CN103172816B - 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 and the purposes of urethane obtained by the method

The application is the divisional application based on following Chinese patent application:

The original bill applying date: on November 30th, 2009

Original bill application number: 200980149060.7(PCT/JP2009/070136)

Original bill application title: the manufacture method of urethane and the purposes of urethane obtained by the method

Technical field

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

Background technology

Urethanes and urethaneureas compound are applied to various field.Urethanes primarily of the polyol of polyester polyol or polyether glycol etc. and the manufacture such as isocyanate compound and the chainextender added as required, whipping agent, foam stabilizer, through being commonly used for the purposes such as polyurethane series spandex fiber or urethaneureas system spandex fiber.Especially, have the fiber of urethaneureas structure, because soft segment component uses polyether glycol, hard segment uses the much higher amine compound of cohesive force, so have the character of elastic properties, stretch recovery excellence., these polyurethane series spandex fibers, because the adhesivity between fiber is high, so easy zbility worsens when spinning, in addition, because frictional force is large, so break in machine in the manufacturing procedure of the spinning-drawing machine of linear contact lay, warper, knitting machine or guide rail.Therefore, easily there is the problems such as broken string in generation in manufacturing procedure.Therefore, in order to reduce the frictional force between the machine of manufacturing procedure and line, have and add as the solid metal soap of finish or the method for oil soluble polymer, higher fatty acid, amino modified polysiloxane etc., or the method be dispersed with as the talcum of smooth agent, silicon-dioxide, colloidal alumina or titanium oxide etc., have further and silicon dibasic alcohol or silicon diamines are imported to (such as, patent documentations 1) such as the methods of a part for polyurethane backbone.

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

On the other hand, the raw material of urethane uses the example with the poly-hydroxy hydrocarbon system polymkeric substance of hydroxyl, for example there are the purposes (patent documentation 2) of the close-burning properties-correcting agent as carbamate system resin for improving polyolefin material, or to mix with polytetramethylene glycol as macromolecule polyol and manufacture urethane, attempt the research (patent documentation 3) of the weather resistance improving polyurethane series spandex fiber., in the method that patent documentation 3 is recorded, the hydrophobicity of macromolecule polyol is too high, worsens with the intermiscibility of polyether glycol, there is gelation when manufacturing urethane, or disperses inhomogenous problem when being made yarn or film.In addition, known, the resistance to chlorine, hot water resistance, excellent in light-resistance etc. of the extendible cloth and silk that the fiber that the urethane that the method adopting patent documentation 3 to record manufactures is formed makes or swimming suit, but use the poly-hydroxy hydrocarbon system polymkeric substance with hydroxyl as raw material, the adhesivity of urethane reduces, the adhesivity of the moldings such as the film be even made up of urethane or spandex fiber reduces, and is not used in the object improving separability.In addition, the polyurethane series spandex fiber that patent documentation 3 is recorded, although illustrate polyvalent alcohol and polyamine as chainextender, but in fact, be by with polyvalent alcohol be chainextender dissolve the spandex fiber obtained that spin processes obtains, use the so-called urethaneureas structure of polyamine to obtain by the method, gel easily occurs during chain extension reaction or three-dimensional cross-linkedly waits abnormal response, existence is difficult to be configured as the fiber of homogeneous or the problem of film.

In addition, on the other hand, complete following research, for the purpose of all physical property improveing polyurethane elastomeric fiber, and improve the material composition of urethane.Such as, as using the example of polyester polyol, propose by there is with side chain glycol constituent that the polyvalent alcohol of alkyl is essential component and taking dimeracid as the hydrophobic polyester polyvalent alcohol (patent documentation 4) that the carboxylic acid constituent of essential component is formed., even if when using these polyester polyols, also still can not get the urethane showing sufficient separability.

Background technology document

Patent documentation

Patent documentation 1: the flat 10-259577 publication of Japanese Laid-Open

Patent documentation 2: the flat 6-158016 publication of Japanese Laid-Open

Patent documentation 3: the flat 11-131325 publication of Japanese Laid-Open

Patent documentation 4: Japanese Laid-Open 2002-212273 publication

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 manufacture urethane and urethaneureas method and to manufacturing the useful new polyester polyol of urethaneureas, when manufacturing urethane from polyether glycol, polyisocyanate compounds and chainextender, urethane and the high function polyurethane applications of urethaneureas to polyurethane elastomeric fiber or film and dress material etc. exceedingly useful, and, adhesivity is low, and separability is high.

For solving the means of problem

The present inventor has carried out conscientious research to solve above-mentioned problem, found that, when manufacturing urethane, by the poly-hydroxy hydrocarbon system polymkeric substance using polyether glycol and molecular end to have at least one hydroxyl, preferably there is the polyester polyol of specific structure and certain oxygen level, more preferably this polyester polyol and polyether glycol is mixed, by reacting with polyisocyanate compounds and chainextender under the coexisting of solvent, obtained urethane and the adhesivity of urethaneureas can be reduced, easy zbility when can improve separability and spin, thus complete the present invention.

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

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

[2] preferred, the manufacture method of the urethane that above-mentioned [1] is recorded, 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 that above-mentioned [1] or [2] are recorded, is characterized in that, the average hydroxyl number that described (a) molecular end has every a part of 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 recorded any one of above-mentioned [1] ~ [3], it is characterized in that, described (c) polyisocyanate compounds is aromatic poly-isocyanate.

[5] preferred, the manufacture method of the urethane recorded any one of above-mentioned [1] ~ [4], it is characterized in that, described (d) chainextender is polyamine compounds.

[6] preferred, the manufacture method of the urethane recorded any one of above-mentioned [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 hydrogenated butadiene polymer.

[7] preferred, the manufacture method of the urethane recorded any one of 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 is the polyester polyol formed containing ester group compound or carboxylated compound with (B) by (A) poly-hydroxy hydrocarbon polymer.

[8] preferred, the manufacture method of the urethane that above-mentioned [7] are recorded, it is characterized in that, in described polyester polyol, described (A) and described (B) form at least one ester bond, further, the oxygen level in this polyester polyol is below 2.0 quality % or more than 20%, 13.5 quality % or 13.5 quality %.

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

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

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

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

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

[14] urethane, is obtained by the manufacture method manufacture of the urethane recorded any one of described [1] ~ [13].

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

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

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

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

[19] film, is characterized in that, the urethane recorded by described [14] or [15] is formed.

[20] fiber, is characterized in that, the urethane recorded by described [14] or [15] is formed.

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

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

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

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

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

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

[27] preferred, the polyester polyol recorded any one of above-mentioned [21] ~ [26], it is characterized in that, the number-average molecular weight of described polyester polyol is more than 500 or 500, less than 5000 or 5000.

[28] preferred, the polyester polyol recorded any one of above-mentioned [21] ~ [27], it is characterized in that, described (A) poly-hydroxy hydrocarbon polymer is hydrogenated polydiene polyol.

[29] polymkeric substance, is characterized in that, at least one forming the hydroxyl of the polyester polyol recorded any one of described [21] ~ [28] forms amino-formate bond.

Invention effect

According to the present invention, simultaneously can maintain the certain intermiscibility with polyether glycol, one side manufactures urethane, can reduce the adhesivity of the urethane obtained.In addition, by obtain polyurethane formed time, molding separability each other can be improved.And, use the spandex fiber be made up 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, blocking frequency that is stained by product, mechanical or utensil reduces the raising bringing operational stability, frictional force reduces, and can expect thus to drive electric power reduction etc.

Embodiment

The explanation of the constitutive requirements below recorded 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 used by the poly-hydroxy hydrocarbon system polymkeric substance (a) of the present invention molecular end with at least 1 hydroxyl and obtain together with (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender.

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

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

[changing 1]

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

Content or the position of the described polymkeric substance in urethane of the present invention are not particularly limited, as long as have the polymkeric substance of said structure in polymeric chain.Compound containing said structure for example there are such as urethane resin, urethaneureas resin or their prepolymer etc.

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

The so-called urethane of the present invention, as long as be not particularly limited, just represent urethane or urethaneureas, these 2 kinds of resins have roughly the same physical property, and this is just known before being.On the other hand, as the difference of structural attitude, urethane is that chainextender uses short-chain polyol manufacture to obtain, and urethaneureas to be chainextender use polyamine compounds manufacture to obtain.

