have the molecular-weight average of number-average molecular weight of the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl

The storage stability of the polyurethane solution that obtains among the present invention is good, is difficult for carrying out gelation, viscosity through the time change little etc., in addition because thixotropy is little, so it is also very convenient to be used to be processed into film, yarn etc.The polyurethane concentration of polyurethane solution is generally 1～99 weight % with respect to the gross weight that is dissolved in the solution in the solvent, preferred 5～90 weight %, more preferably 10～70 weight %, preferred especially 15～50 weight %.The amount of urethane is very few, need remove a large amount of solvents, and productivity has the tendency of decline, and is too much, and the viscosity of solution is too high, and operability or processibility have the tendency of deterioration.

Polyurethane solution do not had specify, but during prolonged preservation, preferably under normal temperature or the temperature below it, under inert gas atmospheres such as nitrogen or argon, preserve.

＜polyurethane formed body and this purposes 〉

Obtain by they are shaped, can obtaining polyurethane formed body after the urethane and this carbamate prepolymer solution of the present invention's manufacturing.

Polyurethane formed body of the present invention is to be got final product by above-mentioned urethane or the molding that is made of the urethane that obtains by above-mentioned manufacturing process, there is no particular limitation, usually, it is characterized in that, be by containing poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least 1 hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) the polyurethane formed body that constitutes of the urethane of chainextender, it is below 0.22 or 0.22 that the atom on the surface of this polyurethane formed body is formed (Sauerstoffatom/carbon atom).

What the atom on the surface of polyurethane formed body was formed (Sauerstoffatom/carbon atom) concrete expression is, for example, by ESCA (electron spectroscopy for chemical analysis, Electron Spectroscopy for Chemical Analysis) or XPS (X ray luminous energy spectrometry, when X-ray Photoelectron Spectroscopy) measuring the molding surface, Sauerstoffatom is with respect to the relative existence ratio of carbon atom.

The atom on the surface of polyurethane formed body of the present invention is formed below the value preferred 0.20 or 0.20 of (Sauerstoffatom/carbon atom), further below preferred 0.16 or 0.16.This value is more little, and the adhesivity of the molding that obtains has the tendency that reduces more, and separability has good more tendency.In addition, more than preferred 0.00 or 0.00, further more than preferred 0.05 or 0.05.This value is big more, and the packing with the molding that obtains when overlapped has the tendency that uprises, and for example, when molding was yarn, the yarn of spooling was difficult for untiing and loses shape.

In addition, as polyurethane formed body of the present invention, it is below 0.22 or 0.22 that the atom on preferred above-mentioned surface is formed (Sauerstoffatom/carbon atom), and the water contact angle on surface is more than 80 degree or 80 are spent.

This surperficial water contact angle is measured like this and is obtained, and the water droplet of several μ L is dropped on the molding surface, the interior angle that constituted with the tangent line and the molding surface of interior this drop of mensuration at 10 seconds.The value of the water contact angle on the surface of polyurethane formed body of the present invention is at 80 degree or more than 80 degree, more than preferred 83 or 83, further more than preferred 86 or 86.This value is big more, and the adhesivity of the molding that obtains has the tendency of reduction more, and separability has good tendency more.In addition, below preferred 180 degree or 180 are spent, further below the preferred 150 or 150 degree degree.This value is more little, and the packing with the molding that obtains when overlapped has the tendency that uprises, and for example, when molding was yarn, the yarn of spooling was difficult for untiing and loses shape.

In addition, urethane of the present invention, carbamate prepolymer solution and polyurethane formed body are because show various characteristic, so can be used for various purposes.For example, can be widely used in foam, elastomerics, Tu material, fiber, tackiness agent, bed material, sealing material, medical material, artificial leather etc.

The urethane of manufacturing of the present invention, urethane urea and this carbamate prepolymer solution can be used for the cast polyurethane elastomerics.As an example, roller classes such as stack, system paper bowl, office equipment, pre-stretching roller are arranged; The solid tyre of fork truck, automobile streetcar (new-tram, a kind of new traffic system), chassis, carrier etc., castor etc.; As Industrial products, travelling belt carrying roller, deflector roll, pulley, steel tubing, ore are arranged with the impeller of rubber screen, gear class, shack, liner, pump, cyclonic separator cone, cyclonic separator lining etc.In addition, the band, paper-feed roll, duplicating that also is applicable to OA (office appliance) equipment is with cleaner plate, snowplow, toothed belt, scooter (サ one Off ロ one ラ one) etc.

