JP5842315B2 - Method for producing polyurethane and use of polyurethane obtained therefrom - Google Patents

Description

  The present invention relates to a polyurethane production method, a polyurethane obtained from the production method, and uses thereof.

  Polyurethane compounds and polyurethaneurea compounds are applied in various fields. Polyurethane compounds are mainly produced from polyhydroxy compounds such as polyester polyols and polyether polyols and isocyanate compounds and, if necessary, chain extenders, foaming agents, foam stabilizers, etc., and are used for polyurethane elastic fibers, polyurethane urea elastic fibers, etc. Often used as In particular, fibers with a polyurethane urea structure use polyether polyol as the soft segment component and use a polyamine compound with high cohesive strength as the hard segment, so they have excellent elastic properties and stretch recovery properties. ing. However, these polyurethane-based elastic fibers have high tackiness between fibers, so that the unwinding property at the time of spinning is poor, and because the frictional resistance is large, the processing process of spinning machines, warping machines, knitting machines, and guides that contact the yarns. Thread breakage occurs in the equipment in. Therefore, problems such as thread breakage are likely to occur in the processing process. Therefore, in order to reduce the frictional resistance between processing equipment and yarn, solid metal soap, oil-soluble polymer, higher fatty acid, amino-modified silicone, etc. are added as an oil agent, and talc, silica, colloidal as a smoothing agent. There are a method of dispersing alumina, titanium oxide and the like, and a method of introducing silicon diol and silicon diamine into a part of the polyurethane main chain (for example, Patent Document 1).

  However, even with this method, a sufficient anti-adhesion effect cannot be obtained, the smoothing agent causes serious wear on the spinning machine, warping machine, knitting machine and guide, and the oil agent component is used in the warping and knitting process. Oligomer in the extracted fiber or solid or high-viscosity component in the oil agent separated as a solid or paste, adheres to the fiber in large quantities, causing product fouling and clogging of machinery and equipment. The problem has been solved, and the problem has not been solved. For this reason, there is a need for a method for producing a polyurethane that reduces adhesiveness, has high unwinding properties during spinning (or peelability between polyurethanes), and has high peelability without using such an oil or smoothing agent. Has been.

  On the other hand, as an example of using a polyhydroxy hydrocarbon polymer having a hydroxyl group as a raw material for polyurethane, it can be used as a modifier of a urethane resin for improving the adhesiveness of a polyolefin resin material (Patent Document 2), Studies have been made to improve durability of polyurethane-based elastic fibers by producing polyurethane by mixing with polytetramethylene glycol as a molecular polyol (Patent Document 3). However, the method described in Patent Document 3 has a problem that since the high-molecular polyol is too hydrophobic, the compatibility with the polyether polyol is poor, and gelation occurs during polyurethane production, and uniform dispersion does not occur during yarn or film production. It was. In addition, stretch fabrics and swimsuits made from polyurethane fibers produced by the method described in Patent Document 3 are known to have excellent chlorine resistance, hot water resistance, light resistance, etc. For the purpose of reducing the adhesiveness of polyurethane by using a polyhydroxy hydrocarbon polymer having a hydroxyl group as a raw material, and further reducing the adhesiveness of molded products such as films and elastic fibers made of polyurethane. It has never been used. The polyurethane-based elastic fiber described in Patent Document 3 includes polyhydric alcohols and polyamines as chain extenders, but elasticity obtained by a melt spinning method using substantially polyhydric alcohols as chain extenders. When we try to obtain a so-called polyurethane urea structure using polyamines, which is a fiber, an abnormal reaction such as gel or three-dimensional crosslinking easily occurs during chain extension reaction, and it is formed into a homogeneous fiber or film. There was a problem that it was difficult to do.

  On the other hand, studies have been made to improve raw material components of polyurethane for the purpose of improving various properties of polyurethane elastic fibers. For example, as an example of using a polyester polyol, a hydrophobic polyester polyol formed from a glycol component having a polyhydric alcohol having a hydrocarbon group as a side chain as an essential component and a carboxylic acid component having a dimer acid as an essential component is proposed. (Patent Document 4). However, even when these polyester polyols are used, a polyurethane exhibiting sufficient peelability has not been obtained.

Japanese Patent Laid-Open No. 10-2559577 JP-A-6-158016 JP-A-11-131325 JP 2002-212273 A

  In view of the above problems, the present invention is extremely useful for high-performance polyurethane applications such as polyurethane elastic fibers, films, and garments when producing polyurethanes from polyether polyols, polyisocyanate compounds, and chain extenders. It is an object of the present invention to provide a method for producing a polyurethane and polyurethane urea that are useful and have low adhesiveness and high peelability, and also to provide a novel polyester polyol useful for producing polyurethane urea.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have produced a polyether polyol and a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular end, preferably a specific polymer. By using a polyester polyol having a structure and a constant oxygen content, more preferably by mixing the polyester polyol and a polyether polyol and reacting with a polyisocyanate compound and a chain extender in the presence of a solvent. The present inventors have found that the tackiness of the obtained polyurethane and polyurethane urea can be reduced, and that the peelability and unwinding property during spinning can be improved, and the present invention has been completed.

That is, the gist of the present invention resides in the following [1] to [ 18 ].
[1] (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at a molecular end, (b) polytetramethylene ether glycol, polytrimethylene ether glycol, 1 to 20 mol% of 3-methyltetrahydrofuran, Addition polymerization reaction of at least one polyether polyol selected from copolymerized polyether polyol of tetrahydrofuran, copolymerized polyether glycol of neopentyl glycol and tetrahydrofuran, (c) polyisocyanate compound, and (d) chain extender Thus, in obtaining polyurethane, (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal and (b) a total of (a) at least one hydroxyl group at the molecular terminal with respect to the polyether polyol. Having polyhydroxy In the presence of a solvent selected from the group consisting of an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylsulfoxide, the proportion of the hydrocarbon polymer being 0.01 to 50.00% by weight. A process for producing polyurethane, characterized by reacting.
[2] The method for producing a polyurethane as described in [1], wherein (a) the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end has a number average molecular weight of 500 to 5,000.
[3] The polyhydroxy hydrocarbon polymer having at least one hydroxyl group at its molecular end (a) has an average number of hydroxyl groups per molecule of 1.5 to 2.7 [1] Or the manufacturing method of the polyurethane as described in [2].
[4] The method for producing a polyurethane according to any one of [1] to [3], wherein the (c) polyisocyanate compound is an aromatic polyisocyanate.
[5] The method for producing a polyurethane according to any one of [1] to [4], wherein the (d) chain extender is a polyamine compound.
[6] The main structure of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end (a) is hydrogenated polybutadiene, according to any one of [1] to [5] Polyurethane production method.
[7] The (a) polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular end comprises: (A) a polyhydroxy hydrocarbon polymer; and (B) an ester group-containing compound or a carboxy group-containing compound. The method for producing a polyurethane according to any one of [1] to [6], wherein the polyurethane is a polyester polyol.
[8] In the polyester polyol, (A) and (B) form at least one ester bond, and the oxygen content in the polyester polyol is 2.0% by mass or more and 13.5% by mass or less. The method for producing a polyurethane as described in [7], wherein
[9] The method for producing a polyurethane as described in [7] or [8], wherein (B) is a polylactone.
[10] The polyester polyol is formed of (A) and (B), (B)
(A) The method for producing a polyurethane as described in any one of [7] to [9], which is a (B) type block copolymer.
[11] The method for producing a polyurethane according to [7] or [8], wherein (B) is a dicarboxylic acid.
[12] The method for producing a polyurethane as described in [11], wherein the dicarboxylic acid has 2 to 15 carbon atoms.
[13] The polyester polyol is (AB) nA type block copolymer (where n is an integer of 1 or more) formed by (A) and (B). 1
0] or the method for producing a polyurethane according to [11] .
[14 ] A polyester polyol formed from (A) a polyhydroxy hydrocarbon polymer and (B) a dicarboxylic acid, wherein (A) and (B) form at least one ester bond, and The polyester polyol, wherein an oxygen content in the polyester polyol is 2.0% by mass or more and 13.5% by mass or less.
[1 5 ] The polyester polyol according to [1 4 ], wherein the dicarboxylic acid has 2 to 15 carbon atoms.
[ 16 ] The polyester polyol is an (AB) nA type block copolymer (where n is an integer of 1 or more) formed of (A) and (B). 1
[ 4 ] or [1 5 ].
[17] Polyester polyol according to any one of a number average molecular weight of the polyester polyol, characterized in that 500 to 5000 [14] - [16].
[18] Polyester polyol according to any one of (A) a polyhydroxy hydrocarbon polymer, which is a hydrogenated polydiene polyol [14] to [17].

  According to the present invention, polyurethane can be produced while maintaining a certain compatibility with the polyether polyol, and the tackiness of the resulting polyurethane can be reduced. Moreover, when the obtained polyurethane is shape | molded, the peelability between molded objects can be improved. As a result, when using elastic fibers made of this polyurethane to form clothing, etc., cost reduction by reducing the amount of oil and smoothing agents used, improvement in operational stability by reducing the frequency of product contamination and clogging of machinery and equipment, friction Reduction of driving power can be expected by reducing the resistance.

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents. The details will be described below.
<Polyurethane>
The polyurethane of the present invention comprises (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular end of the present invention, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain. It is obtained by using with an extender.

  The polyurethane in the present invention includes (a) a polyhydroxy 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. Is included. Further, the weight ratio of the (b) polyether polyol in the polyurethane is not particularly limited, but is usually 54 to 99% by weight, preferably 60 to 90% by weight, and more preferably 70%. ~ 85% by weight. As this ratio increases, the flexibility of the resulting polyurethane tends to improve, while as the ratio decreases, the peelability of the resulting polyurethane tends to improve.

  In the polyurethane of the present invention, (a) the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end of the present invention, or (b) at least one of the hydroxyl groups constituting the polyether polyol is a urethane bond. The polymer forming is included. Preferably, a polymer having the following partial structure, that is, a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular end of the present invention, or (b) two or more hydroxyl groups constituting a polyether polyol. Is a polymer having the following structure in which a urethane bond is formed in the polymer chain.