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

<(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 in the present invention has at least 1 hydroxyl refers to the hydrocarbon skeleton of representative divinyl, isoprene, chloroprene equiconjugate diene and so on be repeating unit polymkeric substance or polyester polyol described later.By they and polyether glycol is used in combination, use them to manufacture urethane, the adhesivity of the urethane obtained, the separability of polyurethane moldings, easy zbility when spinning can be improved.

Take hydrocarbon skeleton as the polymkeric substance of repeating unit, preferable examples has the polymkeric substance obtained as follows, such as passing through with hydrogen peroxide is polymerization starter, make 1,3-divinyl carries out radical polymerization, directly be made the conjugated diene polymer that end has hydroxyl, or use anionic polymerization catalyst, manufacture the reactive polymer of end and basic metal bonding, then by making the reaction such as mono-epoxy compounds or formaldehyde, be made the conjugated diene polymer that end has hydroxyl, the conjugated diene polymer obtained carried out hydrogenation according to well-established law and the polymkeric substance obtained.Further, now, above-mentioned conjugated diolefine can with the vinylbenzene of amount less than 30 % by weight or 30 % by weight, vinyl cyanide, copolymerization such as vinyl monomer such as (methyl) methyl acrylate, vinyl-acetic ester etc.

In addition, for example there are with ozone etc. iso-butylene or iso-butylene and isoprene, 1, the polymkeric substance oxygenolysis process of 3-pentadiene equiconjugate diene, then, carries out reduction treatment by lithium aluminium hydride etc., obtain the isobutylene-based polymer that end has hydroxyl, by well-established law by the polymkeric substance after the polymer hydrogenation that obtains, and, equally by the multipolymer oxygenolysis of the alpha-olefin such as ethene, propylene and diene compound, carry out reduction treatment, carry out the polymkeric substance etc. after hydrogenation.

Molecular end of the present invention has in the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl, preferably, main framing is the poly-hydroxy hydrocarbon system polymkeric substance of hydrogenated butadiene polymer, hydrogenated polyisoprene and polyisobutene, from easily starting with 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, there is the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl and the total amount of polyether glycol, preferably more than 0.01 % by weight or 0.01 % by weight relative to molecular end.More preferably more than 0.03 % by weight or 0.03 % by weight, further preferably more than 0.05 % by weight or 0.05 % by weight, particularly preferably more than 0.07 % by weight or 0.07 % by weight, most preferably 0.1 % by weight.This numerical value is larger, and the adhesivity of the polyurethane based resin obtained more has the tendency of decline.On the other hand, the upper limit preferably less than 50.00 % by weight or 50.00 % by weight.More preferably less than 30.00 % by weight or 30.00 % by weight, further preferably less than 25.00 % by weight or 25.00 % by weight, particularly preferably less than 15.00 % by weight or 15.00 % by weight, most preferably less than 10.00 % by weight or 10.00 % by weight.This value is less, then the adhesivity of the polyurethane based resin obtained declines, but the tendency that its elastic properties or stretch recovery are improved.

The number-average molecular weight of described poly-hydroxy hydrocarbon system polymkeric substance is 500 ~ 5000, preferably 700 ~ 4000, more preferably 900 ~ 3500, and be liquid or wax-like under normal temperature.Number-average molecular weight is too high, has following tendency: the viscosity of polyether glycol or prepolymer, pre-polymer solution becomes too high, cause operability or productivity to worsen, or the polyether polyols with reduced unsaturation obtained physical property at low temperatures worsens.Too low, have following tendency: the polyether polyols with reduced unsaturation obtained is hardening, sufficient flexibility cannot be obtained, or the elastic performance such as intensity or elongation is insufficient, or repeatedly carry out stretching, when recovering, leave excessive residual set.In addition, polyester polyol refers in molecule the material of the hydroxyl of ester bond and more than 2 or 2 with more than at least 2 or 2, and two ends of preferred polyester polyol backbone are hydroxyl.

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

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

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

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

<(A) poly-hydroxy hydrocarbon polymer >

(A) poly-hydroxy hydrocarbon polymer in the present invention refers to hydrocarbon skeleton to be the polymkeric substance of repeating unit, and has the polymkeric substance of at least 2 hydroxyls in above-mentioned polymkeric substance.

The polymkeric substance being repeating unit with above-mentioned hydrocarbon skeleton is had no particular limits, the polymkeric substance can be the hydrocarbon of the halogen alternatively base of element such as chlorine, fluorine, the bromine etc. had beyond carbon and hydrogen being repeating unit, but being preferably repeating unit with the hydrocarbon of carbon and hydrogen evolution, polymkeric substance is (following, sometimes hydrocarbon polymer is referred to as), more preferably aliphatic hydrocarbon polymkeric substance.

Hydrocarbon polymer in the present invention for example there are with the straight-chain hydrocarbon polymkeric substance that is repeating unit or with the polymkeric substance of hydrocarbon for repeating unit in molecule with side chain.

Because the content of the hydrocarbon in molecule with side chain is many, the fusing point of hydrocarbon polymer reduces, and becomes easy process, so the hydrocarbon polymer that the content preferably with the hydrocarbon of side chain is many.

Above-mentioned hydrocarbon polymer can be the self-aggregate of 1 repeating unit polymerization, also can be the multipolymer of repeating unit containing 2 or more than 2.

The carbonatoms of the repeating unit of above-mentioned hydrocarbon is not particularly limited, is generally more than 2 or 2, be preferably more than 3 or 3, be generally below 9 or 9, be preferably less than 6 or 6.

The end importing polymkeric substance can be rolled into a ball from easy high-ranking military officer, easy control molecular weight is considered, the polymkeric substance of poly-hydroxy hydrocarbon polymer in the present invention preferably containing divinyl, iso-butylene, isoprene, chloroprene equiconjugate dienes, more preferably make hydrogenated butadiene polymer, hydrogenated polyisoprene and Parleam etc. conjugated diene is polymerized separately after the polymkeric substance that obtains of hydrogenation is (following again, hydrogenated polydiene), from the viewpoint of the easiness of the easiness of starting with or process, more preferably hydrogenated butadiene polymer.

Poly-hydroxy hydrocarbon polymer in the present invention is the material in the polymer with at least 2 hydroxyls.As long as the quantity of above-mentioned hydroxyl meets the scope of following oxygen level, usually do not limit, but usual more than 2 or 2, less than 6 or 6, preferably less than 3 or 3.The position of hydroxyl is not particularly limited, preferably has hydroxyl in molecular end, more preferably in molecular end, there are more than 2 or 2, more preferably have hydroxyl at two ends of the main chain of hydrocarbon polymer.

Form at least 1 ester bond by the poly-hydroxy hydrocarbon polymer (A) of formation polyester polyol of the present invention, the hydrophobicity of adjustment polyester polyol, can obtain the polyester polyol being polymerized object height with the intermiscibility saturated hydrocarbon ratio of polyether glycol.In addition, the urethane using such polyester polyol to obtain demonstrates high separability.

The number-average molecular weight of the poly-hydroxy hydrocarbon polymer in the present invention is usually more than 100 or 100, preferably more than 200 or 200, further preferably more than 300 or 300, usually below 5000 or 5000, preferably below 4000 or 4000, preferred below 3000 or 3000 further.Less than above-mentioned lower value, there is following tendency: the polyether polyols with reduced unsaturation obtained is hardening, cause flexibility to decline, or cause the elastic performance such as intensity or elongation to decline, or repeatedly carry out stretching, when recovering, leave excessive residual set.Exceed above-mentioned higher limit, have following tendency: the viscosity of polyether glycol or prepolymer, pre-polymer solution becomes too high, operability or productivity decline, or the polyether polyols with reduced unsaturation obtained physical property at low temperatures declines.

Being not particularly limited the proterties of the poly-hydroxy hydrocarbon polymer in the present invention, usually, is liquid or wax-like at normal temperatures.

<(B) containing ester group compound >

As long as what use in the present invention has ester group containing ester group compound, just there is no particular limitation, and usually for example there are the compound that repeating unit is undertaken by ester bond being polymerized, preferred lactone carries out the polylactone that ring-opening polymerization obtains.

< polylactone >

Polylactone in the present invention can by being that raw material carries out known polyreaction to obtain with lactone.

The lactone of concrete use for example there are 6-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylammonium caprolactone, 3,3,5-trimethylammonium caprolactone, beta-propiolactone, gamma-butyrolactone, δ-valerolactone, γ-valerolactone, oenantholacton etc., they can be used alone, also can two or more is used in combination.Wherein, from the viewpoint of easily starting with, reactive high, preferred 6-caprolactone, δ-valerolactone, γ-valerolactone, more preferably 6-caprolactone.