The urethane of manufacturing of the present invention with and carbamate prepolymer solution also be applicable to purposes as thermoplastic elastomer.For example, can be used as pipe in pneumatic compression devices that food, medical field uses, applying device, analytical instrument, physics and chemistry equipment, pump of constant delivery type, water treating equipment, the industrial robot etc. or flexible pipe class, spiral tube, fire hose etc.In addition, bands such as circular band, V-belt, flat rubber belting be can make and various transmission rigs, Weaving device, packaging facilities, printing equipment etc. are used for.In addition, can exemplify the band etc. of equipment parts such as the heel of footwear or sole, junctor, sealing member, column beam joint, axle bush (bush), gear, roller, sporting goods, leisure goods, clock and watch.And, as auto parts, oil brake, wheel casing, dividing plate, chassis part, interior ornaments, tire chain substitute etc.In addition, keyboard film, automobile are with films such as film, spiral covering (カ one Le コ one De), cable sheath, corrugated tube, conveying belt, flexible container, tackiness agent, synthetic leather, dipping (Dipping) product, caking agent etc.

The urethane of manufacturing of the present invention with and carbamate prepolymer solution also can be applied to the purposes that solvent is a two-component coating, can be applied to timber-works such as musical instrument, Fo Tan, furniture, fancy plywood, sporting goods.In addition, as the tar epoxy polyurethane, also can be used for the car repair purposes.

The urethane that the present invention makes with and carbamate prepolymer solution also can be as the onepot coating of wet-cured type; blocked isocyanate series solvent coating; phthalic resin coating; polyurethane-modified synthetic resin coating; compositions such as UV curable paint for example can be used as: plastic bumper coating; Stripable paint; the tape Liniment; floor tile; flooring material; paper; overprint varnish zhes such as grain printing film; timber varnish; high processing coil coating; fiber optic protection coating; the scolder resist; the operplate printing external coating (EC); evaporation priming paint; food cans is with whitewash etc.

The urethane that the present invention makes with and carbamate prepolymer solution, as caking agent, can be applied to food product pack, footwear, footwear, tape tackiness agent, facial tissue, timber, structural member etc., in addition, also can be as the composition of low temperature with caking agent, hot melt adhesive (hot melt).

The urethane that the present invention makes with and carbamate prepolymer solution, as tackiness agent, can be used for magnetic recording media, printing ink, castings, vitrified brick, graft materials, microcapsule, granulated fertilizer, granular pesticide, polymer cement mortar, resin slurry, sheet rubber tackiness agent, regenerated foam, glass fibre school shape etc.

The urethane that the present invention makes with and carbamate prepolymer solution, as the composition of fiber processing agent, can be used for shrink-resistant finish, wrinkle resistant processing, waterproof processing etc.

The urethane that the present invention makes, urethane urea with and carbamate prepolymer solution, as sealing agent and/or caulking agent, can be used for concrete interior wall, induction seam, window frame, wall type PC seam, ALC seam, plate class seam, compound glass with sealing agent, heat insulation window sealing agent, automobile with sealing agent etc.

The urethane that the present invention makes with and carbamate prepolymer solution, can be used as medical material uses, material as compatible blood, can be used for pipe, conduit, artificial heart, artificial blood vessel, artificial valve etc., in addition, as disposable raw material, can be used for conduit, pipe, bag, operation gloves, artificial kidney Embedding Material etc.

The urethane that the present invention makes, urethane urea with and carbamate prepolymer solution, can be at the raw material that make terminal-modified back as UV curable coating, electronic beam solidified coating, the photosensitive polymer combination that flexographic plates is used, the optical fibre packages cover material feed composition of light-cured type etc.

Especially,, be preferred for film or fiber,, be preferred for medical treatment, sanitary material, artificial leather and clothing spandex fiber as these concrete purposes in the elastic performance of the urethane of bringing into play the present invention's manufacturing or the characteristic aspect of water vapour permeability.

More than, narrated used urethane that the present invention makes with and the purposes example of carbamate prepolymer solution, but the present invention is not subjected to the qualification of these purposes.

Put down in writing the manufacture method of film and fiber below, but be not that manufacture method is had special restriction.

The manufacture method of＜film 〉

Manufacture method to film is not particularly limited, and can use known method.For example, the manufacture method of film has for example, and wet type made membrane method is coated on polyurethane resin solution on support or the release materials, extracts the soluble substance of solvent etc. in precipitation bath; And dry type made membrane method, polyurethane resin solution is coated on support or the release materials, by heating or decompression etc., make solvent seasoning.Employed support is not particularly limited during to dry made membrane, can use the paper that is coated with polyethylene or polypropylene film, glass, metal, release liner or cloth etc.Mode to coating is not particularly limited, and can be any of known manner of scraper spreadometer, roller coating machine, spin coater, intaglio plate coating machine etc.Drying temperature can be set arbitrarily according to the ability of drying machine, need to select a temperature range, makes it that dry insufficient or desolventizing tempestuously can not take place.Room temperature～300 ℃ preferably, more preferably 60 ℃～200 ℃ scope.