(In the formula (I), HO-X-OH represents (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end of the present invention, or (b) a polyether polyol.)
The content and position of the polymer in the polyurethane of the present invention are not particularly limited as long as the polymer has the above structure in the polymer chain. As a compound containing the said structure, a polyurethane resin, a polyurethane urea resin, those prepolymers, etc. are mentioned, for example.

Further, in the present invention, “(a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular end, (b) a polyether polyol (c) a polyisocyanate compound, and (d) a chain extender is included. “Polyurethane” is a polymer compound having a urethane bond (—NHCOO—) in the repeating unit of the main chain, and the repeating structural unit of the main chain is derived from both the compounds (a) and (b). In addition, polyurethane as a polymer compound derived only from (a), polyurethane as a polymer compound derived only from (b), and a mixture thereof may be used. Moreover, unreacted (a), (b), (c), or (d) and the said high molecular compound may be mixed.

  The polyurethane in the present invention indicates polyurethane or polyurethane urea unless otherwise specified, and it has been conventionally known that these two types of resins have substantially the same physical properties. On the other hand, as structural differences, polyurethane is produced using a short-chain polyol as a chain extender, and polyurethane urea is produced using a polyamine compound as a chain extender. is there.

  Each composition ratio is usually represented by the total number of moles of (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end and (b) the hydroxyl group of the polyether polyol relative to polyurethane. c) When the number of moles of isocyanate group of the polyisocyanate compound is B, and (d) the number of moles of active hydrogen substituents (hydroxyl group and amino group) of the chain extender is C, A: B is usually 1:10. A range of 1: 1, preferably 1: 5 to 1: 1.05, more preferably 1: 3 to 1: 1.1, still more preferably 1: 2.5 to 1: 1.2, particularly preferably 1 : 2 to 1: 1.2, and (B-A): C is usually 1: 0.1 to 1: 5, preferably 1: 0.8 to 1: 2, more preferably 1: 0. .9 to 1: 1.5, more preferably 1: 0.95 to 1: 1.2, particularly preferably 1. 0.98 to 1: in the range of 1.1.

<(A) Polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal>
In the present invention, the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal is typically a heavy chain having a hydrocarbon skeleton such as a conjugated diene such as butadiene, isoprene or chloroprene as a repeating unit. It is a coalescence or a polyester polyol described later. These can be used in admixture with polyether polyols to produce polyurethanes, which can improve the tackiness of the resulting polyurethane, the peelability of polyurethane moldings, and the unwinding properties during spinning. it can.
The polymer having a hydrocarbon skeleton as a repeating unit is preferably, for example, a conjugated diene system having a hydroxyl group at the terminal directly by radical polymerization of 1,3-butadiene using hydrogen peroxide as a polymerization initiator. Or a conjugated diene polymer having a hydroxyl group at the terminal by producing a living polymer having an alkali metal bonded to the terminal using an anionic polymerization catalyst, and then reacting with a monoepoxy compound or formaldehyde, What obtained by hydrogenating the obtained conjugated diene-type polymer by a conventional method is mentioned. At that time, vinyl monomers such as styrene, acrylonitrile, methyl (meth) acrylate, vinyl acetate and the like may be copolymerized with the conjugated diene in an amount of 30% by weight or less.

  In addition, isobutylene or a polymer of isobutylene and a conjugated diene such as isoprene or 1,3-pentadiene is subjected to an oxidative decomposition treatment with ozone and the like, followed by a reduction treatment with lithium aluminum hydride or the like, and isobutylene having a hydroxyl group at the terminal. A hydrogenated polymer obtained by a conventional method and a copolymer of an α-olefin such as ethylene and propylene and a diene compound are similarly oxidized and decomposed and reduced, and hydrogenated. Added ones and the like.

Among the polyhydroxy hydrocarbon polymers having at least one hydroxyl group at the molecular end of the present invention, preferably, the polyhydroxy hydrocarbon polymer having a main skeleton of hydrogenated polybutadiene, hydrogenated polyisoprene, and polyisobutylene. The main skeleton is more preferably hydrogenated polybutadiene in view of availability and ease of handling.
The ratio of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal used in the present invention is the sum of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal and the polyether polyol. It is preferable that it is 0.01 weight% or more with respect to quantity. More preferably, it is 0.03 weight% or more, More preferably, it is 0.05 weight% or more, Especially preferably, it is 0.07 weight% or more, Most preferably, it is 0.1 weight%. As this value increases, the tackiness of the resulting polyurethane resin tends to decrease. On the other hand, the upper limit is preferably 50.00% by weight or less. More preferably, it is 30.00 weight% or less, More preferably, it is 25.00 weight% or less, Especially preferably, it is 15.00 weight% or less, Most preferably, it is 10.00 weight% or less. The smaller this value is, the lower the tackiness of the resulting polyurethane resin, but the tendency is to improve the elastic properties and stretch recovery properties.

  The polyhydroxy hydrocarbon polymer has a number average molecular weight of 500 to 5000, preferably 700 to 4000, more preferably 900 to 3500, and is liquid or waxy at room temperature. If the number average molecular weight is too high, the viscosity of the polyether polyol, prepolymer, or prepolymer solution becomes too high, and the operability and productivity tend to be poor, or the properties of the resulting polyurethane polymer at low temperatures tend to be poor. . If it is too low, the resulting polyurethane polymer will be hard and sufficient flexibility will not be obtained, elastic properties such as strength and elongation will not be sufficient, and excessive residual strain will remain when repeated stretching and recovery Tend. Further, the polyester polyol has at least two or more ester bonds and two or more hydroxyl groups in the molecule, and preferably has both ends of the polyester polyol main chain are hydroxyl groups.

  The polyester polyol of the present invention is a polyester polyol formed from (A) a polyhydroxy hydrocarbon polymer, which will be described later, and (B) an ester group-containing compound or a carboxy group-containing compound. Specifically, (A) polyhydroxy The hydrocarbon polymer forms at least one ester bond with the (B) ester group-containing compound or carboxy group-containing compound.

The number of ester bonds formed by the (A) polyhydroxy hydrocarbon polymer contained in one molecule of the polyester polyol of the present invention is usually 1 or more.
Specifically, (A) one molecule of a polyhydroxy hydrocarbon polymer may form a plurality of ester bonds at the molecular end, or a plurality of polyhydroxy hydrocarbon polymers (A) may form an ester bond. The total number of ester bonds contained in one molecule of the polyester polyol may be 2 or more.

Hereinafter, the requirements for constituting the polyester polyol of the present invention will be described separately.
<(A) polyhydroxy hydrocarbon polymer>
The (A) polyhydroxy hydrocarbon polymer in the present invention is a polymer having a hydrocarbon skeleton as a repeating unit, and has at least two hydroxyl groups in the polymer.

  The polymer having the hydrocarbon skeleton as a repeating unit is not particularly limited, and an element other than carbon and hydrogen, for example, a hydrocarbon having a halogen such as chlorine, fluorine, bromine or the like as a substituent is repeated. The polymer may be a unit, but is preferably a polymer having a repeating unit of a hydrocarbon formed of carbon and hydrogen (hereinafter sometimes referred to as a hydrocarbon polymer), more preferably an aliphatic hydrocarbon. It is a polymer.

Examples of the hydrocarbon polymer in the present invention include a polymer having a linear hydrocarbon as a repeating unit, or a polymer having a hydrocarbon having a side chain in the molecule as a repeating unit.
A hydrocarbon polymer having a high content of hydrocarbons having side chains is preferred because a high content of hydrocarbons having side chains in the molecule reduces the melting point of the hydrocarbon polymer and facilitates handling. .

The hydrocarbon polymer may be a homopolymer with one repeating unit or a copolymer containing two or more repeating units.
The number of carbon atoms of the hydrocarbon repeating unit is not particularly limited, but is usually 2 or more, preferably 3 or more, usually 9 or less, preferably 6 or less.
The polyhydroxy hydrocarbon polymer in the present invention is preferably a polymer containing a conjugated diene such as butadiene, isobutylene, isoprene, chloroprene and the like because it is easy to introduce a functional group at the end of the polymer and to easily control the molecular weight. More preferably, a hydrogenated polybutadiene, a hydrogenated polyisoprene, a hydrogenated polyisobutylene, and the like are homopolymerized and then hydrogenated polymer (hereinafter, hydrogenated polydiene). Of these, hydrogenated polybutadiene is preferred in terms of availability and ease of handling.

  The polyhydroxy hydrocarbon polymer in the present invention has at least two hydroxyl groups in the polymer. The number of hydroxyl groups is not usually limited as long as it satisfies the following oxygen content, but is usually 2 or more and 6 or less, and preferably 3 or less. The position of the hydroxyl group is not particularly limited, but those having a hydroxyl group at the molecular end are preferred, those having two or more at the molecular end are more preferred, and those having both ends of the main chain of the hydrocarbon polymer are more preferred.

  The polyhydroxy hydrocarbon polymer (A) constituting the polyester polyol of the present invention forms at least one ester bond to adjust the hydrophobicity of the polyester polyol, so that the polyether polyol is more stable than the saturated hydrocarbon polymer. A polyester polyol having high compatibility can be obtained. Moreover, the polyurethane obtained by using such a polyester polyol shows high peelability.

The number average molecular weight of the polyhydroxy hydrocarbon polymer in the present invention is usually 100 or more, preferably 200 or more, more preferably 300 or more, and usually 5000 or less, preferably 4000 or less, more preferably 3000 or less. If it is less than the lower limit value, the resulting polyurethane polymer becomes hard and causes a decrease in flexibility, a decrease in elastic performance such as strength and elongation, or an excessive residual strain when it is repeatedly stretched and recovered. There is a tendency. When the upper limit is exceeded, the viscosity of the polyether polyol, prepolymer, and prepolymer solution becomes too high, and the operability and productivity tend to decrease, or the properties of the resulting polyurethane polymer at low temperatures tend to decrease.