Below, as by poly-hydroxy hydrocarbon polymer with containing the polyester polyol that ester group compound is formed, be described for the polyester polyol formed by poly-hydroxy hydrocarbon polymer and polylactone.

The polyester polyol > that < is formed by poly-hydroxy hydrocarbon polymer and polylactone

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

The copolymerized form of above-mentioned poly-hydroxy hydrocarbon polymer and polylactone is not particularly limited, is preferably made up of the polyester polyol of the segmented copolymer of (B) (A) (B) type (A) poly-hydroxy hydrocarbon polymer part and (B) polylactone moiety.(B) be the ring-opening polymerization polymer of lactone, (A) and (B) carries out bonding by ester bond.

The polymerization degree of (A) or (B) is not particularly limited, as long as make the value that the oxygen level in polyester polyol and molecular weight become desired, considers that the molecular weight of raw material carries out determining.

According to the physical property of desired urethane resin, by regulating the polymerization degree of described (A) or (B), molecular weight or the oxygen level of generated polyester polyol easily can be changed.Manufacture method is not particularly limited, can by under solvent-free, under the existence of the catalyzer such as titanium isopropylate or tetrabutyl titanate, make poly-hydroxy hydrocarbon polymer and lactone carry out reaction to obtain with requirement ratio.

<(B) carboxylated compound >

As long as the carboxylated compound used in the present invention has carboxyl, be not particularly limited, usually, for example there are the substituted carboxylic acid compound etc. of monocarboxylic acid compound, dicarboxylic acid compound, alcohol acid or alcoxyl acid etc., preferred dicarboxylic compound.

< dicarboxylic acid >

The dicarboxylic acid compound used in the present invention can be any one in aliphatic dicarboxylic acid, aromatic dicarboxylic acid, 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.Concrete example has propanedioic acid, succsinic acid, maleic acid, FUMARIC ACID TECH GRADE, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1,9-nonane dicarboxylic acid (1,9-ノ Na メ チ レ Application ジ カ Le ボ Application acid), 1,10-decamethylene dicarboxylic acid, 1,11-11 supports dicarboxylic acid, 1,12-ten two methylene dicarboxylic acid etc.In addition, aromatic dicarboxylic acid for example there are phthalic acid, m-phthalic acid, terephthalic acid, naphthalene diacid, anthracene diacid or luxuriant and rich with fragrance diacid etc. particularly.These can a kind ofly use, and also can use as two or more mixture.In addition, the halogen substituents etc. of the acid anhydrides of these dicarboxylic acid, alkyl ester or unsaturated link(age) can also be used.Wherein, from easily starting with and the consideration of thermostability height, 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 formed by poly-hydroxy hydrocarbon polymer and carboxylated compound, be described for the polyester polyol formed by poly-hydroxy hydrocarbon polymer and dicarboxylic acid.

The polyester polyol > that < is formed by poly-hydroxy hydrocarbon polymer and dicarboxylic acid

The polyester polyol of ester bond is formed respectively between at least one hydroxyl that the polyester polyol formed by poly-hydroxy hydrocarbon polymer and dicarboxylic acid in the present invention normally has separately at 2 molecular polyhydroxyl hydrocarbon polymers and 2 carboxyls that 1 molecular dicarboxylic acids comprises.

(AB) that preferably formed by poly-hydroxy hydrocarbon polymer (A) and dicarboxylic acid (B) _nthe polyester polyol of A type.(A) and (B) carry out bonding by ester bond, also can by the carboxylic acid derivative manufacture of carboxylic acid diesters etc.

Usually, n is the integer of more than 1 or 1, the polyester polyol of the ABA type of each and a part poly-hydroxy hydrocarbon polymer bonding of two ends when being more preferably equivalent to said n=1, dicarboxylic acid.

The molecular weight of the poly-hydroxy hydrocarbon polymer that usually can obtain is comparatively large, and minimum also more than 1500 or 1500, two ends and the poly-hydroxy hydrocarbon polymer of dicarboxylic acid react and generate polyester polyol, and molecular weight is more than 3000 or 3000.This is because, when n value becomes large, the molecular weight of polyester polyol becomes excessive, has following tendency: the viscosity of prepolymer or pre-polymer solution is too high, operability during manufacture urethane or productivity decline, or the physical property of the polyether polyols with reduced unsaturation obtained in low temperature declines.

The structure beyond said structure can be had in the molecule of polyester polyol of the present invention, but preferably not containing the polyester polyol of other structures except above-mentioned part.

In addition, detail the construct (A) for the formation of ester bond and (B), but polyester polyol of the present invention is not limited to this in above-mentioned record, as long as the molecular structure obtained is identical, it can be the material obtained by any raw material, reaction method.

< oxygen level >

Oxygen level in polyester polyol of the present invention refers to the oxygen level in 1 molecule polyester polyol, typically refers to the ratio of the molecular weight of Sauerstoffatom contained in molecule and 1 molecule polyester polyol.Such as, when there is 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 more than 2.0 quality % or 2.0 quality %, the scope of below 13.5 quality % or 13.5 quality %, preferably more than 2.2 quality % or 2.2 quality %, more preferably more than 2.5 quality % or 2.5 quality %, preferred more than 3.0 quality % or 3.0 quality % further, preferably below 13 quality % or 13 quality %, more preferably below 12 quality % or 12 quality %, further preferred 11.0 quality %.Not enough above-mentioned in limited time lower, with the intermiscibility of polyether glycol or solvability in a solvent insufficient, exceed above-mentioned in limited time upper, the adhesivity of the polyurethane based resin obtained increases, thus undesirable.

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

The physical property > of < polyester polyol

The number-average molecular weight of polyester polyol of the present invention can be adjusted by the kind of (A) or (B) of use or amount.Number-average molecular weight is generally more than 500 or 500, and preferably more than 600 or 600, further preferably more than 800 or 800, be generally below 10000 or 10000, be preferably less than 7000 or 70000, further preferably less than 5000 or 5000.Number-average molecular weight represents the molecular-weight average of each molecule.Number-average molecular weight exceedes above-mentioned higher limit, has following tendency: the viscosity of prepolymer, pre-polymer solution becomes too high, and operability or productivity decline, or the polyether polyols with reduced unsaturation obtained physical property at low temperatures declines.Less than above-mentioned lower limit, have following tendency: the polyether polyols with reduced unsaturation sometimes obtained is hardening, sufficient flexibility cannot be obtained, or the elastic performance such as intensity or elongation is insufficient sometimes, repeatedly carry out stretching, when recovering, leave excessive residual set.

<(b) polyether glycol >

Polyether glycol in the present invention is the oxy-compound in intramolecular main framing with at least one or more than one ehter bond, repeating unit in main framing can be any one of stable hydrocarbon or unsaturated hydrocarbons, for example there are such as, 1, 4-butyleneglycol unit, 2-methyl isophthalic acid, 4-butyleneglycol unit, 3-methyl isophthalic acid, 4-butyleneglycol unit, 1, ammediol unit, 1, 2-propylene glycol units, 2-methyl isophthalic acid, ammediol unit, 2, 2-dimethyl-1, ammediol unit, 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, 1, 10-decanediol unit, 1, 4-cyclohexanedimethanol unit etc.

Wherein, form in the polyol unit of polyether glycol, the copolyether dibasic alcohol etc. of the copolyether polyvalent alcohol of preferred polytetramethylene ether diol or polytrimethylene ether glycol, the 3-methyltetrahydrofuran of 1 ~ 20 % by mole and tetrahydrofuran (THF) (such as, soil conservation ヶ paddy chemistry society produce " PTG-L1000 ", " PTG-L2000 ", " PTG-L3500 " etc.) or neopentyl glycol and tetrahydrofuran (THF).

<(c) polyisocyanate compounds >

The polyisocyanate compounds used in the present invention for example there are such as, 2,4-or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4 '-diphenylmethanediisocyanate (MDI), 2,4'-MDI, to phenylene vulcabond, 1,5-naphthalene diisocyanate, the aromatic diisocyanate of tolidine diisocyanate etc., α, α, α ', the aliphatic diisocyanate with aromatic nucleus of α '-tetramethyl-xylylene diisocyanate etc., methylene diisocyanate, trimethylene diisocyanate, lysinediisocyanate, 2,2,4-or 2,4,4-trimethyl hexamethylene diisocyanate, the aliphatic diisocyanate of 1,6-hexamethylene diisocyanate etc., Isosorbide-5-Nitrae-cyclohexyl diisocyanate, methylcyclohexane diisocyanate (hydrogenation TDI), 1-isocyanic ester-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (IPDI), 4,4 '-double-hexyl methane vulcabond, the alicyclic diisocyanate etc. of isopropylidene dicyclohexyl-4,4 '-vulcabond etc.They can be used alone, also can 2 kinds or two or more also use.