The rerum natura of＜film 〉

The thickness of film of the present invention is generally 10～1000 μ m, preferred 10～500 μ m, more preferably 10～100 μ m.The thickness of film is blocked up, and the tendency that can not get sufficient water vapour permeability is arranged, and in addition, crosses when thin, forms pin hole easily, perhaps the easy adhesion of film and reluctant tendency is arranged.In addition, this film can be preferred for medical adhesive film or sanitary material, wrapping material, decoration with film, other water vapour permeability raw materials etc.In addition, film also can be coated on the supports such as cloth or non-woven fabrics.At this moment, also can be thinner than 10 μ m.

Elongation at break is generally more than 100% or 100%, is preferably more than 200% or 200%, more preferably more than 300% or 300%, further more than preferred 500% or 500%.Breaking tenacity is generally 5MPa or more than the 5MPa, is preferably 10MPa or more than the 10MPa, more preferably 20MPa or more than the 20MPa, further preferred 30MPa or more than the 30MPa.

In the 300% elongation-contraction repetition test under 23 ℃, the elasticity conservation rate (Hr1/H1) that the ratio of the stress when 150% the when stress when 150% when being shunk by the first time extended extended with respect to the first time extended obtains is generally more than 10% or 10%, be preferably more than 20% or 20%, more preferably more than 30% or 30%, further more than preferred 40% or 40%.In the same manner, the elasticity conservation rate (Hr5/H5) that the ratio of the stress when 150% the when stress when 150% when shrinking by the 5th time extended extends with respect to the 5th time extended obtains is generally more than 30% or 30%, be preferably more than 50% or 50%, more preferably more than 70% or 70%, further more than preferred 85% or 85%.

In addition, in the 300% elongation-contraction repetition test under 23 ℃, the elasticity conservation rate (H2/H1) that the ratio of the stress when 150% the when stress when 150% when being extended by the second time extended extended with respect to the first time extended obtains is generally more than 20% or 20%, be preferably more than 40% or 40%, more preferably more than 50% or 50%, more preferably more than 60% or 60%.

In addition, the secondary residual set in the 300% elongation-contraction repetition test under 23 ℃ is generally below 40% or 40%, is preferably below 30% or 30%, more preferably below 25% or 25%, is preferably especially below 20% or 20%.In addition, the 5th time residual set is generally below 50% or 50%, is preferably below 35% or 35%, more preferably below 30% or 30%, is preferably especially below 25% or 25%.

In addition, the rerum natura of polyurethane film and yarn has very confidential relation, and the physics value that is obtained by test of film etc. is even also show same tendency in yarn (fiber).

The purposes of＜polyurethane fiber 〉

For having used the fiber of urethane of the present invention, more specifically exemplify purposes, be preferred for the purposes such as extensibility clothes, swimming suit, tights of the stocking leg (レ Star グ), pants, panty hose, cover of diaper, paper diaper, sweat shirt, underwear, socks, stylishness excellence.This is because excellences such as stretching is restorative, elasticity, hydrolytic resistance, photostabilization, scale resistance, oil-proofness, processibilities.

Embodiment

Below, more specifically describe according to embodiments of the invention, but the present invention is only otherwise exceed its purport, is not subjected to the qualification of these embodiment.In addition, following embodiment and the analysis in the comparative example, measure and carry out according to following method.

The number-average molecular weight of＜poly-hydroxy hydrocarbon system polymkeric substance and polyether glycol 〉

The hydroxyl value that the poly-hydroxy hydrocarbon system polymkeric substance that uses among the present invention and the number-average molecular weight of the polyether glycol acetylation method by foundation JIS K 1557-1:2007 carries out (try to achieve by KOH (mg)/g) measuring method.

The molecular weight of＜urethane and urethane urea 〉

The following mensuration of the molecular weight of urethane that obtains or urethane urea, the dimethylacetamide solution of preparation urethane or urethane urea, (eastern ソ one society makes to use the GPC device, ProductName " HLC-8220 " (chromatographic column: Tskgel G MH-XL (2)), measure the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) that convert with polystyrene standard.

＜stripping test method 〉

With 2 film overlaies that obtain, utilize the test film tapping and plugging machine, obtain the film of the long 4cm of sample (lap that comprises long part of the solid periodic initial test of the long tensile testing machine of 1.5cm and 2.5cm respectively), wide 1cm.For test film, film overlay is partly being added 200g/cm ²Pressure status under, under the condition of 25 ℃ of temperature, relative humidity 50%, placed 10 minutes, then, use tensile testing machine (FUDOH makes " レ オ メ one タ one NRM-2003J "), underproof film is stretched, measure T type stripping strength by the speed of dividing with 300mm/.