The properties of the polyhydroxy hydrocarbon polymer in the present invention are not particularly limited, but are usually liquid or waxy at room temperature.
<(B) Ester group-containing compound>
The ester group-containing compound used in the present invention is not particularly limited as long as it has an ester group, and usually includes a compound in which a repeating unit is polymerized through an ester bond, preferably a lactone. It is a polylactone obtained by ring-opening polymerization.

<Polylactone>
The polylactone in the present invention can be obtained by performing a known polymerization reaction using lactone as a raw material.
Specific examples of lactones used include ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone. , Γ-valerolactone, enanthlactone and the like. These may be used alone or in combination of two or more. Of these, ε-caprolactone, δ-valerolactone, and γ-valerolactone are preferable because they are easily available and highly reactive, and ε-caprolactone is more preferable.

Hereinafter, as a polyester polyol formed from a polyhydroxy hydrocarbon polymer and an ester group-containing compound, a polyester polyol formed from a polyhydroxy hydrocarbon polymer and a polylactone will be described as an example.
<Polyester polyol formed from polyhydroxy hydrocarbon polymer and polylactone>
Among the polyester ester polyols of the present invention, one of preferred embodiments is that one or more ester groups are formed between the polyhydroxy hydrocarbon polymer and the following polylactone, preferably polyhydroxy hydrocarbon polymer 1 At least one of the hydroxyl groups of the molecule
One having an ester bond with polylactone and having a plurality of ester bonds in one molecule in total, more preferably at least one of the terminal hydroxyl groups of one molecule of the polyhydroxy hydrocarbon polymer is In this case, an ester bond is formed with polylactone, and the total number of ester bonds is one molecule.

  The type of copolymerization of the polyhydroxy hydrocarbon polymer and polylactone is not particularly limited, but preferably (A) the polyhydroxy hydrocarbon polymer moiety and (B) the polylactone moiety are (B) ( A) Polyester polyol constituting the (B) type block copolymer. (B) is a lactone ring-opening polymer, and (A) and (B) are bonded via an ester bond.

The degree of polymerization of (A) or (B) is not particularly limited, and may be determined in consideration of the molecular weight of the raw material so that the oxygen content and molecular weight in the polyester polyol have desired values.
It is possible to easily change the molecular weight and oxygen content of the polyester polyol to be produced by adjusting the degree of polymerization of the above (A) or (B) according to the desired physical properties of the polyurethane resin. Although the production method is not particularly limited, it can be generally obtained by reacting a polyhydroxy hydrocarbon polymer and a lactone at a predetermined ratio in the absence of a solvent and in the presence of a catalyst such as tetraisopropyl titanate or tetrabutyl titanate. it can.

<(B) Carboxy group-containing compound>
The carboxy group-containing compound used in the present invention is not particularly limited as long as it has a carboxy group, but is usually a monocarboxylic acid compound, a dicarboxylic acid compound, a substituted carboxylic acid compound such as a hydroxy acid or an alkoxy acid. The dicarboxylic acid compound is preferable.

<Dicarboxylic acid>
The dicarboxylic acid compound used in the present invention may be either an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but the aliphatic dicarboxylic acid usually has 2 or more carbon atoms, preferably 3 or more, more preferably 4 or more. Yes, usually 16 or less, preferably 15 or less, more preferably 14 or less. Specifically, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonamethylene dicarboxylic acid, 1,10-decamethylene dicarboxylic acid Examples include acid, 1,11-undecamethylene dicarboxylic acid, and 1,12-dodecamethylene dicarboxylic acid. Specific examples of the aromatic dicarboxylic acid include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid. These may be used alone or as a mixture of two or more. Further, anhydrides of these dicarboxylic acids, alkyl esters, halogen-substituted products of unsaturated bonds, and the like can also be used. Among these, aliphatic dicarboxylic acids are preferred because they are easily available and have high thermal stability, more preferably malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and more preferred. Are succinic acid and adipic acid.
Hereinafter, as a polyester polyol formed from a polyhydroxy hydrocarbon polymer and a carboxy group-containing compound, a polyester polyol formed from a polyhydroxy hydrocarbon polymer and a dicarboxylic acid will be described as an example.

<Polyester polyol formed from polyhydroxy hydrocarbon polymer and dicarboxylic acid>
In the present invention, the polyester polyol formed from the polyhydroxy hydrocarbon polymer and the dicarboxylic acid usually has at least one hydroxyl group each contained in two molecules of the polyhydroxy hydrocarbon polymer and two carboxy groups contained in one molecule of the dicarboxylic acid. Polyester polyol that forms an ester bond between the two.

Preferably, it is a (AB) _n A type polyester polyol formed from the polyhydroxy hydrocarbon polymer (A) and the dicarboxylic acid (B). (A) and (B) should just be couple | bonded through the ester bond, and may be manufactured from carboxylic acid derivatives, such as carboxylic acid diester.
Usually, n may be an integer of 1 or more, more preferably an ABA-type polyester in which a polyhydroxy hydrocarbon polymer is bonded to both ends of the dicarboxylic acid, corresponding to the case where n = 1. It is a polyol.

The molecular weight of a generally available polyhydroxy hydrocarbon polymer is as large as at least 1500, and when the polyhydroxy hydrocarbon polymer reacts at both ends of the dicarboxylic acid to produce a polyester polyol, the molecular weight becomes 3000 or more. When the value of n increases, if the molecular weight of the polyester polyol becomes too large, the viscosity of the prepolymer or prepolymer solution becomes too high, and the operability and productivity at the time of polyurethane production decrease, or the resulting polyurethane weight This is because the physical properties of the coalescence at a low temperature tend to decrease.

Although the polyester polyol of this invention may have structures other than said structure in a molecule | numerator, Preferably the polyester polyol which does not contain other structures other than the said site | part is preferable.
In the above description, (A) and (B) are described in detail as constituents for forming an ester bond, but the polyester polyol of the present invention is not limited to this, and the obtained molecular structure is the same. Any raw material and reaction method may be used.

<Oxygen content>
The oxygen content in the polyester polyol of the present invention refers to the oxygen content in one molecule of the polyester polyol, and usually refers to the ratio of oxygen atoms contained in the molecule to the molecular weight of one molecule of the polyester polyol. For example, when 10 oxygen atoms are present in a polyester polyol having a molecular weight of 2000, (10 × 16/2000) × 100 = 8.0% by mass.

  The polyester polyol of the present invention has an oxygen content of 2.0% by mass or more and 13.5% by mass or less, preferably 2.2% by mass or more, more preferably 2.5% by mass or more, Preferably it is 3.0 mass% or more, Preferably it is 13 mass% or less, More preferably, it is 12 mass% or less, More preferably, it is 11.0 mass%. If it is less than the lower limit, the compatibility with the polyether polyol and the solubility in a solvent are insufficient, and if it exceeds the upper limit, the adhesiveness of the resulting polyurethane resin increases, which is not preferable.

  The ratio of the polyhydroxy hydrocarbon polymer in the polyester polyol of the present invention is not particularly limited, but is usually 10.0% by mass or more, preferably 20.0% by mass or more as a mass ratio. More preferably, it is 30.0 mass% or more, More preferably, it is 40.0 mass% or more, Most preferably, it is 45.0 mass%. As the mass ratio of the polyhydroxy hydrocarbon polymer in the polyester polyol of the present invention increases, the tackiness of the resulting polyurethane tends to decrease. On the other hand, the upper limit is not particularly limited, but is 99.5% by mass or less, preferably 99.0% by mass or less, more preferably 98.5% by mass or less, and still more preferably 98.2% by mass. It is 9 mass% or less, Most preferably, it is 98.0 mass% or less. As the mass ratio decreases, the compatibility with the polyether polyol and the solubility in polar solvents tend to improve.

<Physical properties of polyester polyol>
The number average molecular weight of the polyester polyol of the present invention can be adjusted by the type and amount of (A) or (B) used. The number average molecular weight is usually 500 or more, preferably 600 or more, more preferably 800 or more, and usually 10,000 or less, preferably 7000 or less, more preferably 5000 or less. The number average molecular weight indicates an average molecular weight per molecule. When the number average molecular weight exceeds the above upper limit, the viscosity of the prepolymer and the prepolymer solution becomes too high, and the operability and productivity tend to decrease, or the properties of the resulting polyurethane polymer at low temperatures tend to decrease. If the amount is less than the lower limit, the obtained polyurethane polymer may be hard and sufficient flexibility may not be obtained, or the elastic performance such as strength and elongation may not be sufficient, or when elongation and recovery are repeated. Excessive residual strain tends to remain.

<(B) Polyether polyol>
The polyether polyol in the present invention is a hydroxy compound having at least one ether bond in the main skeleton in the molecule, and the repeating unit in the main skeleton may be either a saturated hydrocarbon or an unsaturated hydrocarbon. Well, for example, 1,4-butanediol unit, 2-methyl-1,4-butanediol unit, 3-methyl-1,4-butanediol unit, 1,3-propanediol unit, 1,2-propylene glycol Unit, 2-methyl-1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 3-methyl-1,5-pentanediol unit, 1,2-ethylene glycol unit, 1, 6-hexanediol unit, 1,7-heptanediol unit, 1,8-octanediol unit, 1,9-nonanediol unit, 1 , 10-decanediol unit, 1,4-cyclohexanedimethanol unit and the like.

  Among these, among the polyol units constituting the polyether polyol, polytetramethylene ether glycol, polytrimethylene ether glycol, BR> A 1 to 20 mol% of a copolymer polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya Chemical Co., Ltd. "PTG-L1000", "PTG-L2000", "PTG-L3500" etc.) or the copolymer polyether glycol of neopentyl glycol and tetrahydrofuran is preferable.