In the present invention, particularly preferably reactive high aromatic poly-isocyanate, particularly preferably tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI).In addition, it can be a material part for the NCO base of polymeric polyisocyanate being changed into carbamate, urea, biuret, allophanate, carbodiimide, oxazolidone, acid amides, imines etc., further, in polykaryon, also comprise isomer than that described above.

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

The words that the usage quantity of polymeric polyisocyanate is too much, unreacted isocyanate group carries out undesirable reaction, has the tendency being difficult to obtain desired physical property, very few words, the molecular weight of urethane and urethaneureas is insufficiently large, has the tendency that desired performance does not manifest.

<(d) chainextender >

In the present invention, the chainextender of indication is mainly divided into the compound of the hydroxyl with more than 2 or 2, has compound, the water of the amino of more than 2 or 2.Wherein, the preferred short-chain polyol of polyurethane applications, is specially the compound of the hydroxyl with more than 2 or 2, and the preferred polyamine compounds of urethaneureas purposes specifically preferably has the compound of the amino of more than 2 or 2.Wherein, in order to carry out with making stable reaction, preferably water is reduced as far as possible.

In addition, urethane resin of the present invention and with molecular weight (number-average molecular weight) be the compound of less than 500 or 500 as chainextender, the caoutchouc elasticity of polyurethane elastomer is improved, therefore in physical property more preferably.

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

The compound with the amino of more than 2 or 2 for example there are such as, 2, 4-or 2, 6-tolylene diamine, xylylene diamine, 4, the aromatic diamine of 4 '-diphenylmethanediamiand etc., quadrol, 1, 2-propylene diamine, 1, 6-hexanediamine, 2, 2-dimethyl-1, 3-propylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1, 3-1,5-DAP, 2, 2, 4-or 2, 4, 4-trimethylhexane diamine, 2-butyl-2-ethyl-1, 5-pentamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, the aliphatie diamine of 10-decamethylene diamine 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, 4-diamino-cyclohexane, 1, the alicyclic diamine etc. of the two aminomethyl cyclohexane of 3-etc.These chainextenders can be used alone, also can more than 2 kinds or 2 and use.Wherein, preferred quadrol, propylene diamine, 1,3-1,5-DAP, 2-methyl isophthalic acid in the present invention, 5-pentamethylene diamine, wherein, more preferably quadrol, propylene diamine.

To the usage quantity of these chainextenders, there is no particular limitation, when the equivalent that the equivalent that the hydroxyl equivalent of the total from (a) and (b) deducts polyisocyanate compounds obtains is used as 1, be generally more than 0.1 equivalent or 0.1 equivalent, below 5.0 equivalents or 5.0 equivalents.Preferably more than 0.8 equivalent or 0.8 equivalent, below 2.0 equivalents or 2.0 equivalents, more preferably more than 0.9 equivalent or 0.9 equivalent, below 1.5 equivalents or 1.5 equivalents.The words that usage quantity is too much, there is following tendency: the urethane obtained and urethaneureas become really up to the mark, can not get desired characteristic, or be difficult to be dissolved in solvent, processing becomes difficulty, very few, has following tendency: too soft, can not get sufficient intensity, elastic recovery properties or elasticity retention, or hot properties worsens.

Using when being used for the high-performance polyurethane elastomer purposes of polyurethane elastomeric fiber or synthetic leather etc. as the urethane of the target in the present invention and urethaneureas, the combination of raw material for example there are following example.

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

Other additives of < >

In urethane of the present invention in addition to the foregoing, other additives can also be added as required.These additives for example there are " CYANOX1790 " (manufacture of CYANAMID society), " IRGANOX245 ", " IRGANOX1010 " (being manufactured by チ バ ス ペ シ ャ リ テ ィ ー ケ ミ カ Le ズ society above), the antioxidant of " SumilizerGA-80 " (manufacture of Sumitomo Chemical society) or 2,6-dibutyl-4-methylphenol (BHT) etc., " TINUVIN622LD ", " TINUVIN765 " (being manufactured by チ バ ス ペ シ ャ リ テ ィ ー ケ ミ カ Le ズ society above), " SANOLLS-2626 ", " SANOLLS-765 " (more than, three Gong She System) etc. photostabilizer, " TINUVIN328 ", the ultraviolet Line absorption agent of " TINUVIN234 " (being manufactured by チ バ ス ペ シ ャ リ テ ィ ー ケ ミ カ Le ズ society above) etc., the silicon compound of dimethyl siloxane polyoxyalkylene copolymers etc., red phosphorus, organo phosphorous compounds, organic compound containing 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 preventing agent of carbodiimide compound etc., 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 poly-hydroxy hydrocarbon polymer to manufacture.Poly-hydroxy hydrocarbon polymer itself is known compound, can manufacture according to usual used method.In addition, these commercially available compounds also can be adopted to use.Representationally for example there are the polymkeric substance obtained as follows, , by taking hydrogen peroxide as polymerization starter, make divinyl, isoprene, chloroprene equiconjugate diene, preferably 1, 3-divinyl carries out radical polymerization, directly be made the conjugated diolefin polymer that end has hydroxyl thus, or use anionic polymerization catalyst, manufacture the reactive polymer of end and basic metal bonding, then by making the reaction such as mono-epoxy compounds or formaldehyde, be made the conjugated diolefin polymer that end has hydroxyl, the conjugated diene polymer obtained is carried out hydrogenation according to well-established law and the polymkeric substance obtained.Further, now, above-mentioned conjugated diolefine can with the vinylbenzene of amount below 30 quality % or 30 quality %, vinyl cyanide, copolymerization such as vinyl monomer such as (methyl) methyl acrylate, vinyl-acetic ester etc.

In addition, for example there are with ozone etc. the polymkeric substance of iso-butylene or iso-butylene and isoprene, 1, the polymkeric substance oxygenolysis process of 3-pentadiene equiconjugate diene, then, carry out reduction treatment by lithium aluminium hydride etc., obtain the isobutylene-based polymer that end has hydroxyl, by well-established law by the polymkeric substance after the polymer hydrogenation that obtains and, equally by the multipolymer oxygenolysis of the alpha-olefin such as ethene, propylene and diene compound, carry out reduction treatment, carry out the polymkeric substance etc. after hydrogenation.

The manufacture of polyester polyol of the present invention can adopt known esterification techniques in the past.Such as, have following methods: the method for method, under reduced pressure esterification that polyvalent alcohol and lactone or dicarboxylic acid are reacted at ambient pressure, under the inert solvent of toluene and so on exists, carry out esterification after, condensation water or condensation alcohol and solvent azeotropic are removed, makes it the method etc. outside reaction system.

The temperature of reaction of the esterification normally scope of 100 ~ 250 DEG C.Preferably 120 ~ 240 DEG C, preferably 140 ~ 230 DEG C further, the particularly preferably scope of 150 ~ 220 DEG C.Temperature of reaction is too low, and esterification is insufficient carries out, too high, and the painted of resultant likely becomes large.

Reaction is preferably carried out under the inert gas atmosphere of nitrogen or argon gas etc.Reaction pressure is any, can implement under normal or reduced pressure according to object.As the reaction polyvalent alcohol and dicarboxylic acid or dicarboxylic ester, because generate water or alcohol in reaction, so in order to promote that they depart from from reaction system, rare gas element can be made to circulate in reaction system.

< catalyzer >

The form of described esterification is not particularly limited, carries out esterification in the system that also can exist at catalyst-free, usually, successfully carry out to make esterification, the whole catalyzer usually used in esterification is used and transesterify is used can be used, such as, mineral acid or organic acid; The fatty acid salt of the muriate of the 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 acetic acid, 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.; Or 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, the most preferably Titanium series catalyst of isopropyl titanate or tetrabutyl titanate etc.The usage quantity of catalyzer now relative to all raw material total amounts of the described polyester diol of preparation, preferably 0.00001 ~ 5.0 quality %, further preferably 0.0001 ~ 2.0 quality %, most preferably 0.001 ~ 1.0 quality %.This amount is very few, and form the time that polyester polyol needs extremely to grow, resultant is easily painted.On the other hand, catalyzer usage quantity is too much, likely shows the reaction promoter action of the surplus to 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 or reduced pressure according to object.As the reaction polyvalent alcohol and dicarboxylic acid or dicarboxylic ester, because generate water or alcohol in reaction, so in order to promote that they depart from from reaction system, rare gas element can be made to circulate in reaction system.