＜film rerum natura 〉

Urethane or urethane urea test sheet are made the rectangle of wide 10mm, long 100mm, thick about 50 μ m, according to JIS K6301, (オ リ エ Application テ Star Network society makes to use tensile testing machine, ProductName " テ Application シ ロ Application UTM-III-100 "), under the condition of dividing apart from 50mm, draw speed 500mm/ between chuck, when measuring the following tensile break strength of temperature 23 ℃ (relative humidity 55%), tension fracture elongation rate, 100% elongation and 300% intensity when extending.

＜surface atom is formed 〉

The surface atom composition is measured by ESCA (Electron Spectroscopy for Chemical Analysis) and is tried to achieve.Measure and use the ESCA device " PHI Model 5800 " of ア Le バ Star Network-Off ア イ Co., Ltd. to implement.Condition determination is as follows.

X ray excited: monochromatic AlK α line (1486.6eV)

X ray output: (filament (filament)) 14kV, 350W (7mm)

In and rifle: use (being used to prevent static)

Input lens is set (Lens Area Mode): Minimum Area Mode

Analytical model (LENS MODE): 5 (Minimum Area patterns)

Aperture numbering: 5

(sample normal and detector centre axle angulation) used in emission: 45 degree

Logical energy (PassEnergy): 23.5eV

Electric charge moves revisal: the bonded energy that makes c h bond close the C1s peak of carbon meets 285.0eV ground to carry out.

About the relative existence ratio of Sauerstoffatom, calculate by following formula with respect to carbon atom.

Exist than O/C=(the peak revisal relative sensitivity coefficient at the peak area of oxygen O1s/oxygen O1s peak)/(the peak revisal relative sensitivity coefficient at the peak area of carbon C1s/carbon C1s peak) relatively

In addition, oxygen O1s and following the obtaining of each peak area of carbon C1s, using appts accessory MultiPak Ver.8.2C software has adopted the smoothing processing (9 point) of Savitzky-Golay algorithm, uses the background curves of shirley method to obtain.The revisal relative sensitivity coefficient separately that is used for calculating the oxygen O1s of relative existence ratio and carbon C1s peak bonded energy and uses at MultiPak Ver.8.2C software is as follows.

O1s: near bonded energy=532.5eV,

Revisal relative sensitivity coefficient=13.118

C1s: near bonded energy=285.0eV,

Revisal relative sensitivity coefficient=5.220

Peak area about carbon C1s, the area that has used following area addition to obtain, promptly adopt shirley, the peak that links the area that near the minimum value 280eV and the 290.5eV obtains and adopt that shirley links that near 290.5eV and the 293eV minimum value obtains from the shake up of phenyl ring (near 291～293eV〉the area addition obtain.

＜water contact angle 〉

The automatic contact angle instrument DM-300 that uses consonance interface science Co., Ltd. to make is dropped in the polyurethane film surface with the water droplet of 1.5～2.0 μ L, after 5 seconds, measures the tangent line of water droplet and the interior angle of molding surface formation.Change the place of film, repeat 5 times identical operations, with the mean value of 5 points obtaining as water contact angle.

＜embodiment 1 〉

At capacity is to add in the flask of 1L to mix to heat in advance to 40 ℃ the polytetramethylene ether diol (number-average molecular weight of being calculated by hydroxyl value 1968, the manufacturing of Mitsubishi Chemical society) hydrogenated butadiene polymer polyvalent alcohol (trade(brand)name " the Port リ テ one Le HA " number-average molecular weight: 2187 of 142.5 weight parts, the manufacturing of Mitsubishi Chemical society, the average bonding number of the hydroxyl of per 1 molecule: 1.8) 7.5 weight parts, with this mixture as making the raw material that urethane is used." Port リ テ one Le HA " is 5 weight % with respect to the ratio of this mixture.Then, heat to 40 ℃ 4,4 '-diphenylmethanediisocyanate (below, abbreviate " MDI " sometimes as) 31 weight parts.The reaction equivalence ratio of the NCO/ active hydrogen base (polyether glycol and chainextender) of this moment is 1.6.And, this flask being placed in 45 ℃ the oil bath, one side stirs with anchor type agitating wing under nitrogen atmosphere, and one side is lasted 1 hour temperature with oil bath and is risen to 70 ℃, keeps 3 hours down at 70 ℃ then.The residual NCO base and the dibutylamine of excess quantity are reacted, then, residual dibutylamine is carried out back titration by utilizing hydrochloric acid, the reactivity of confirming NCO surpasses after 99%, removes oil bath, adds N in flask, the N-N,N-DIMETHYLACETAMIDE (below, abbreviate " DMAC " sometimes as.The manufacturing of Northeast chemistry society) 271 parts, at room temperature stirring and dissolving prepares urethane prepolymer solution.