<(C) Polyisocyanate compound>
Examples of the polyisocyanate compound used in the present invention include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-MDI, paraphenylene. Aromatic diisocyanates such as diisocyanate, 1,5-naphthalene diisocyanate and tolidine diisocyanate, aliphatic diisocyanates having an aromatic ring such as α, α, α ', α'-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and other aliphatic diisocyanates, 1,4-cyclohexane San diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4 ' Examples include alicyclic diisocyanates such as diisocyate. These may be used alone or in combination of two or more.
In the present invention, a highly reactive aromatic polyisocyanate is particularly preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferable. Further, a part of the NCO group of the polyisocyanate may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc., and the polynuclear substance contains isomers other than those described above. The thing which is included is also included.

  The amount of these polyisocyanate compounds used is as follows: (a) the total of hydroxyl groups of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end and (b) polyether polyol, and the hydroxyl group and amino group of the chain extender. Usually, 0.1 equivalents to 5 equivalents, preferably 0.8 equivalents to 2 equivalents, more preferably 0.9 equivalents to 1.5 equivalents, and even more preferably 0.95 equivalents to 1 equivalent based on the total of the groups. 1.2 equivalents, most preferably 0.98 equivalents to 1.1 equivalents.

If the amount of polyisocyanate used is too large, the unreacted isocyanate group will react unfavorably and the desired physical properties tend to be difficult to obtain. If it is too small, the molecular weight of polyurethane and polyurethane urea will not be sufficiently large. The desired performance tends not to be expressed.
<(D) Chain extender>
The chain extender referred to in the present invention is mainly classified into a compound having two or more hydroxyl groups, a compound having two or more amino groups, and water. Of these, short-chain polyols, specifically compounds having two or more hydroxyl groups, are preferred for polyurethane applications, and polyamine compounds, specifically compounds having two or more amino groups, are preferred for polyurethane urea applications. Among these, water is preferably reduced as much as possible in order to carry out the reaction stably.
In the polyurethane resin of the present invention, it is more preferable in view of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less as a chain extender because the rubber elasticity of the polyurethane elastomer is improved.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2 -Propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl -1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8 -Aliphatic glycols such as octanediol and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene.

  Examples of the compound having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, ethylenediamine, 1,2- Propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or 2, Aliphatic diamines such as 4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethanedia Down (hydrogenated MDA), isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, alicyclic diamines such as 1,3-bis-aminomethyl cyclohexane. These chain extenders may be used alone or in combination of two or more. Among these, ethylenediamine, propylenediamine, 1,3-diaminopentane, and 2-methyl-1,5-pentanediamine are preferable in the present invention, and among these, ethylenediamine and propylenediamine are more preferable.

  The amount of these chain extenders used is not particularly limited, but when the equivalent of subtracting the equivalent of the polyisocyanate compound from the total hydroxyl equivalent of (a) and (b) is 1, usually 0.1 equivalent or more, 5.0 equivalents or less. Preferably it is 0.8 equivalent or more and 2.0 equivalent or less, More preferably, it is 0.9 equivalent or more and 1.5 equivalent or less. If the amount used is too large, the obtained polyurethane and polyurethane urea will be too hard and the desired properties will not be obtained, or it will be difficult to dissolve in the solvent and difficult to process, and if it is too small, it will be too soft and sufficient. There is a tendency that strength, elastic recovery performance and elastic retention performance cannot be obtained, and high-temperature characteristics are deteriorated.

When the polyurethane and polyurethane urea which are the object of the present invention are used for high performance polyurethane elastomer applications such as polyurethane elastic fiber and synthetic leather, the following examples are given as combinations of raw materials.
For the purpose of controlling the molecular weight of polyurethane, a chain terminator having one active hydrogen group can be used as necessary. Examples of these chain terminators include aliphatic monools such as ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having an amino group. Is done. These may be used alone or in combination of two or more.

<Other additives>
In addition to the above, other additives may be added to the polyurethane of the present invention as necessary. These additives include “CYANOX 1790” (manufactured by Cyanamid), “IRGANOX 245”, “IRGANOX 1010” (manufactured by Ciba Specialty Chemicals), “Sumizer GA-80” (manufactured by Sumitomo Chemical), or 2 , 6
-Antioxidants such as dibutyl-4-methylphenol (BHT), "TINUVIN 622LD", "TINUVIN 765" (manufactured by Ciba Specialty Chemicals), "SANOL LS-2626", "SANOL LS-765" ( As mentioned above, light stabilizers such as “Sankyo Co., Ltd.”, UV absorbers such as “TINUVIN 328” and “TINUVIN 234” (manufactured by Ciba Specialty Chemicals), silicon compounds such as dimethylsiloxane polyoxyalkylene copolymer, Addition of red phosphorus, organic phosphorus compounds, phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc. and reactive flame retardants, pigments such as titanium dioxide, dyes, carbon black Colorants such as carbojiimi Compounds of hydrolysis-preventing agent, glass wool, carbon fibers, alumina, talc, graphite, melamine, fillers clay such as lubricants, oils, surfactants, other inorganic extenders, organic solvents and the like.

<Production method of polyurethane>
The polyester polyol of this invention and the manufacturing method of a polyurethane are explained in full detail below.
<Method for producing polyester polyol>
The polyester polyol of the present invention is produced using a polyhydroxy hydrocarbon polymer. The polyhydroxy hydrocarbon polymer is a compound known per se and can be produced according to a commonly used method. Moreover, it can also be used using these commercially available compounds. Typically, a conjugated diene polymer having a hydroxyl group at the terminal directly by radical polymerization of a conjugated diene such as butadiene, isoprene or chloroprene, preferably 1,3-butadiene using hydrogen peroxide as a polymerization initiator. Or by producing a living polymer having an alkali metal bonded to the terminal using an anionic polymerization catalyst, and then reacting with a monoepoxy compound or formaldehyde to obtain a conjugated diene polymer having a hydroxyl group at the terminal. Examples thereof include hydrogenated conjugated diene polymers by a conventional method. In this case, a vinyl monomer such as styrene, acrylonitrile, methyl (meth) acrylate, vinyl acetate or the like may be copolymerized with the conjugated diene in an amount of 30% by mass or less.

  Further, a polymer of isobutylene or of isobutylene and a conjugated diene such as isoprene or 1,3-pentadiene is subjected to an oxidative decomposition treatment with ozone and the like, and then subjected to a reduction treatment with lithium aluminum hydride or the like to form a hydroxyl group at the terminal. The obtained isobutylene polymer is obtained, and the obtained polymer is hydrogenated by a conventional method, and a copolymer of an α-olefin such as ethylene and propylene and a diene compound is similarly oxidized and decomposed and reduced. , Hydrogenated ones, and the like.

  The polyester polyol of the present invention can be produced by employing a conventionally known esterification technique. For example, a method of reacting a polyol with a lactone or a dicarboxylic acid under normal pressure, a method of esterifying under a reduced pressure, or esterification in the presence of an inert solvent such as toluene, and then condensing condensed water or a condensed alcohol with a solvent. There is a method of removing it from the reaction system by boiling.

The reaction temperature for esterification is usually in the range of 100 to 250 ° C. Preferably it is 120-240 degreeC, More preferably, it is 140-230 degreeC, Most preferably, it is the range of 150-220 degreeC. If the reaction temperature is too low, the esterification reaction does not proceed sufficiently, and if it is too high, the coloring of the product may increase.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and the reaction can be performed under normal pressure or reduced pressure depending on the purpose. In reactions such as polyols and dicarboxylic acids or dicarboxylic acid esters, water and alcohol are produced during the reaction. To promote their elimination from the reaction system, an inert gas is passed through the reaction system. Also good.

<Catalyst>
The form of the esterification reaction is not particularly limited, and it is possible to carry out the esterification reaction in a system in which no catalyst is present. Usually, however, in order to make the esterification reaction proceed smoothly, an inorganic acid or Organic acids; Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al,
Metal chlorides, oxides, hydroxides or acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Sn, Sb or Pb Fatty acid salts such as sodium methoxide, sodium ethoxide, aluminum triisopropoxide, alcohols such as isopropyl titanate or n-butyl titanate; phenols such as sodium phenolate; or Al, Ti, Zn, Sn, Zr or It can be carried out with all catalysts used for normal esterification and transesterification, such as other organometallic compounds of metals such as Pb. A titanium-based catalyst such as isopropyl titanate or n-butyl titanate is most preferred because it is easily available and has low toxicity and is widely used in esterification reactions. In this case, the amount of the catalyst used is preferably 0.00001 to 5.0% by mass, more preferably 0.0001 to 2.0% by mass, and more preferably 0.001 to 1. 0% by mass is most preferred. If this amount is too small, it takes a very long time to form the polyester polyol, and the product tends to be colored. On the other hand, if the amount of the catalyst used is too large, there is a possibility of exhibiting an excessive reaction promoting action for the polyurethane reaction.

  The esterification reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and the reaction can be performed under normal pressure or reduced pressure depending on the purpose. In reactions such as polyols and dicarboxylic acids or dicarboxylic acid esters, water and alcohol are produced during the reaction. To promote their elimination from the reaction system, an inert gas is passed through the reaction system. Also good.

The esterification reaction time varies depending on the amount of catalyst used, the reaction temperature, the substrate to be reacted, the desired properties of the polyester polyol to be produced, etc., but the lower limit is usually 0.5 hours, preferably 1 hour, the upper limit is usually 30 hours Preferably it is 20 hours.
When a catalyst is used during the esterification reaction, the (titanium-based) catalyst used in the reaction remains in the obtained polyester polyol product. Since the removal of the catalyst usually involves complicated steps, the produced polyester polyol is generally often used as it is for the production of polyurethane without separating the (titanium-based) catalyst.

However, it is preferable to deactivate the titanium catalyst in the polyester polyol when the content of the catalyst is large or depending on the use of the polyurethane. Examples of the method for deactivating the titanium-based catalyst in the polyester polyol include (1) a method in which the polyester polyol is brought into contact with water under heating; (2) the polyester polyol in phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid. The method of processing with phosphorus compounds, such as acid ester, etc. can be mentioned. And when it is based on the method of said (1) made to contact with water, for example, 1 mass% or more of water is added to polyester polyol, and it is 70-150 degreeC, Preferably it is about 90-130 degreeC for about 1-3 hours. Heat it up. The deactivation treatment by heating at that time may be performed under normal pressure or under pressure, and when the system is depressurized after the deactivation treatment, the water used for deactivation can be smoothly removed from the polyester polyol. .