The matrix of described reaction time of esterification according to the usage quantity of catalyzer, temperature of reaction, reaction, the difference to the physical property desired by the polyester polyol generated etc. and different, lower limit is generally 0.5 hour, preferably 1 hour, the upper limit was generally 30 hours, preferably 20 hours.

When using catalyzer during described esterification, in the polyester polyol resultant obtained, remain (titanium system) catalyzer that reaction uses.Because the removing of above-mentioned catalyzer is usually along with the operation of complexity, so the polyester polyol generated generally is not separated (titanium system) catalyzer, great majority are directly used in the manufacture of urethane like this.

Just, when the content of catalyzer is more or according to polyurethane applications, the titanium catalyst inactivation in polyester polyol is preferably made.Method for deactivating as the Titanium series catalyst in polyester polyol there can be exemplified such as the method that (1) makes polyester polyol and contacts with water under heating; (2) by the method etc. that the phosphorus compound of phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid ester etc. processes polyester polyol.Further, when adopting the method for described (1) contacted with water, such as, in polyester polyol, add the water of more than 1 quality % or 1 quality %, at the temperature of 70 ~ 150 DEG C, preferably 90 ~ 130 DEG C, heat 1 ~ 3 hours.Now, can carry out at ambient pressure by heating the inactivation process carried out, also can carry out under elevated pressure, after inactivation process, system being reduced pressure, can successfully the moisture that inactivation uses be removed from polyester polyol.

The manufacture method > of < urethane

In the present invention, when manufacturing urethane, main production of raw material for use use (a) molecular end has the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl, (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender.

When manufacturing above-mentioned urethane, under the condition that generally can coexist at solvent, manufacture urethane.In the present invention, preferably manufacture urethane under the coexisting of aprotic polar solvent.

Further, the usage quantity of each compound is not particularly limited, uses the amount of above-mentioned record.Below, the lower manufacture method that coexists of display aprotic polar solvent one routine, as long as but under the coexisting of aprotic polar solvent, be just not particularly limited.

To the aprotic polar solvent in the present invention, there is no particular limitation, considers from deliquescent viewpoint, preferably uses the solvent being selected from acid amides series solvent, N-Methyl pyrrolidone, N-ethyl pyrrolidone and methyl-sulphoxide in aprotic polar solvent.The concrete example of acid amides series solvent is N,N-dimethylacetamide, DMF and their 2 kinds or mixture of more than two kinds, particularly preferably dimethyl formamide or N,N-DIMETHYLACETAMIDE.

As an example of manufacture method, for example there are and make (a) and (b), method (single stage method) that (c) and (d) reacts or first mix (a) and (b), this mixture and (c) are reacted, prepare the prepolymer that two ends are isocyanate group, then, the method (two-step approach) that this prepolymer and (d) are reacted, make after (b) and (c) react, mix with (a), the method for reacting with (d), (b) (c) (d) is reacted after the method that mixes with (a).Wherein, two-step approach through such operation, namely by make polyether glycol in advance with 1 equivalent or 1 equivalent more than polymeric polyisocyanate react, prepare the intermediate closed with two terminal isocyanates of the soft chain segment being equivalent to urethane.By preparing prepolymer for the time being, then make it to react with chainextender, the molecular weight of soft chain segment part easily adjusts, and soft chain segment and being separated of hard segment easily become abundant, have the feature easily demonstrated as elastomeric performance.Especially, when chainextender is diamines, compared with the hydroxyl of polyether glycol, there is larger difference with the speed of response of isocyanate group, so more preferably adopt two-step approach (prepolymer method) to implement urethaneureas.

< single stage method >

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

Reaction makes each composition react at 0 ~ 250 DEG C usually, and its temperature is different according to the difference of the amount of solvent, the reactivity, conversion unit etc. of use raw material.Temperature is too low, and the carrying out of reaction is excessively slow, or due to raw material or structure adaptability low, productivity worsens, again, too high, and the decomposition of side reaction or urethane resin and not preferred occurs.Reaction can under reduced pressure froth breaking (deaeration) one side be carried out.In addition, reaction also can add catalyzer, stablizer etc. as required.Catalyzer has such as triethylamine, Tributylamine, dibutyl tin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid etc.; stablizer for example there are such as 2,6-dibutyl-4-methylphenols, thio-2 acid two (octadecanoyl) ester, two betanaphthyl phenylenediamines, three (dinonylphenyl) phosphide etc.

< two-step approach >

Two-step approach is also referred to as prepolymer method, usually, also can make it to react in two stages, namely polisocyanate component and polyhydroxy reactant is made to react than=1.0 ~ 10.00 with reaction equivalent in advance, manufacture prepolymer, then, toward wherein adding polisocyanate component or polyvalent alcohol, amine compound isoreactivity hydrogen compound composition.Especially, following method is useful, makes, relative to the polyisocyanate compounds reaction of polyhydroxy reactant more than equivalent, to prepare two end NCO prepolymers, then, makes to play a role as the short chain glycol of chainextender or diamines, obtains urethane.

In the present invention, two-step approach can be implemented under solvent coexists, but preferably carry out under non-protonic solvent coexists, concrete example has acid amides series solvent or N-Methyl pyrrolidone, N-ethyl pyrrolidone, dimethylsulfoxide solvent and their 2 kinds or mixture of more than two kinds.

In the present invention, when manufacturing urethane, consider from deliquescent viewpoint, preferred aprotic polar solvent in these solvents.Further, in aprotic polar solvent, preferred amide series solvent or N-Methyl pyrrolidone, N-ethyl pyrrolidone, methyl-sulphoxide, acid amides series solvent will exemplify concrete example, more preferably N,N-dimethylacetamide, N, dinethylformamide, particularly preferably DMF or N,N-dimethylacetamide.

During synthesis prepolymer, (1) like this, first, can not use solvent, makes polyisocyanate compounds and polyether glycol direct reaction, and synthesis prepolymer, directly uses like this; (2) with the method synthesis prepolymer of (1), then can be dissolved in solvent and using; (3) solvent can be used from the beginning to make polymeric polyisocyanate and polyether Glycols reaction.(1) situation, in the present invention, importantly, when making it with chainextender effect, by making chainextender be dissolved in solvent, or importing the medium method of solvent by prepolymer and chainextender simultaneously, obtaining the urethane of the form coexisted with solvent.

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

Be not particularly limited the usage quantity of chainextender, but relative to the equivalent of the NCO base contained by prepolymer, the lower limit of the scope of usage quantity is generally 0.1, preferably 0.8, the upper limit is generally 5.0, and preferably 2.0.

In addition, the organic amine of mono-functional or alcohol also can be made during reaction to coexist.

Chain extension reaction makes each composition react at 0 ~ 250 DEG C usually, and its temperature is different according to the difference of the amount of solvent, the reactivity, conversion unit etc. of use raw material.Temperature is too low, and the carrying out of reaction is excessively slow, or due to raw material or structure adaptability low, therefore productivity worsens, again, too high, side reaction or urethane resin occurs and to decompose and not preferred.Reaction can under reduced pressure a froth breaking one side be carried out.

In addition, reaction also can add catalyzer, stablizer etc. as required.Catalyzer has such as triethylamine, Tributylamine, dibutyl tin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid etc.; stablizer for example there are such as 2,6-dibutyl-4-methylphenols, thio-2 acid two (octadecanoyl) ester, two betanaphthyl phenylenediamines, three (dinonylphenyl) phosphide etc.But, when chainextender is the reactivity of short-chain fat race amine etc. high compound, does not preferably add catalyzer and implement.

The physical property > of < urethane

The urethane obtained by above-mentioned manufacture method is owing to reacting in the presence of solvent, so generally obtain with the state be dissolved in solution, but physics value does not limit state, is not particularly limited solution state, solid state.