Above-mentioned urethane prepolymer solution 380 weight parts are cooled to 10 ℃, keep this temperature, on the other hand, preparation is as the 0.6%DMAC solution of quadrol (EDA)/diethylamine (DEA)=89/11 (the mol ratio)=1.72/0.27 (weight ratio) of chainextender use.The limit high-speed stirring is cooled to and remains on 10 ℃ above-mentioned urethane prepolymer solution limit adds it in this 0.6%DMAC solution to, obtains the urethane urea DMAC solution of polymer concentration 20%.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 17.2 ten thousand, molecular weight distribution is 2.4.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 78 weight %.

The urethane urea soln that obtains is like this cast on the sheet glass, make it dry, obtain the water white film of the about 50 μ m of thickness at 60 ℃.The thickness of film is measured by thickness tester.

This film is carried out stripping test, and peeling off needed stress is 5.7g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 1.In addition, the surface atom of this film consists of 0.089, and water contact angle is 90 degree.The results are shown in table 1.

＜embodiment 2 〉

Among the embodiment 1, adding and mix the urethane production of raw material for use is polytetramethylene ether diol (number-average molecular weight 1968, the Mitsubishi Chemical society of being calculated by hydroxyl value make) 148.5 weight parts, " Port リ テ one Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of per 1 molecule: 1.8) 1.5 weight parts (ratio of " Port リ テ one Le HA " in this mixture is 1 weight %), and be set at quadrol/diethylamine=1.81/0.28 (weight ratio), in addition, obtain prepolymer and urethane urea soln similarly to Example 1.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 20.2 ten thousand, molecular weight distribution is 2.5.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 81 weight %.

Obtain the water white urethane urea film that thickness is about 50 μ m by this urethane urea soln.

This film is carried out stripping test, and peeling off needed stress is 5.7g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 1.In addition, the surface atom of this film consists of 0.119, and water contact angle is 89 degree.The results are shown in table 1.

＜embodiment 3 〉

Among the embodiment 2, adding and mix the urethane production of raw material for use is polytetramethylene ether diol (number-average molecular weight 1968, the Mitsubishi Chemical society of being calculated by hydroxyl value make) 149.85 weight parts, " Port リ テ one Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of per 1 molecule: 1.8) 0.15 weight part (ratio of " Port リ テ one Le HA " in this mixture is 0.1 weight %), in addition, obtain prepolymer and urethane urea soln similarly to Example 2.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 19.8 ten thousand as a result, molecular weight distribution is 2.4.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 82 weight %.

Obtain the water white urethane urea film that thickness is about 50 μ m by this urethane urea soln.

This film is carried out stripping test, and peeling off needed stress is 33g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 1.In addition, the surface atom of this film consists of 0.194.The results are shown in table 1.

＜embodiment 4 〉

Among the embodiment 1, add and mix polytetramethylene ether diol (number-average molecular weight 1968, the Mitsubishi Chemical society of being calculated by hydroxyl value make) 105 weight parts, " Port リ テ one Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of per 1 molecule: 1.8) 45 weight parts (ratio of " Port リ テ one Le HA " in this mixture is 30 weight %), in addition, obtain prepolymer and urethane urea soln similarly to Example 1.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 19.8 ten thousand, molecular weight distribution is 2.4.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 57 weight %.

Obtain the urethane urea film that thickness is about the gonorrhoea a little of 50 μ m by this urethane urea soln.

This film is carried out stripping test, and peeling off needed stress is 33g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 1.

＜comparative example 1 〉

Among the embodiment 1, do not use " Port リ テ one Le HA ", with polytetramethylene ether diol (number-average molecular weight of being calculated by hydroxyl value 1968, Mitsubishi Chemical society make) 150 weight parts as the urethane production of raw material for use, in addition, obtain prepolymer and urethane urea soln similarly to Example 1.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 19.1 ten thousand, molecular weight distribution is 2.6.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 78 weight %.

Obtain the water white urethane urea film that thickness is about 50 μ m by this urethane urea soln.

This film is carried out stripping test, and peeling off needed stress is 50g/cm, when peeling off, observes 12% the film long with respect to initial test and extends.The characteristic of the Elastic Film that obtains in addition, is as shown in table 1.In addition, the surface atom of this film consists of 0.239, and water contact angle is 76 degree.The results are shown in table 1.