<Production method of polyurethane>
In the present invention, a polyurethane can be produced by (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d). Chain extenders are mainly used as raw materials for production.
In general, the polyurethane can be produced in the presence of a solvent. In the present invention, the polyurethane is preferably produced in the presence of an aprotic polar solvent.
In addition, as long as there is no restriction | limiting in particular in the usage-amount of each compound, what is necessary is just to use the said amount. An example of a production method in the presence of an aprotic polar solvent is shown below, but is not particularly limited as long as it is in the presence of an aprotic polar solvent.

  The aprotic polar solvent in the present invention is not particularly limited, but from the viewpoint of solubility, among the aprotic polar solvents, from the group consisting of amide solvents, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylsulfoxide. The selected solvent is preferably used. Specific examples of the amide solvent include N, N-dimethylacetamide, N, N-dimethylformamide, and a mixture of two or more thereof, and dimethylformamide or dimethylacetamide is particularly preferable.

  As an example of the production method, (a), (b), (c) and (d) are reacted together (one-stage method), (a) and (b) are first mixed, After reacting (c) to prepare a prepolymer having both ends isocyanate groups, the prepolymer and (d) are reacted (two-stage method), and (b) and (c) are reacted ( Examples thereof include a method of mixing a) and reacting with (d), and a method of mixing (a) after reacting (b), (c) and (d). Among these, the two-stage method involves a step of preparing an intermediate sealed with both end isocyanates corresponding to the soft segment of polyurethane by reacting the polyether polyol with one or more equivalents of polyisocyanate in advance. . By preparing the prepolymer once and reacting with the chain extender, it is easy to adjust the molecular weight of the soft segment part, and the phase separation of the soft segment and the hard segment is easy to be established, and the characteristics as an elastomer are easily obtained. is there. In particular, when the chain extender is a diamine, the reaction rate with the isocyanate group is greatly different from that of the hydroxyl group of the polyether polyol. Therefore, it is more preferable to carry out polyurethane urea formation by a two-stage method (prepolymer method). preferable.

<One-step method>
The one-stage method is also called a one-shot method, and is a method in which the reaction is performed by charging (a), (b), (c), and (d) together. The amount of each compound used may be the amount described above.

In the reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment and the like. If the temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor. On the other hand, if the temperature is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure. Moreover, a catalyst, a stabilizer, etc. can also be added for reaction as needed. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. Examples of the stabilizer include 2,6-dibutyl-4. -Methylphenol, distearylthiodipropionate, di-betanaphthylphenylenediamine, tri (dinonylphenyl) phosphite and the like.

<Two-stage method>
The two-stage method is also called a prepolymer method, and a prepolymer obtained by reacting a polyisocyanate component and a polyol component in advance at a reaction equivalent ratio of usually 1.0 to 10.00 is prepared, and then the polyisocyanate component or A two-stage reaction in which an active hydrogen compound component such as a polyhydric alcohol or an amine compound is added can also be performed. In particular, a method is useful in which a polyol component is reacted with an equivalent amount or more of a polyisocyanate compound to form an NCO prepolymer at both ends, and then a chain extender such as a short chain diol or diamine is allowed to act to obtain a polyurethane.

In the present invention, the two-stage method can be carried out in the presence of a solvent, but is preferably carried out in the presence of an aprotic solvent. Specifically, an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl And sulfoxide solvents, and mixtures of two or more thereof.
In the present invention, among these solvents, when a polyurethane is produced, an aprotic polar solvent is preferable from the viewpoint of solubility. Further, among aprotic polar solvents, amide solvents, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide are preferable, and specific examples of amide solvents include N, N-dimethylacetamide, N, N-dimethylformamide is more preferable, and N, N-dimethylformamide or N, N-dimethylacetamide is particularly preferable.

  When synthesizing a prepolymer, (1) First, a polyisocyanate compound and a polyether polyol may be directly reacted without using a solvent to synthesize the prepolymer and used as it is, or (2) by the method of (1) The prepolymer may be synthesized and then dissolved in a solvent before use. (3) The polyisocyanate and the polyether glycol may be reacted using a solvent from the beginning. In the case of (1), in the present invention, when the chain extender is allowed to act, the polyurethane is used as a solvent by dissolving the chain extender in a solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is important to obtain it in a coexisting form.

  As for the reaction equivalent ratio of NCO / active hydrogen group (polyol), the lower limit is usually 1, preferably 1.05, and the upper limit is usually 10, preferably 5, more preferably 3. If this ratio is too small, the molecular weight of the resulting prepolymer will be too large, and there will tend to be insufficient stretchability due to the low amount of hard segments described below. As the value increases, sufficient flexibility tends not to be obtained.

The amount of chain extender used is not particularly limited, but the lower limit is usually 0.1, preferably 0.8, and the upper limit is usually 5.0, relative to the equivalent amount of NCO groups contained in the prepolymer. Preferably it is the range of 2.0.
Further, a monofunctional organic amine or alcohol may coexist during the reaction.
In the chain extension reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment and the like. If the temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor, and if it is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added for reaction as needed. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. Examples of the stabilizer include 2,6-dibutyl-4-methylphenol. , Distearyl thiodipropionate, di-betanaphthyl phenylenediamine, tri (dinonylphenyl) phosphite and the like. However, when the chain extender is highly reactive, such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.

<Physical properties of polyurethane>
Since the polyurethane obtained by the above production method is reacted in the presence of a solvent, it is generally obtained in a state dissolved in a solution. However, physical properties are not particularly limited in a solution state or a solid state. Unless otherwise, it is not limited to the state.
The weight average molecular weight of the polyurethane varies depending on the use, but is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 100,000 to 300,000 as the polyurethane polymerization solution. is there. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, and more preferably 1.8 to 3. As a fiber, a film, and a moisture-permeable resin molding, the weight average molecular weight of polyurethane is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 to 40. It is ten thousand. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, and more preferably 1.8 to 3.

  Further, the polyurethane obtained by the above production method preferably contains 1 to 20% by weight, more preferably 3 to 15% by weight, based on the total weight of the polyurethane polymer. More preferably, it is 4 to 12% by weight, and particularly preferably 5 to 10% by weight. When the amount of the hard segment is too large, the obtained polyurethane polymer does not exhibit sufficient flexibility and elastic performance, or when using a solvent, it tends to be difficult to dissolve and difficult to process. If the amount is too small, the urethane polymer tends to be too soft and difficult to process, and sufficient strength and elastic performance tend not to be obtained.

In the present invention, the hard segment refers to P.I. J. et al. Based on Flory, Journal of American Chemical Society, 58, 1877-1885 (1936), the weight of isocyanate and amine bond portion relative to the total weight is calculated by the following formula.
Hard segment (%) = [(R−1) (Mdi + Mda) / {Mp + R · Mdi + (R−1) · Mda}] × 100
here,
R = number of moles of isocyanate / (number of moles of hydroxyl group of polyether polyol + number of moles of hydroxyl group of polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular terminal)

Mdi = number average molecular weight of diisocyanate
Mda = number average molecular weight of chain extender
Mp = average molecular weight of the number average molecular weight of the polyether polyol and the number average molecular weight of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end The polyurethane solution obtained in the present invention is less prone to gelation, Storage stability is good, such as a small change in viscosity over time, and thixotropy is also small, which is convenient for processing into films, yarns, and the like. The polyurethane concentration of the polyurethane solution is usually 1 to 99% by weight, preferably 5 to 90% by weight, more preferably 10 to 70% by weight, particularly preferably 15 to 50% by weight, based on the total weight of the solution dissolved in the solvent. %. If the amount of polyurethane is too small, it is necessary to remove a large amount of solvent and the productivity tends to be low. If it is too large, the viscosity of the solution is too high and the operability and workability tend to be poor. .
The polyurethane solution is not particularly specified, but when it is stored for a long period of time, it is preferably stored in an inert gas atmosphere such as nitrogen or argon at room temperature or lower.

<Polyurethane moldings / uses>
After obtaining the polyurethane and its urethane prepolymer solution produced in the present invention, a polyurethane molded product can be obtained by molding them.
The polyurethane molded article of the present invention is not particularly limited as long as it is a molded article made of the above-mentioned polyurethane or polyurethane obtained by the above-mentioned production method. Usually, (a) it has at least one hydroxyl group at the molecular end. A polyurethane molded article comprising a polyurethane containing a polyhydroxy hydrocarbon polymer, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, the atomic composition of the surface of the polyurethane molded article (Oxygen atom / carbon atom) is 0.22 or less. Specifically, the atomic composition (oxygen atom / carbon atom) on the surface of the polyurethane molded body is, for example, when the surface of the molded body is measured by ESCA (Electron Spectroscopic for Chemical Analysis) or XPS (X-ray Photoelectron Spectroscopy). The relative abundance ratio of oxygen atoms to carbon atoms is shown.

The value of the atomic composition (oxygen atom / carbon atom) on the surface of the polyurethane molded product of the present invention is preferably 0.20 or less, more preferably 0.16 or less. As this value becomes smaller, the tackiness of the resulting molded article tends to be reduced and the peelability tends to be better. Moreover, Preferably it is 0.00 or more, More preferably, it is 0.05 or more. As this value increases, the packing property when the obtained molded bodies are stacked tends to be higher. For example, when the molded body is a yarn, the wound yarn is released and it is difficult to cause a loss of shape.
In addition to the above-mentioned surface atomic composition (oxygen atom / carbon atom) being 0.22 or less, the surface water contact angle of the polyurethane molded article of the present invention is preferably 80 degrees or more.