The weight-average molecular weight of urethane is different according to the difference of purposes, as urethane polymeric solution, is generally 10,000 ~ 1,000,000, and preferably 50,000 ~ 500,000, more preferably 100,000 ~ 400,000, particularly preferably 100,000 ~ 300,000.As molecular weight distribution, Mw/Mn=1.5 ~ 3.5, preferably 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 preferably 50,000 ~ 500,000, more preferably 100,000 ~ 400,000, particularly preferably 150,000 ~ 400,000.As molecular weight distribution, Mw/Mn=1.5 ~ 3.5, preferably 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 % by weight relative to the gross weight of polyether polyols with reduced unsaturation, more preferably 3 ~ 15 % by weight, further preferably 4 ~ 12 % by weight, particularly preferably 5 ~ 10 % by weight.This hard segment amount is too much, and the polyether polyols with reduced unsaturation obtained has following tendency: do not show sufficient flexibility or elastic performance, and not soluble during use solvent, processing becomes difficulty.Very few, have following tendency: urethane polymer is too soft, processing becomes difficulty, or can not obtain sufficient intensity or elastic performance.

In addition, in the present invention, so-called hard segment is with P.J.Flory, JournalofAmericanChemicalSociety, 58,1877 ~ 1885(1936) based on, according to following formula, the weight of isocyanic ester relative to gross weight and amine bonding part is calculated.

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

Here,

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

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 the number-average molecular weight of the poly-hydroxy hydrocarbon system polymkeric substance of at least 1 hydroxyl

The storage stability of the polyurethane solution obtained in the present invention is good, not easily carries out gelation, and the rheological parameters' change with time of viscosity is little, and in addition, because thixotropy is little, institute is also very convenient for being processed into film, yarn etc.The polyurethane concentration of polyurethane solution, relative to the gross weight of the solution dissolved in a solvent, is generally 1 ~ 99 % by weight, and preferably 5 ~ 90 % by weight, more preferably 10 ~ 70 % by weight, particularly preferably 15 ~ 50 % by weight.The amount of urethane is very few, needs to remove a large amount of solvents, and productivity has the tendency of decline, too much, and the viscosity of solution is too high, and operability or processibility have the tendency of deterioration.

To polyurethane solution without specifying, but when preserving for a long time, at the temperature preferably below normal temperature or its, preserve under the inert gas atmosphere such as nitrogen or argon.

The polyurethane formed body of < and this purposes >

Obtain the present invention manufacture urethane and this carbamate pre-polymer solution after, by by they be shaped, polyurethane formed body can be obtained.

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

What atom composition (Sauerstoffatom/carbon atom) on the surface of polyurethane formed body specifically represented is, such as, by ESCA(electron spectroscopy for chemical analysis, or XPS(X ray luminous energy spectrometry ElectronSpectroscopyforChemicalAnalysis), when X-rayPhotoelectronSpectroscopy) measuring molding surface, Sauerstoffatom is relative to the relative existence ratio of carbon atom.

The value preferably less than 0.20 or 0.20 of atom composition (Sauerstoffatom/carbon atom) on the surface of polyurethane formed body of the present invention, further preferably less than 0.16 or 0.16.This value is less, and the adhesivity of the molding obtained has the tendency more reduced, and separability has better tendency.In addition, preferably more than 0.00 or 0.00, further preferably more than 0.05 or 0.05.This value is larger, packaging time overlapped for the molding obtained is had the tendency uprised, and such as, when molding is yarn, the yarn spooled not easily is untied and loses shape.

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

The water contact angle on this surface measures like this and obtains, and makes the water droplet of several μ L drop on molding on the surface, measures tangent line and the surperficial interior angle formed of molding of this drop within 10 seconds.The value of the water contact angle on the surface of polyurethane formed body of the present invention more than 80 degree or 80 degree, preferably more than 83 or 83, further preferably more than 86 or 86.This value is larger, and the adhesivity of the molding obtained more has the tendency of reduction, and separability more has good tendency.In addition, preferably less than 180 degree or 180 degree, further preferably below 150 or 150 degree of degree.This value is less, packaging time overlapped for the molding obtained is had the tendency uprised, and such as, when molding is yarn, the yarn spooled not easily is untied and loses shape.

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

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

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

The urethane of manufacture of the present invention and its carbamate pre-polymer solution also can be applied to the purposes of solvent system two-component coating, can be applied to the timber-works such as musical instrument, Fo Tan, furniture, fancy plywood, sporting goods.In addition, as tar epoxy polyurethane, also may be used for car repair purposes.

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

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

The urethane that the present invention manufactures and its carbamate pre-polymer solution, as tackiness agent, may be used for magnetic recording media, 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 manufactures and its carbamate pre-polymer solution, as the composition of fiber processing agent, may be used for shrink-resistant finish, wrinkle resistant processing, waterproof processing etc.

The urethane that the present invention manufactures, urethaneureas and its carbamate pre-polymer solution, as sealing agent and/or caulking agent, may be used for concrete inner wall, induction seam, window frame, wall type PC seam, ALC seam, plate class seam, compound glass sealing agent, heat-insulation window sealing agent, automobile sealing agent etc.

The urethane that the present invention manufactures and its carbamate pre-polymer solution, can use as medical material, as the material of compatible blood, may be used for pipe, conduit, artificial heart, artificial blood vessel, artificial valve etc., in addition, as disposable raw material, may be used for conduit, pipe, bag, surgical glove, artificial kidney Embedding Material etc.

The urethane that the present invention manufactures, urethaneureas and its carbamate pre-polymer solution, can make the terminal-modified rear raw material being used as UV curable coating, electronic beam solidified coating, the photosensitive polymer combination of flexographic plates, the optical fibre packages cover material feed composition of light-cured type etc.

Especially, playing the elastic performance of urethane or the characteristic aspect of water vapour permeability of the present invention's manufacture, being preferred for film or fiber, as these concrete purposes, being preferred for medical treatment, sanitary material, artificial leather and clothing spandex fiber.

Above, describe the purposes example of urethane and its carbamate pre-polymer solution employing the present invention's manufacture, but the present invention is by the restriction of these purposes.

Describe the manufacture method of film and fiber below, but be not have special restriction to manufacture method.

The manufacture method > of < film

The manufacture method of film is not particularly limited, known method can be used.Such as, the manufacture method of film for example there are, wet type made membrane method, is coated on by polyurethane resin solution in support or release materials, the soluble substance of Extraction solvent etc. in precipitation bath; And dry type made membrane method, polyurethane resin solution being coated in support or release materials, by heating or decompression etc., making solvent seasoning.The support used during dry made membrane is not particularly limited, the paper or cloth etc. that are coated with polyethylene or polypropylene film, glass, metal, release liner can be used.Being not particularly limited the mode of coating, can be any one of the known manner of doctor blade applicator, roller coating machine, spin coater, gravure coater etc.Drying temperature can set arbitrarily according to the ability of drying machine, needs selection temperature range, makes it that dry insufficient or desolventizing tempestuously can not occur.Preferably room temperature ~ 300 DEG C, the scope of more preferably 60 DEG C ~ 200 DEG C.

The physical property > of < film

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

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

At 23 DEG C 300% extends-shrinks in repetition test, the elastic retention (Hr1/H1) that the ratio of stress when stress when being extended by 150% when shrinking for the first time extends relative to 150% during first time elongation obtains is generally more than 10% or 10%, be preferably more than 20% or 20%, more preferably more than 30% or 30%, further preferably more than 40% or 40%.In the same manner, the elastic retention (Hr5/H5) that the ratio of stress when stress when being extended by 150% during the 5th contraction extends relative to 150% during the 5th elongation obtains is generally more than 30% or 30%, be preferably more than 50% or 50%, more preferably more than 70% or 70%, further preferably more than 85% or 85%.

In addition, at 23 DEG C 300% extend-shrink in repetition test, the elastic retention (H2/H1) that the ratio of stress when stress when being extended by 150% when extending for the second time extends relative to 150% during first time elongation obtains is generally more than 20% or 20%, be preferably more than 40% or 40%, be more preferably more than 50% or 50%, more preferably more than 60% or 60%.

In addition, secondary residual set that 300% at 23 DEG C extend-shrink in repetition test is generally below 40% or 40%, is preferably less than 30% or 30%, is more preferably below 25% or 25%, is particularly preferably below 20% or 20%.In addition, the residual set of the 5th time is generally below 50% or 50%, is preferably less than 35% or 35%, is more preferably below 30% or 30%, is particularly preferably below 25% or 25%.

In addition, the physical property of polyurethane film and yarn has very close relationship, the physics value obtained by the test etc. of film, even if also show same tendency in yarn (fiber).

The purposes > of < polyurethane fiber

For the fiber employing urethane of the present invention, more specifically exemplify purposes, be preferred for the purposes such as extensibility clothes, swimming suit, tights of pants, panty hose, cover of diaper, paper diaper, sweat shirt, underwear, socks, stylishness excellence.This is because excellences such as stretch recovery, elasticity, hydrolytic resistance, photostabilization, scale resistance, oil-proofness, processibilities.