[table 1]

＜embodiment 5 〉

[manufacturing of polyester polyol]

Measure the 6-caprolactone (Across society) of the tetrabutyl titanate (the East capital changes into society) of 1.2mg, the hydrogenated butadiene polymer polyvalent alcohol GI-1000 of 30g (20.0mmol) (Japanese Cao Da society, molecular weight 1500), 10g (87.6mmol), add 100mL four-hole round-bottomed flask to stirrer, return line and nitrogen ingress pipe are installed, reaction vessel is immersed in the oil bath, be warming up to 190 ℃ in 30 minutes, make it to react 7h down, as polyester polyol 1 at 190 ℃.The theoretical molecular of this polyester polyol 1, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

At capacity is to add in the flask of 1L and mix to heat in advance to 40 ℃ the polytetramethylene ether diol (number-average molecular weight of being calculated by hydroxyl value 1955, Mitsubishi Chemical society makes) 123.9 weight parts, the above-mentioned synthetic polyester polyol 1 of 6.52 weight parts, with this mixture as making the raw material that urethane is used.Polyester polyol 1 is 5 weight % with respect to the ratio of this mixture.Then, heat to 40 ℃ 4,4 '-diphenylmethanediisocyanate (below, abbreviate " MDI " as) 26.8 weight parts.The reaction equivalence ratio of the NCO/ active hydrogen base (polyether glycol and chainextender) of this moment is 1.6.Then, this flask is placed in 45 ℃ the oil bath, one side stirs with anchor type agitating wing under nitrogen atmosphere, and one side is lasted 1 hour temperature with oil bath and risen to 70 ℃, keeps 3 hours down at 70 ℃ then.The residual NCO base and the dibutylamine of excess quantity are reacted, then, residual dibutylamine is carried out back titration by utilizing hydrochloric acid, the reactivity of confirming NCO surpasses after 99%, removes oil bath, adds N in flask, the N-N,N-DIMETHYLACETAMIDE (below, abbreviate " DMAC " sometimes as.The manufacturing of Northeast chemistry society) 236 parts, at room temperature stirring and dissolving prepares urethane prepolymer solution.

Above-mentioned urethane prepolymer solution is cooled to 10 ℃, keeps this temperature, on the other hand, preparation is as the 0.5%DMAC solution of quadrol (EDA)/diethylamine (DEA)=89/11 (the mol ratio)=1.66/0.24 (weight ratio) of chainextender use.Limit high-speed stirring cooling and remain on 10 ℃ above-mentioned urethane prepolymer solution limit it is added in this 0.5%DMAC solution obtains the urethane urea DMAC solution of polymer concentration 20%.

After 25 ℃ of one evenings of following slaking, adopt GPC to measure weight-average molecular weight and molecular weight distribution this solution, weight-average molecular weight is 21.9 ten thousand, molecular weight distribution is 2.7.The ratio of (b) polytetramethylene ether diol in the urethane that obtains in addition, is 78 weight %.

The urethane urea soln that obtains is like this cast on the sheet glass, make it dry, obtain the water white film of the about 50 μ m of thickness at 60 ℃.The thickness of film is measured by thickness tester.

This film is carried out stripping test, and peeling off needed stress is 4.4g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.097, and water contact angle is 95 degree.The results are shown in table 3.

＜embodiment 6 〉

[manufacturing of polyester polyol]

Use the GI-2000 (Japanese Cao Da society, molecular weight 2100) of 60g (28.6mmol) to replace GI-1000, the tetrabutyl titanate usage quantity is decided to be 3.6mg, the usage quantity of 6-caprolactone is decided to be 12g (105mmol), in addition, makes polyester polyol 2 identically with embodiment 5.The theoretical molecular of this polyester polyol 2, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

Press the raw material charging capacity of the manufacturing urethane shown in the table 3, obtain urethane urea soln and film the samely with embodiment 5.This film is carried out stripping test, and peeling off needed stress is 6.7g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.094, and water contact angle is 94 degree.The results are shown in table 3.

＜embodiment 7 〉

[polyester polyol manufacturing]

Use the tetrabutyl titanate of GI-2000, the 2.5mg of 51.3g (24.4mmol), the 6-caprolactone of 22g (193mmol), in addition, make polyester polyol 3 identically with embodiment 6.The theoretical molecular of this polyester polyol 3, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

Raw material charging capacity when pressing the manufacturing urethane shown in the table 3 obtains urethane urea soln and film with embodiment 5 the samely.This film is carried out stripping test, and peeling off needed stress is 3.6g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.100, and water contact angle is 95 degree.The results are shown in table 3.