The water contact angle on the surface is obtained by dropping a few μl of water droplets on the surface of the molded body and measuring the inner angle formed by the tangent of the droplet and the surface of the molded body within 10 seconds. The value of the water contact angle on the surface of the polyurethane molded product of the present invention is 80 degrees or more, preferably 83 or more, and more preferably 86 or more. As this value increases, the tackiness of the resulting molded article tends to be reduced and the peelability tends to be good. Moreover, it is preferably 180 degrees or less, more preferably 150 degrees or less. The smaller this value is, the higher the packing property when the obtained molded bodies are overlapped with each other. For example, when the molded body is a yarn, the wound yarn is unwound and it is difficult to cause a loss of shape.
Moreover, since the polyurethane of this invention, a urethane prepolymer solution, and a polyurethane molding express a various characteristic, it can be used for various uses. For example, it can be widely used for foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, and the like.

  The polyurethane, polyurethane urea and urethane prepolymer solution produced in the present invention can be used for cast polyurethane elastomers. Examples include rolls such as rolling rolls, papermaking rolls, office equipment, pretension rolls, forklifts, solid tires for casters, vehicles, etc., casters, industrial products such as conveyor belt idlers, guide rolls, pulleys Steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. It is also applied to OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, and surface rollers.

  The polyurethane and its urethane prepolymer solution produced in the present invention are also applied for use as a thermoplastic elastomer. For example, it can be used as tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment, industrial robots and the like used in the food and medical fields. Also, as belts such as round belts, V-balts, flat belts, etc., they are used in various transmission mechanisms, spinning machines, packing equipment, printing machines and the like. Further, examples include footwear heel tops, shoe soles, couplings, packings, pole joints, bushes, gears, rolls and other equipment parts, sports equipment, leisure goods, watch belts, and the like. Furthermore, examples of automobile parts include oil stoppers, gear boxes, spacers, chassis parts, interior parts, tire chain substitutes, and the like. Further examples include keyboard films, films such as automobile films, curl cords, cable sheaths, bellows, transport belts, flexible containers, binders, synthetic leather, depinning products, and adhesives.

The polyurethane and its urethane prepolymer solution produced in the present invention can also be used as a solvent-based two-component paint, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sports equipment. It can also be used for automobile repair as tar epoxy urethane.
The polyurethane and its urethane prepolymer solution produced in the present invention can be used as components of moisture-curable one-component paints, block isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet curable paints, etc. For example, plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring materials, overprint varnishes such as paper and wood grain printing films, wood varnishes, coil coats for high processing, optical fiber protective coatings , Solder resist, metal printing top coat, vapor deposition base coat, food can white coat and the like.

The polyurethane and its urethane prepolymer solution produced in the present invention are applied as adhesives to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. It can also be used as a component of a melt.
The polyurethane and its urethane prepolymer solution produced in the present invention are magnetic recording medium, ink, casting, fired brick, graft material, microcapsule, granular fertilizer, granular agricultural chemical, polymer cement mortar, resin mortar, rubber chip binder. It can be used for recycled foam and glass fiber sizing.

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as a component of a fiber processing agent for shrink-proofing, anti-molding, water-repellent processing and the like.
The polyurethane, polyurethane urea and its urea prepolymer solution produced in the present invention are used as a sealant caulking for concrete wall, induction joint, sash area, wall-type PC joint, ALC joint, board joint, composite glass Can be used for sealant, heat insulating sash sealant, automotive sealant, etc.

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as medical materials, such as tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc. as blood compatible materials, and catheters as disposable materials. , Tubes, bags, surgical gloves, artificial kidney potting materials, etc.
The polyurethane, polyurethane urea, and urethane prepolymer solution produced in the present invention are modified with UV curable paint, electron beam curable paint, photosensitive resin composition for flexographic printing plate, photocurable It can be used as a raw material for the optical fiber coating material composition.

In particular, it is preferable to use the elastic performance and moisture permeability characteristics of the polyurethane produced by the present invention to be used for films and fibers. Specific examples of these applications include medical, hygiene materials, artificial leather, and clothing. It is preferable to use for these elastic fibers.
As mentioned above, although the usage example using the polyurethane manufactured by this invention and its urethane prepolymer solution was described, this invention is not limited to these uses.
Although the manufacturing method of a film and a fiber is described below, a manufacturing method is not necessarily restrict | limited.

<Film production method>
The method for producing the film is not particularly limited, and a known method can be used. For example, as a film manufacturing method, a polyurethane resin solution is applied to a support or a release material, and a solvent or other soluble material is extracted in a coagulation bath, and a polyurethane resin solution is applied to the support or a release material. And a dry film forming method in which the solvent is dried by heating or reduced pressure. The support used for dry film formation is not particularly limited, but polyethylene, polypropylene film, glass, metal, paper coated with a release material, cloth or the like is used. The application method is not particularly limited, and any known method such as a knife coater, a roll coater, a spin coater, or a gravure coater may be used. The drying temperature can be arbitrarily set depending on the ability of the dryer, but it is necessary to select a temperature range in which drying is insufficient or rapid desolvation does not occur. Preferably it is the range of room temperature-300 degreeC, More preferably, it is the range of 60 degreeC-200 degreeC.

<Physical properties of film>
The thickness of the film of the present invention is usually 10 to 1000 μm, preferably 10 to 500 μm, more preferably 10 to 100 μm. When the film is too thick, there is a tendency that sufficient moisture permeability cannot be obtained. When the film is too thin, pinholes are likely to be formed or the film tends to be blocked and difficult to handle. Moreover, this film can be preferably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. The film may be applied to a support such as cloth or nonwoven fabric. In this case, it may be thinner than 10 μm.

The elongation at break is usually 100% or more, preferably 200% or more, more preferably 300% or more, and still more preferably 500% or more. The breaking strength is usually 5 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and further preferably 30 MPa or more.
In a 300% elongation-shrinkage repetition test at 23 ° C., the elastic retention rate (Hr1 / H1), which is grasped by the ratio of the stress at 150% elongation at the first contraction to the stress at 150% elongation at the first elongation, is usually It is 10% or more, preferably 20% or more, more preferably 30% or more, and further preferably 40% or more. Similarly, the elastic retention rate (Hr5 / H5) captured by the ratio of the stress at 150% elongation at the fifth contraction to the stress at 150% elongation at the fifth elongation is usually 30% or more, preferably 50% or more. Preferably it is 70% or more, More preferably, it is 85% or more.

Also, in the 300% elongation-shrinkage repetition test at 23 ° C., the elastic retention rate (H2 / H1), which is grasped by the ratio of the stress at 150% elongation at the second elongation to the stress at 150% elongation at the first elongation, is Usually, it is 20% or more, preferably 40% or more, more preferably 50% or more, and further preferably 60% or more.
The second residual strain in the 300% stretch-shrink repeated test at 23 ° C. is usually 40% or less, preferably 30% or less, more preferably 25% or less, and particularly preferably 20% or less. The residual strain at the fifth time is usually 50% or less, preferably 35% or less, more preferably 30% or less, and particularly preferably 25% or less.
The physical properties of the polyurethane film and the yarn have a very good correlation, and the physical properties obtained by the film test and the like show the same tendency in the yarn (fiber).

<Uses of polyurethane fibers>
The fiber using the polyurethane of the present invention is more specifically used for leg, panty / stocking, diaper cover, paper diaper, sports clothing, underwear, socks, fashionable stretch clothing, swimwear, It is preferably used for applications such as leotard. This is because it is excellent in stretch recovery, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, workability, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. The analysis and measurement in the following examples and comparative examples were based on the following methods.
<Number average molecular weight of polyhydroxy hydrocarbon polymer and polyether polyol>
The number average molecular weights of the polyhydroxy hydrocarbon polymer and polyether polyol used in the present invention were determined by a hydroxyl value (KOH (mg) / g) measurement method by an acetylation method based on JIS K1557-1: 2007. .

<Molecular weight of polyurethane and polyurethane urea>
The molecular weight of the obtained polyurethane or polyurethane urea was prepared by preparing a dimethylacetamide solution of polyurethane or polyurethane urea, and using a GPC apparatus [manufactured by Tosoh Corporation, product name “HLC-8220” (column: Tskel GMH-XL (2)] The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Peeling test method>
Two pieces of the obtained films are overlapped, and a sample length of 4 cm (including an initial test length portion and a 2.5 cm overlap portion when fixed to a tensile tester having a length of 1.5 cm) and a width of 1 cm with a test piece punching machine. A film was obtained. The test piece was allowed to stand for 10 minutes at a temperature of 25 ° C. and a relative humidity of 50% in a state where a pressure of 200 g / cm ² was applied, and then a tensile tester (FU
The T-type peel strength was measured by pulling the test film at a speed of 300 mm / min using a DOH “Rheometer NRM-2003J”).

<Physical properties of film>
The polyurethane or polyurethane urea test piece is a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm, and in accordance with JIS K6301, using a tensile tester (product name “Tensilon UTM-III-100” manufactured by Orientec Co., Ltd.). The tensile breaking strength at a temperature of 23 ° C. (relative humidity 55%), tensile breaking elongation, and strength at 100% elongation and 300% elongation were measured at a chuck distance of 50 mm and a tensile speed of 500 mm / min.
<Surface atomic composition>
The surface atomic composition was determined by ESCA (Electron Spectroscopy for Chemical Analysis) measurement. The measurement was performed using an ULVAC-PHI Co., Ltd. ESCA apparatus “PHI Model 5800”. The measurement conditions are as follows.
Excitation X-ray: monochromatic AlKα ray (1486.6 eV)
-X-ray output: (filament) 14kV, 350W (7mm)
・ Neutralizing gun: Use (for antistatic)
・ Input lens setting (Lens Area Mode): Minimum Area Mode
・ Analysis mode (LENS MODE): 5 (minimum area mode)
・ Aperture number: 5
・ Emission angle (angle formed by the sample normal to the center axis of the detector): 45 degrees ・ PassEnergy: 23.5 eV
Charge shift correction: The C1s peak binding energy of CH-bonded carbon was adjusted to 285.0 eV.