Embodiment

Below, be more specifically described according to embodiments of the invention, but the present invention only otherwise exceed its purport, not by the restriction of these embodiments.In addition, the analysis in following embodiment and 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 poly-hydroxy hydrocarbon system polymkeric substance used in the present invention and the number-average molecular weight of polyether glycol hydroxyl value (the KOH(mg)/g by carrying out according to the acetylation method of JISK1557-1:2007) measuring method tries to achieve.

The molecular weight > of < urethane and urethaneureas

The urethane obtained or the molecular weight of urethaneureas measure as follows, prepare the dimethylacetamide solution of urethane or urethaneureas, (Dong ソ ー society manufactures to use GPC device, ProductName " HLC-8220 " (chromatographic column: TskgelGMH-XL(2 root)), the number-average molecular weight (Mn) that mensuration converts with polystyrene standard and weight-average molecular weight (Mw).

< stripping test method >

By the film overlay that 2 obtain, utilize test film tapping and plugging machine, obtain the initial test long portion that the long 4cm(of sample comprises when the long tensile testing machine of 1.5cm is fixed respectively and divide the lap with 2.5cm), the film of wide 1cm.For test film, to the additional 200g/cm of film overlay part ²pressure state under, under the condition of temperature 25 DEG C, relative humidity 50%, place 10 minutes, then, use tensile testing machine (FUDOH manufactures " レ オ メ ー タ ー NRM-2003J "), by the speed of dividing with 300mm/, underproof film is stretched, measure T-shaped stripping strength.

< film physical property >

Urethane or urethaneureas test film are made wide 10mm, long 100mm, the rectangle of thick about 50 μm, according to JISK6301, (オ リ エ ンテック society manufactures to use tensile testing machine, ProductName " テ Application シ ロ Application UTM-III-100 "), under the condition that jaw separation divides from 50mm, draw speed 500mm/, the intensity when tensile break strength under mensuration temperature 23 DEG C (relative humidity 55%), tension fracture elongation rate, 100% extend and when 300% extends.

< surface atom composition >

Surface atom composition is by ESCA(Electron Spectroscopy for Chemical Analysis) measure and try to achieve.Measure and use the ESCA device " PHIModel5800 " of ア Le バ ッ Network-Off ァ イ Co., Ltd. to implement.Condition determination is as follows.

X ray excited: monochromaticAlK α line (1486.6eV)

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

In and rifle: use (for preventing electrostatic)

Input lens setting (LensAreaMode): MinimumAreaMode

Analytical model (LENSMODE): 5(Minimum Area pattern)

Aperture is numbered: 5

Launch with (sample normal and detector centre axle angulation): 45 degree

Logical energy (PassEnergy): 23.5eV

Electric charge moves correction: the bonded energy making c h bond close the C1s peak of carbon carries out with meeting 285.0eV.

About the relative existence ratio of Sauerstoffatom relative to carbon atom, calculated by following formula.

Relative existence is than the peak correction relative sensitivity coefficient at the peak area/oxygen O1s peak of O/C=(oxygen O1s)/(the peak correction relative sensitivity coefficient at the peak area/carbon C1s peak of carbon C1s)

In addition, oxygen O1s and each peak area of carbon C1s are obtained as follows, the MultiPakVer.8.2C software that using appts is attached, carry out the smoothing processing (9 point) that have employed Savitzky-Golay algorithm, use the background curves of shirley method to obtain.For calculating the oxygen O1s and carbon C1s peak bonded energy that relatively there is ratio and the respective correction relative sensitivity coefficient used in MultiPakVer.8.2C software is as follows.

O1s: near bonded energy=532.5eV,

Correction relative sensitivity coefficient=13.118

C1s: near bonded energy=285.0eV,

Correction relative sensitivity coefficient=5.220

About the peak area of carbon C1s, employ following area and be added the area obtained, namely adopt shirley, link area that the minimum value near 280eV and 290.5eV obtains and adopt shirley to link the peak of the shakeup from phenyl ring that the minimum value near 290.5eV and 293eV obtains that (near 291 ~ 293eV, the area addition of > obtains.

< water contact angle >

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

< embodiment 1>

Be add mixing in the flask of 1L to heat to the polytetramethylene ether diol (number-average molecular weight 1968 calculated by hydroxyl value of 40 DEG C in advance at capacity, society of Mitsubishi Chemical manufacture) 142.5 weight parts, society of Mitsubishi Chemical manufacture hydrogenated butadiene polymer polyvalent alcohol (trade(brand)name " Port リ テ ー Le HA " number-average molecular weight: 2187, the average bonding number of hydroxyl of every 1 molecule: 1.8) 7.5 weight parts, using this mixture as the raw material manufacturing urethane." Port リ テ ー Le HA " is 5 % by weight relative to the ratio of this mixture.Then, add heat to 40 DEG C 4,4 '-diphenylmethanediisocyanate (following, sometimes referred to as " MDI ") 31 weight parts.The reaction equivalent ratio of NCO/ active hydrogen base (polyether glycol and chainextender) is now 1.6.Further, be placed on by this flask in the oil bath of 45 DEG C, one side anchor type agitating wing stirs in a nitrogen atmosphere, and one side is lasted 1 hour and the temperature of oil bath is risen to 70 DEG C, then keeps 3 hours at 70 DEG C.The dibutylamine of residual NCO base and excess quantity being reacted, then, by utilizing hydrochloric acid, back titration being carried out to residual dibutylamine, after confirming that the reactivity of NCO is more than 99%, removing oil bath, adds N in flask, N-N,N-DIMETHYLACETAMIDE (following, sometimes referred to as " DMAC ".Northeast chemistry society manufactures) 271 parts, at room temperature stirring and dissolving, prepares polyurethane prepolymers solution.

Above-mentioned polyurethane prepolymers solution 380 weight part is cooled to 10 DEG C, keep this temperature, on the other hand, prepare as chainextender use quadrol (EDA)/diethylamine (DEA)=89/11(mol ratio)=1.72/0.27(weight ratio) and 0.6%DMAC solution.Limit high-speed stirring is cooled to and the above-mentioned polyurethane prepolymers solution limit remaining on 10 DEG C is added in this 0.6%DMAC solution, obtains the urethaneureas DMAC solution of polymer concentration 20%.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, weight-average molecular weight is 17.2 ten thousand, molecular weight distribution is 2.4.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 78 % by weight.

By the urethaneureas solution-cast that obtains like this on a glass, make it dry at 60 DEG C, obtain the water white film of thickness about 50 μm.The thickness of film is measured by thickness tester.

Carry out stripping test to this film, the stress required for stripping is 5.7g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 1.

< embodiment 2>

In embodiment 1, add and mix urethane production of raw material for use and polytetramethylene ether diol (number-average molecular weight 1968 calculated by hydroxyl value, society of Mitsubishi Chemical manufacture) 148.5 weight parts, " Port リ テ ー Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of every 1 molecule: 1.8) 1.5 weight parts (ratio of " Port リ テ ー Le HA " in this mixture is 1 % by weight), and be set as quadrol/diethylamine=1.81/0.28(weight ratio), in addition, prepolymer and urethaneureas solution is obtained similarly to Example 1.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, weight-average molecular weight is 20.2 ten thousand, molecular weight distribution is 2.5.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 81 % by weight.

The water white urethaneureas film that thickness is about 50 μm is obtained by this urethaneureas solution.

Carry out stripping test to this film, the stress required for stripping is 5.7g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 1.

< embodiment 3>

In embodiment 2, add and mix urethane production of raw material for use and polytetramethylene ether diol (number-average molecular weight 1968 calculated by hydroxyl value, society of Mitsubishi Chemical manufacture) 149.85 weight parts, " Port リ テ ー Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of every 1 molecule: 1.8) 0.15 weight part (ratio of " Port リ テ ー Le HA " in this mixture is 0.1 % by weight), in addition, prepolymer and urethaneureas solution is obtained similarly to Example 2.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, result weight-average molecular weight is 19.8 ten thousand, molecular weight distribution is 2.4.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 82 % by weight.

The water white urethaneureas film that thickness is about 50 μm is obtained by this urethaneureas solution.

Carry out stripping test to this film, the stress required for stripping is 33g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained is as shown in table 1.In addition, the surface atom of this film consists of 0.194.Result is shown in table 1.