＜embodiment 8 〉

[manufacturing of polyester polyol]

Use " エ Port one Le " (the emerging product of bright dipping, molecular weight 1800) of 60g (27.9mmol) to replace GI-1000 as the hydrogenated polyisoprene polyvalent alcohol, the tetrabutyl titanate usage quantity is decided to be 3.6mg, the 6-caprolactone usage quantity is decided to be 10g (87.6mmol), in addition, make polyester polyol 4 with embodiment 5 identically.The theoretical molecular of this polyester polyol 4, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

Raw material charging capacity when pressing the manufacturing urethane shown in the table 3 obtains urethane urea soln and film with embodiment 5 the samely.This film is carried out stripping test, and peeling off needed stress is 4.5g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.154, and water contact angle is 88 degree.The results are shown in table 3.

＜embodiment 9 〉

[manufacturing of polyester polyol]

Measure the dimethyl adipate (Tokyo changes into society) of the tetrabutyl titanate (Tokyo changes into society) of 4.2mg, the hydrogenated butadiene polymer polyvalent alcohol GI-1000 of 66.0g (44.0mmol) (Japanese Cao Da society, molecular weight 1500), 3.8g (22.0mmol), add 100mL four-hole round-bottomed flask to stirrer.Return line and nitrogen ingress pipe are installed, reaction vessel is immersed in the oil bath, be warming up to 190 ℃ in 30 minutes, make it to react 7h down, as polyester polyol 5 at 190 ℃.In the reaction, with band heater the portion of distillating is heated to 120 ℃, the methyl alcohol that reaction is generated follows the nitrogen distillation to remove.The theoretical molecular of this polyester polyol 5, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

Raw material charging capacity when pressing the manufacturing urethane shown in the table 3 obtains urethane urea soln and film with embodiment 5 the samely.This film is carried out stripping test, and peeling off needed stress is 10.8g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.072, and water contact angle is 96 degree.The results are shown in table 3.

[0089]

＜embodiment 10 〉

[manufacturing of polyester polyol]

Use the Succinic acid dimethylester (Tokyo changes into society) of 3.09g (21.1mmol) to replace dimethyl adipate, the GI-1000 usage quantity is decided to be 63.4g (42.3mmol), the tetrabutyl titanate usage quantity is decided to be 2.2mg, in addition, makes polyester polyol 6 with embodiment 9 identically.The theoretical molecular of this polyester polyol 6, theoretical oxygen level have been shown in the table 2 in the lump.

[manufacturing of urethane urea]

Raw material charging capacity when pressing the manufacturing urethane shown in the table 3 obtains urethane urea soln and film with embodiment 5 the samely.This film is carried out stripping test, and peeling off needed stress is 13.0g/cm, and separability is good.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.083, and water contact angle is 98 degree.The results are shown in table 3.

＜comparative example 2 〉

[manufacturing of urethane urea]

Raw material charging capacity when pressing the urethane shown in the table 3 and making is not contained the urethane urea soln and the film of polyester polyol with embodiment 5 the samely.This film is carried out stripping test, and peeling off needed stress is 66.3g/cm, and separability is bad.The characteristic of the Elastic Film that obtains in addition, is as shown in table 3.In addition, the surface atom of this film consists of 0.239, and water contact angle is 76 degree.The results are shown in table 3.

[table 2]

[table 3]

The present invention is had been described in detail, and also with reference to specific embodiment, but in addition various changes or modification will be readily apparent to persons skilled in the art without departing from the spirit and scope of the present invention.

The application speciallys permit application (the special 2008-306247 of hope) based on the Japan that applied on December 01st, 2008 and the Japan that applied on 07 31st, 2009 speciallys permit application (the special 2009-179463 of hope), and these contents are introduced in conduct reference here.

Utilizability on the industry

According to the present invention, can simultaneously keep the certain intermiscibility with polyether glycol, one side is made urethane, can reduce the adhesivity of the urethane that obtains.In addition, with obtain polyurethane formed the time, can improve molding separability each other.And, the spandex fiber that use is made of this urethane, when being configured as dress material etc., because the reduction of the usage quantity of finish or smooth agent etc. brings cost cutting, the obstruction frequency of, machinery stained by product or utensil reduces the raising that brings operational stability, frictional force reduces, and can expect to drive electric power reduction etc. thus.Therefore, industrial value of the present invention is remarkable.

Claims (29)

1. the manufacture method of a urethane, it is characterized in that, make (a) molecular end have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) raw material of chainextender carry out polyaddition reaction, when obtaining urethane, (a) to have the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl for (a) molecular end be 0.01～50.00 weight % with (b) ratio of the total of polyether glycol to the poly-hydroxy hydrocarbon system polymer phase of molecular end with at least one hydroxyl, is being selected from the acid amides series solvent, N-Methyl pyrrolidone, the coexistence of the solvent of N-ethyl pyrrolidone and methyl-sulphoxide is reaction down.