The relative abundance ratio of oxygen atoms to carbon atoms was calculated by the following formula.
Surface atomic composition (relative abundance ratio O / C) = (peak area of oxygen O1s / peak corrected relative sensitivity coefficient of oxygen O1s peak) / (peak area of carbon C1s / peak corrected relative sensitivity coefficient of carbon C1s peak)
In addition, the area of each peak of oxygen O1s and carbon C1s is the MultiPak Ver. The smoothing process (9 points) using the Savitzky-Golay algorithm was performed using 8.2C software, and it calculated | required using the background curve of a shirley method. Oxygen O1s and carbon C1s peak binding energies and MultiPak Ver. The respective corrected relative sensitivity coefficients used in the 8.2C software are as follows.
O1s: binding energy = around 532.5 eV,
-Corrected relative sensitivity coefficient = 13.118
C1s: binding energy = around 285.0 eV,
Corrected relative sensitivity coefficient = 5.220
Regarding the peak area of carbon C1s, it is derived from the shape of the benzene ring shale up obtained by connecting the local minimum values around 280 eV and 290.5 eV with shirley and the local minimum values near 290.5 eV and 293 eV with shirley. What added the area of the peak (near 291-293eV) was used.

<Water contact angle>
Using an automatic contact angle meter DM-300 manufactured by Kyowa Interface Science Co., Ltd., 1.5 to 2.0 μL of water droplets were dropped on the surface of the polyurethane film, and the internal angle formed by the tangent of the water droplets and the surface of the molded product was measured after 5 seconds. The same operation was repeated five times while changing the film location, and the average value of the obtained five points was defined as the water contact angle.

<Example 1>
142.5 parts by weight of polytetramethylene ether glycol (number average molecular weight 1968 calculated from hydroxyl value, manufactured by Mitsubishi Chemical Corporation) previously heated to 40 ° C. in a 1 L flask, and hydrogenated polybutadiene polyol manufactured by Mitsubishi Chemical Corporation (Trade name “Polytail HA” number average molecular weight: 2187, average number of hydroxyl group bonds per molecule: 1.8) 7.5 parts by weight were added and mixed, and this mixture was used as a raw material for polyurethane production. The ratio of polytail HA to this mixture was 5% by weight. Thereafter, 31 parts by weight of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) heated to 40 ° C. was added. The reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) at this time was 1.6. The flask was set in a 45 ° C. oil bath, and the temperature of the oil bath was raised to 70 ° C. over 1 hour while stirring with a vertical stirring blade in a nitrogen atmosphere.
For 3 hours. After the residual NCO group was reacted with an excess amount of dibutylamine and then the residual dibutylamine was back titrated with hydrochloric acid to confirm that the NCO reaction rate exceeded 99%, the oil bath was removed, and N, A polyurethane prepolymer solution was prepared by adding 271 parts of N-dimethylacetamide (hereinafter sometimes abbreviated as “DMAC”; manufactured by Kanto Chemical Co., Inc.) and stirring and dissolving at room temperature.

  380 parts by weight of the polyurethane prepolymer solution was cooled and held at 10 ° C., while ethylenediamine (EDA) / diethylamine (DEA) used as a chain extender = 89/11 (molar ratio) = 1.72 / 0. A 27% (by weight) 0.6% DMAC solution was prepared. The polyurethane prepolymer solution cooled and held at 10 ° C. was added to the 0.6% DMAC solution while stirring at high speed to obtain a polyurethane urea DMAC solution having a polymer concentration of 20%.

The solution was aged at 25 ° C. overnight, and the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 172,000 and the molecular weight distribution was 2.4. The proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.
The polyurethaneurea solution thus obtained was cast on a glass plate and dried at 60 ° C. to obtain a colorless and transparent film having a thickness of about 50 μm. The thickness of the film was measured with a thickness meter.

When this film was peeled, the stress required for peeling was 5.7 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 1. The film had a surface atomic composition of 0.089 and a water contact angle of 90 degrees. The results are shown in Table 1.
<Example 2>
In Example 1, 148.5 parts by weight of polytetramethylene ether glycol (number average molecular weight 1968 calculated from hydroxyl value, manufactured by Mitsubishi Chemical Corporation) as a raw material for producing polyurethane and “polytail HA” (number average molecular weight: 2187, 1 1.5 parts by weight of the average number of hydroxyl group bonds per molecule: 1.8 parts by weight were added and mixed (the proportion of polytail HA in this mixture was 1% by weight), and ethylenediamine / diethylamine = 1.81 / 0.28 ( A prepolymer and a polyurethane urea solution were obtained in the same manner as in Example 1 except that the weight ratio was changed.

After this solution was aged at 25 ° C. overnight, the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 202,000 and the molecular weight distribution was 2.5. The proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 81% by weight.
A colorless and transparent polyurethane urea film having a thickness of about 50 μm was obtained from this polyurethane urea solution.

When this film was peeled, the stress required for peeling was 5.7 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 1. The film had a surface atomic composition of 0.119 and a water contact angle of 89 degrees. The results are shown in Table 1.
<Example 3>
In Example 2, 149.85 parts by weight of polytetramethylene ether glycol (number average molecular weight calculated from hydroxyl value, 1968, manufactured by Mitsubishi Chemical Corporation) as a raw material for polyurethane production, and “polytail HA” (number average molecular weight: 2187, 1 Prepolymer and polyurethane urea in the same manner except that 0.15 parts by weight of hydroxyl group average molecular weight per molecule was added and mixed (the ratio of polytail HA in the mixture was 0.1% by weight). A solution was obtained.

The solution was aged at 25 ° C. overnight, and then the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 198,000 and the molecular weight distribution was 2.4. Further, the proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 82% by weight.
A colorless and transparent polyurethane urea film having a thickness of about 50 μm was obtained from this polyurethane urea solution.

When this film was peeled, the stress required for peeling was 33 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 1. The surface atomic composition of this film was 0.194. The results are shown in Table 1.
<Example 4>
In Example 1, 105 parts by weight of polytetramethylene ether glycol (number average molecular weight calculated from hydroxyl value 1968, manufactured by Mitsubishi Chemical Corporation) and “polytail HA” (number average molecular weight: 2187, average bond of hydroxyl groups per molecule) Number: 1.8) 45 parts by weight was added and mixed (the proportion of polytail HA in the mixture was 30% by weight), and a prepolymer and a polyurethane urea solution were obtained in the same manner.

The solution was aged at 25 ° C. overnight, and then the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 198,000 and the molecular weight distribution was 2.4. Further, the proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 57% by weight.
From this polyurethane urea solution, a slightly cloudy polyurethane urea film having a thickness of about 50 μm was obtained.

When this film was peeled, the stress required for peeling was 33 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 1.
<Comparative Example 1>
In Example 1, it is the same except that 150 parts by weight of polytetramethylene ether glycol (number average molecular weight 1968 calculated from hydroxyl value, manufactured by Mitsubishi Chemical Corporation) is used as a raw material for polyurethane production without using “polytail HA”. Thus, a prepolymer and a polyurethane urea solution were obtained.

After this solution was aged at 25 ° C. overnight, the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 191,000 and the molecular weight distribution was 2.6. The proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.
A colorless and transparent polyurethane urea film having a thickness of about 50 μm was obtained from this polyurethane urea solution.

  When this film was peeled, the stress required for peeling was 50 g / cm. At the time of peeling, the film was stretched by 12% with respect to the initial test length. Further, the obtained elastic film had characteristics as shown in Table 1. The film had a surface atomic composition of 0.239 and a water contact angle of 76 degrees. The results are shown in Table 1.

＜実施例５＞
［ポリエステルポリオールの製造］
撹拌子を備えた１００mL四つ口丸底フラスコに１．２ｍｇのテトラブチルオルトチタネート(東京化成社)、３０ｇ（２０．０ｍｍｏｌ）の水添ポリブタジエンポリオールＧＩ−１０００（日本曹達社、分子量１５００)、１０ｇ（８７．６ｍｍｏｌ）のε-カプロラクトン (Aｃｒｏｓｓ社)を測り取った。還流管および窒素導入管を取り付け、反応容器をオイルバスに浸して３０分で１９０℃まで昇温し、１９０℃で７ｈ反応させてポリエステルポリオール１とした。表２にこのポリエステルポリオール１の理論分子量、理論酸素含有量も併せて示す。
［ポリウレタンウレアの製造］
容量が１Ｌのフラスコにあらかじめ４０℃に加温したポリテトラメチレンエーテルグリコール（水酸基価より算出した数平均分子量１９５５、三菱化学社製）１２３．９重量部と、上記で合成したポリエステルポリオール１を６．５２重量部加えて混合し、この混合物をポリウレタン製造用の原料とした。この混合物に対するポリエステルポリオール１の割合は５重量％であった。その後、４０℃に加温した４，４´−ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記することがある。）２６．８重量部を加えた。このときの、ＮＣＯ／活性水素基（ポリエーテルポリオールと鎖延長剤）の反応当量比は１．６であった。そして、このフラスコを４５℃のオイルバスにセットし、窒素雰囲気下にて碇型攪拌翼で攪拌しつつ、1時間かけてオイルバスの温度を７０℃まで昇温し、その後７０℃にて3時間保持した。残存ＮＣＯ基を過剰量のジブチルアミンと反応させその後残存ジブチルアミンを塩酸により逆滴定することによりＮＣＯの反応率が９９％を越えていることを確認した後に、オイルバスを取り去り、フラスコにＮ，Ｎ−ジメチルアセトアミド（以下、「ＤＭＡＣ」と略記することがある。関東化学社製）２３６部を加え、室温にて攪拌し溶解させることでポリウレタンプレポリマー溶液を調製した。

<Example 5>
[Production of polyester polyol]
In a 100 mL four-necked round bottom flask equipped with a stir bar, 1.2 mg of tetrabutyl orthotitanate (Tokyo Kasei Co., Ltd.), 30 g (20.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Co., Ltd., molecular weight 1500), 10 g (87.6 mmol) of ε-caprolactone (Across) was weighed. A reflux pipe and a nitrogen introduction pipe were attached, the reaction vessel was immersed in an oil bath, heated to 190 ° C. in 30 minutes, and reacted at 190 ° C. for 7 hours to obtain polyester polyol 1. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of this polyester polyol 1.
[Production of polyurethane urea]
Polytetramethylene ether glycol (number average molecular weight 1955 calculated from hydroxyl value, 1955, manufactured by Mitsubishi Chemical Corp.) 123.9 parts by weight preheated to 40 ° C. in a 1 L flask and 6 of the polyester polyol 1 synthesized above .52 parts by weight was added and mixed, and this mixture was used as a raw material for polyurethane production. The ratio of polyester polyol 1 to this mixture was 5% by weight. Thereafter, 26.8 parts by weight of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) heated to 40 ° C. was added. The reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) at this time was 1.6. The flask was set in an oil bath at 45 ° C., and the temperature of the oil bath was raised to 70 ° C. over 1 hour while stirring with a vertical stirring blade in a nitrogen atmosphere. Held for hours. After the residual NCO group was reacted with an excess amount of dibutylamine and then the residual dibutylamine was back titrated with hydrochloric acid to confirm that the NCO reaction rate exceeded 99%, the oil bath was removed, and N, A polyurethane prepolymer solution was prepared by adding 236 parts of N-dimethylacetamide (hereinafter sometimes abbreviated as “DMAC”; manufactured by Kanto Chemical Co., Inc.) and stirring and dissolving at room temperature.