< embodiment 4>

In embodiment 1, add and mix polytetramethylene ether diol (number-average molecular weight 1968 calculated by hydroxyl value, society of Mitsubishi Chemical manufacture) 105 weight parts, " Port リ テ ー Le HA " (number-average molecular weight: 2187, the average bonding number of the hydroxyl of every 1 molecule: 1.8) 45 weight parts (ratio of " Port リ テ ー Le HA " in this mixture is 30 % by weight), in addition, prepolymer and urethaneureas solution is obtained similarly to Example 1.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, weight-average molecular weight is 19.8 ten thousand, molecular weight distribution is 2.4.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 57 % by weight.

The urethaneureas film that thickness is about the gonorrhoea a little of 50 μm is obtained by this urethaneureas solution.

Carry out stripping test to this film, the stress required for stripping is 33g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained is as shown in table 1.

< comparative example 1>

In embodiment 1, do not use " Port リ テ ー Le HA ", using polytetramethylene ether diol (number-average molecular weight 1968 calculated by hydroxyl value, society of Mitsubishi Chemical manufacture) 150 weight parts as urethane production of raw material for use, in addition, prepolymer and urethaneureas solution is obtained similarly to Example 1.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, weight-average molecular weight is 19.1 ten thousand, molecular weight distribution is 2.6.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 78 % by weight.

The water white urethaneureas film that thickness is about 50 μm is obtained by this urethaneureas solution.

Carry out stripping test to this film, the stress required for stripping is 50g/cm, and during stripping, the film observing long relative to initial test 12% extends.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 1.

[table 1]

< embodiment 5>

[manufacture of polyester polyol]

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

[manufacture of urethaneureas]

Be add in the flask of 1L and mix the polytetramethylene ether diol (number-average molecular weight 1955 calculated by hydroxyl value of heating in advance to 40 DEG C at capacity, society of Mitsubishi Chemical manufactures) 123.9 weight parts, the above-mentioned synthesis of 6.52 weight part polyester polyol 1, using this mixture as manufacturing the raw material of urethane.Polyester polyol 1 is 5 % by weight relative to the ratio of this mixture.Then, add heat to 40 DEG C 4,4 '-diphenylmethanediisocyanate (hreinafter referred to as " MDI ") 26.8 weight parts.The reaction equivalent ratio of NCO/ active hydrogen base (polyether glycol and chainextender) is now 1.6.Then, be placed on by this flask in the oil bath of 45 DEG C, one side anchor type agitating wing stirs in a nitrogen atmosphere, and one side is lasted 1 hour and the temperature of oil bath is risen to 70 DEG C, then keeps 3 hours at 70 DEG C.The dibutylamine of residual NCO base and excess quantity being reacted, then, by utilizing hydrochloric acid, back titration being carried out to residual dibutylamine, after confirming that the reactivity of NCO is more than 99%, removing oil bath, adds N in flask, N-N,N-DIMETHYLACETAMIDE (following, sometimes referred to as " DMAC ".Northeast chemistry society manufactures) 236 parts, at room temperature stirring and dissolving, prepares polyurethane prepolymers solution.

Above-mentioned polyurethane prepolymers solution is cooled to 10 DEG C, keeps this temperature, on the other hand, prepare as chainextender use quadrol (EDA)/diethylamine (DEA)=89/11(mol ratio)=1.66/0.24(weight ratio) and 0.5%DMAC solution.The cooling of limit high-speed stirring and the above-mentioned polyurethane prepolymers solution limit remaining on 10 DEG C are added in this 0.5%DMAC solution, obtain the urethaneureas DMAC solution of polymer concentration 20%.

By this solution at 25 DEG C after slaking one Dinner, adopt GPC to measure weight-average molecular weight and molecular weight distribution, weight-average molecular weight is 21.9 ten thousand, molecular weight distribution is 2.7.In addition, the ratio of (b) polytetramethylene ether diol in the urethane obtained is 78 % by weight.

By the urethaneureas solution-cast that obtains like this on a glass, make it dry at 60 DEG C, obtain the water white film of thickness about 50 μm.The thickness of film is measured by thickness tester.

Carry out stripping test to this film, the stress required for stripping is 4.4g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

< embodiment 6>

[manufacture of polyester polyol]

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

[manufacture of urethaneureas]

By the raw material charging capacity of the manufacture urethane shown in table 3, obtain urethaneureas solution and film in the same manner as in Example 5.Carry out stripping test to this film, the stress required for stripping is 6.7g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

< embodiment 7>

[polyester polyol manufacture]

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

[manufacture of urethaneureas]

By raw material charging capacity during manufacture urethane shown in table 3, obtain urethaneureas solution and film in the same manner as in Example 5.Carry out stripping test to this film, the stress required for stripping is 3.6g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

< embodiment 8>

[manufacture of polyester polyol]

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

[manufacture of urethaneureas]

By raw material charging capacity during manufacture urethane shown in table 3, obtain urethaneureas solution and film in the same manner as in Example 5.Carry out stripping test to this film, the stress required for stripping is 4.5g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

< embodiment 9>

[manufacture of polyester polyol]

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

[manufacture of urethaneureas]

By raw material charging capacity during manufacture urethane shown in table 3, obtain urethaneureas solution and film in the same manner as in Example 5.Carry out stripping test to this film, the stress required for stripping is 10.8g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

[0089]

< embodiment 10>

[manufacture of polyester polyol]

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

[manufacture of urethaneureas]

By raw material charging capacity during manufacture urethane shown in table 3, obtain urethaneureas solution and film in the same manner as in Example 5.Carry out stripping test to this film, the stress required for stripping is 13.0g/cm, and separability is good.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

< comparative example 2>

[manufacture of urethaneureas]

Raw material charging capacity when manufacturing by the urethane shown in table 3, obtains in the same manner as in Example 5 not containing urethaneureas solution and the film of polyester polyol.Carry out stripping test to this film, the stress required for stripping is 66.3g/cm, and separability is bad.In addition, the characteristic of the Elastic Film obtained 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.Result is shown in table 3.

[table 2]

[table 3]

To invention has been detailed description, also have references to specific embodiment, but various change or amendment will be readily apparent to persons skilled in the art in addition without departing from the spirit and scope of the present invention.

The application, based on the Japanese Patent application (Patent 2008-306247) applied on December 01st, 2008 and the Japanese Patent application (Patent 2009-179463) applied for on 07 31st, 2009, introduces these contents as reference here.

Utilizability in industry

According to the present invention, simultaneously can maintain the certain intermiscibility with polyether glycol, one side manufactures urethane, can reduce the adhesivity of the urethane obtained.In addition, by obtain polyurethane formed time, molding separability each other can be improved.And, use the spandex fiber be made up 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, blocking frequency that is stained by product, mechanical or utensil reduces the raising bringing operational stability, frictional force reduces, and can expect thus to drive electric power reduction etc.Therefore, industrial value of the present invention is remarkable.

Claims (10)

1. a urethane, it is characterized in that, containing (a) polyester polyol, (b) polyether glycol, (c) polyisocyanate compounds and (d) chainextender, the part by weight shared by (b) polyether glycol in urethane is 54 % by weight ~ 99 % by weight, described polyester polyol is formed containing ester group compound or carboxylated compound by (A) poly-hydroxy hydrocarbon polymer and (B), described (A) and described (B) form at least one ester bond, and the oxygen level in described polyester polyol is more than 2.0 quality %, below 13.5 quality %.

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

3. polyester polyol according to claim 2, is characterized in that, described (B) is polylactone.

4., according to the polyester polyol that claim 2 or 3 is recorded, it is characterized in that, described polyester polyol forms the segmented copolymer of (B) (A) (B) type by described (A) and described (B).

5. polyester polyol according to claim 2, is characterized in that, described (B) is dicarboxylic acid.

6. polyester polyol according to claim 5, is characterized in that, the carbonatoms of described dicarboxylic acid is more than 2, less than 15.

7. according to the polyester polyol that claim 5 or 6 is recorded, it is characterized in that, described polyester polyol is formed (AB) by described (A) and described (B) _nthe segmented copolymer of A type, wherein, n is the integer of more than 1.

8., according to the polyester polyol that claim 2 or 3 is recorded, it is characterized in that, the number-average molecular weight of described polyester polyol is more than 500, less than 5000.

9., according to the polyester polyol that claim 2 or 3 is recorded, it is characterized in that, described (A) poly-hydroxy hydrocarbon polymer is hydrogenated polydiene polyol.

10. a polymkeric substance, is characterized in that, at least one forming the hydroxyl of the polyester polyol that claim 2 or 3 is recorded forms amino-formate bond.