2. according to the manufacture method of the urethane of claim 1 record, it is characterized in that the number-average molecular weight that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is 500～5000.

3. according to the manufacture method of urethane of claim 1 or 2 records, it is characterized in that the average hydroxyl number of each molecule that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is 1.5～2.7.

4. according to the manufacture method of the urethane of each record in the claim 1～3, it is characterized in that described (c) polyisocyanate compounds is an aromatic poly-isocyanate.

5. according to the manufacture method of the urethane of each record in the claim 1～4, it is characterized in that described (d) chainextender is a polyamine compounds.

6. according to the manufacture method of the urethane of each record in the claim 1～5, it is characterized in that the main framing that described (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least one hydroxyl is a hydrogenated butadiene polymer.

7. according to the manufacture method of the urethane of each record in the claim 1～6, it is characterized in that, the poly-hydroxy hydrocarbon system polymkeric substance that described (a) molecular end has at least one hydroxyl be by (A) poly-hydroxy hydrocarbon polymer with (B) contain the polyester polyol that ester group compound or carboxylated compound form.

8. according to the manufacture method of the urethane of claim 7 record, it is characterized in that in the described polyester polyol, described (A) and described (B) form at least one ester bond, and the oxygen level in this polyester polyol be 2.0 quality % above, below the 13.5 quality %.

9. according to the manufacture method of claim 7 or 8 urethane of putting down in writing, it is characterized in that described (B) is polylactone.

10. according to the manufacture method of the urethane of each record in the claim 7～9, it is characterized in that described polyester polyol forms (B) (A) segmented copolymer of (B) type by described (A) and described (B).

11. the manufacture method according to claim 7 or 8 urethane of putting down in writing is characterized in that described (B) is dicarboxylic acid.

12. the manufacture method according to the urethane of claim 11 record is characterized in that the carbonatoms of described dicarboxylic acid is more than 2, below 15.

13. the manufacture method according to claim 10 or 11 urethane of putting down in writing is characterized in that described polyester polyol forms (AB) by described (A) and described (B) _nThe segmented copolymer of A type, wherein, n is the integer more than 1.

14. a urethane, the manufacture method manufacturing of the urethane by each record in the claim 1～13 obtains.

15. urethane, it is characterized in that, contain poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender, the shared part by weight of (b) polyether glycol in the urethane is 54 weight %～99 weight %.

16. a polyurethane formed body is characterized in that, is made of claim 14 or 15 urethane of putting down in writing.

17. polyurethane formed body, it is characterized in that, by contain poly-hydroxy hydrocarbon system polymkeric substance that (a) molecular end has at least one hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) urethane of chainextender constitute, it is that Sauerstoffatom/carbon atom is below 0.22 that the atom on the surface of this polyurethane formed body is formed.

18. the polyurethane formed body according to claim 17 record is characterized in that, the water contact angle on the surface of described polyurethane formed body is more than 80 degree.

19. a film is characterized in that, is made of claim 14 or 15 urethane of putting down in writing.

20. a fiber is characterized in that, is made of claim 14 or 15 urethane of putting down in writing.

21. polyester polyol, it is characterized in that, by (A) poly-hydroxy hydrocarbon polymer with (B) contain ester group compound or carboxylated compound forms, described (A) and described (B) form at least one ester bond, and the oxygen level in the described polyester polyol is more than the 2.0 quality %, below the 13.5 quality %.

22. the polyester polyol according to claim 21 record is characterized in that described (B) is polylactone.

23. the polyester polyol according to claim 21 or 22 records is characterized in that described polyester polyol forms (B) (A) segmented copolymer of (B) type by described (A) and described (B).

24. the polyester polyol according to claim 21 record is characterized in that described (B) is dicarboxylic acid.

25. the polyester polyol according to claim 24 record is characterized in that the carbonatoms of described dicarboxylic acid is more than 2, below 15.

26. the polyester polyol according to claim 24 or 25 records is characterized in that described polyester polyol forms (AB) by described (A) and described (B) _nThe segmented copolymer of A type, wherein, n is the integer more than 1.

27. the polyester polyol according to each record in the claim 21～26 is characterized in that, the number-average molecular weight of described polyester polyol is more than 500, below 5000.

28. the polyester polyol according to each record in the claim 21～27 is characterized in that, described (A) poly-hydroxy hydrocarbon polymer is a hydrogenation polydiene polyvalent alcohol.

29. a polymkeric substance is characterized in that, the one at least that constitutes the hydroxyl of the polyester polyol of each record in the claim 21～28 forms amino-formate bond.