  The polyurethane prepolymer solution was cooled and held at 10 ° C., while ethylenediamine (EDA) / diethylamine (DEA) used as a chain extender = 89/11 (molar ratio) = 1.66 / 0.24 ( Weight ratio) of 0.5% DMAC solution. The polyurethane prepolymer solution cooled and held at 10 ° C. was added to this 0.5% DMAC solution while stirring at high speed to obtain a polyurethane urea DMAC solution having a polymer concentration of 20%.

The solution was aged at 25 ° C. overnight, and then the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 21,000,000 and the molecular weight distribution was 2.7. The proportion of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.
The polyurethaneurea solution thus obtained was cast on a glass plate and dried at 60 ° C. to obtain a colorless and transparent film having a thickness of about 50 μm. The thickness of the film was measured with a thickness meter.

When this film was peeled, the stress required for peeling was 4.4 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.097 and a water contact angle of 95 degrees. The results are shown in Table 3.
<Example 6>
[Production of polyester polyol]
Instead of GI-1000, 60 g (28.6 mmol) of GI-2000 (Nippon Soda Co., Ltd., molecular weight 2100) was used, the amount of tetrabutyl orthotitanate used was 3.6 mg, and the amount of ε-caprolactone used was 12 g (105 mmol). A polyester polyol 2 was produced in the same manner as in Example 5 except that. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of this polyester polyol 2.
[Production of polyurethane urea]
A polyurethane urea solution and a film were obtained in the same manner as in Example 5 with the raw material charge for polyurethane production shown in Table 3. When this film was peeled, the stress required for peeling was 6.7 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.094 and a water contact angle of 94 degrees. The results are shown in Table 3.

<Example 7>
[Production of polyester polyol]
Example 6 except that 51.3 g (24.4 mmol) GI-2000, 2.5 mg tetrabutyl orthotitanate, 22 g (193 mmol) ε-caprolactone were used.
Polyester polyol 3 was produced in exactly the same manner. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of this polyester polyol 3.
[Production of polyurethane urea]
A polyurethane urea solution and a film were obtained in the same manner as in Example 5 with the raw material charging amounts shown in Table 3 at the time of polyurethane production. When this film was peeled, the stress required for peeling was 3.6 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. This film had a surface atomic composition of 0.100 and a water contact angle of 95 degrees. The results are shown in Table 3.

<Example 8>
[Production of polyester polyol]
Instead of GI-1000, 60 g (27.9 mmol) of hydrogenated polyisoprene polyol Epol (Idemitsu Kosan, molecular weight 1800) was used, tetrabutyl orthotitanate was used in 3.6 mg, and ε-caprolactone was used in 10 g. A polyester polyol 4 was produced in the same manner as in Example 5 except that the amount was changed to (87.6 mmol). Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of this polyester polyol 4.

[Production of polyurethane urea]
A polyurethane urea solution and a film were obtained in the same manner as in Example 5 with the raw material charging amounts shown in Table 3 at the time of polyurethane production. When this film was peeled, the stress required for peeling was 4.5 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.154 and a water contact angle of 88 degrees. The results are shown in Table 3.

<Example 9>
[Production of polyester polyol]
In a 100 mL four-necked round bottom flask equipped with a stir bar, 4.2 mg of tetrabutyl orthotitanate (Tokyo Kasei Co., Ltd.), 66.0 g (44.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Co., Ltd., molecular weight 1500) ) 3.8 g (22.0 mmol) of dimethyl adipate (Tokyo Kasei Co., Ltd.) was measured. A reflux pipe and a nitrogen introduction pipe were attached, the reaction vessel was immersed in an oil bath, heated to 190 ° C. in 30 minutes, and reacted at 190 ° C. for 7 hours to obtain polyester polyol 5. During the reaction, the distillate was heated to 120 ° C. with a tape heater, and methanol produced by the reaction was entrained with nitrogen and distilled off. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of this polyester polyol 5.

[Production of polyurethane urea]
A polyurethane urea solution and a film were obtained in the same manner as in Example 5 with the raw material charging amounts shown in Table 3 at the time of polyurethane production. When this film was peeled, the stress required for peeling was 10.8 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.072 and a water contact angle of 96 degrees. The results are shown in Table 3.

<Example 10>
[Production of polyester polyol]
Instead of dimethyl adipate, 3.09 g (21.1 mmol) of dimethyl succinate (Tokyo Kasei Co., Ltd.) was used, GI-1000 usage was 63.4 g (42.3 mmol), and tetrabutyl orthotitanate usage was 2. A polyester polyol 6 was produced in the same manner as in Example 9, except that the amount was 2 mg. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 6.

[Production of polyurethane urea]
A polyurethane urea solution and a film were obtained in the same manner as in Example 5 with the raw material charging amounts shown in Table 3 at the time of polyurethane production. When this film was peeled, the stress required for peeling was 13.0 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.083 and a water contact angle of 98 degrees. The results are shown in Table 3.

<Comparative Example 2>
[Production of polyurethane urea]
A polyurethane urea solution and a film containing no polyester polyol were obtained in the same manner as in Example 5 with the amounts of raw materials charged in the production of polyurethane shown in Table 3. When this film was peeled, the stress required for peeling was 66.3 g / cm, and the peelability was poor. Further, the obtained elastic film had characteristics as shown in Table 3. The film had a surface atomic composition of 0.239 and a water contact angle of 76 degrees. The results are shown in Table 3.

Claims (18)

(A) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) polytetramethylene ether glycol, polytrimethylene ether glycol, 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran A polymerization polyether polyol, a copolymer of neopentyl glycol and tetrahydrofuran, and at least one polyether polyol selected from polyether glycol, (c) a polyisocyanate compound, and (d) a chain extender raw material are subjected to an addition polymerization reaction, In obtaining polyurethane, (a) polyhydroxy hydrocarbon having at least one hydroxyl group at the molecular end relative to the total of (a) polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end and (b) polyether polyol. Carbonization The reaction is carried out in the presence of a solvent selected from the group consisting of an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylsulfoxide, wherein the proportion of the base polymer is 0.01 to 50.00% by weight. A process for producing a polyurethane, characterized in that   2. The method for producing a polyurethane according to claim 1, wherein (a) the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at a molecular end has a number average molecular weight of 500 to 5,000.   3. The polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end (a) has an average number of hydroxyl groups per molecule of 1.5 to 2.7. The manufacturing method of the polyurethane of description.   The method for producing a polyurethane according to any one of claims 1 to 3, wherein the (c) polyisocyanate compound is an aromatic polyisocyanate.   The method for producing a polyurethane according to any one of claims 1 to 4, wherein the (d) chain extender is a polyamine compound.   The method for producing a polyurethane according to any one of claims 1 to 5, wherein the main skeleton of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end (a) is hydrogenated polybutadiene. . The (a) polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end is formed from (A) a polyhydroxy hydrocarbon polymer and (B) an ester group-containing compound or a carboxy group-containing compound. The method for producing a polyurethane according to any one of claims 1 to 6, wherein the polyurethane is a polyester polyol.   In the polyester polyol, (A) and (B) form at least one ester bond, and the oxygen content in the polyester polyol is 2.0% by mass or more and 13.5% by mass or less. The method for producing a polyurethane according to claim 7.   The method for producing a polyurethane according to claim 7 or 8, wherein (B) is a polylactone. The polyester polyol is formed of (A) and (B), (B) (A)
It is a (B) type block copolymer, The manufacturing method of the polyurethane in any one of Claims 7-9 characterized by the above-mentioned.   The method for producing a polyurethane according to claim 7 or 8, wherein (B) is a dicarboxylic acid.   The method for producing a polyurethane according to claim 11, wherein the dicarboxylic acid has 2 to 15 carbon atoms. The polyurethane according to claim 10 or 11, wherein the polyester polyol is a block copolymer of (AB) nA type (where n is an integer of 1 or more) formed by (A) and (B). Manufacturing method.   (A) A polyester polyol formed from a polyhydroxy hydrocarbon polymer and (B) a dicarboxylic acid, wherein (A) and (B) form at least one ester bond, and the polyester polyol. A polyester polyol having an oxygen content of 2.0% by mass or more and 13.5% by mass or less. Polyester polyol according to claims 1 to 4 carbon atoms, and wherein the at 2 to 15 of the dicarboxylic acid. Wherein the polyester polyol is said (A) and is formed by (B), (AB) nA type block copolymer (where, n is an integer of 1 or more) according to claim 1 4, characterized in that the
Or the polyester polyol according to 15 . Polyester polyol according to any one of claims 1 4-16 a number average molecular weight of the polyester polyol, characterized in that 500 to 5,000. (A) the polyhydroxy hydrocarbon polymer is a polyester polyol according to any one of claims 1 4-17, which is a hydrogenated polydiene polyols.