CN103172816B - Method for producing polyurethane and use of polyurethane obtained by the method - Google Patents

Abstract

The subject of the invention is to provide: a method for producing polyurethane urea comprising a polyether polyol, a polyisocyanate compound and a chain extender, wherein polyurethane and polyurethane urea having low adhesion and high releasability are produced. The method for producing a polyurethane of the present invention is characterized in that, when a polyurethane is produced using a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at a molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, the production is carried out in the presence of an aprotic polar solvent.

Description

Method for producing polyurethane and use of polyurethane obtained by the method

This application is a divisional application based on the following Chinese patent application:

Date of original filing: November 30, 2009

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

Title of original application: Method for producing polyurethane and use of polyurethane obtained by the method

technical field

The present invention relates to a method for producing polyurethane, a polyurethane obtained by the method, and the use thereof.

Background technique

Polyurethane compounds and polyurethane urea compounds are used in various fields. Polyurethane compounds are mainly made of polyols such as polyester polyols or polyether polyols and isocyanate compounds, and chain extenders, foaming agents, foam stabilizers, etc. added as needed, and are often used as polyurethane elastic fibers or polyurethane urea Department of elastic fiber and other purposes. In particular, fibers having a polyurethane urea structure have excellent elastic properties and stretch recovery properties because polyether polyol is used as a soft segment component and a polyamine compound with high cohesive force is used as a hard segment. However, these polyurethane-based elastic fibers have poor unwinding properties at the time of spinning due to high adhesion between fibers. In addition, due to high friction, spinning machines, warping machines, knitting machines, or guide rails that are in contact with the line Disconnection occurred in the machine in the processing process. Therefore, problems such as disconnection during the processing process easily occur. Therefore, in order to reduce the friction between the machine and the wire in the processing process, there is a method of adding solid metal soap or oil-soluble polymers, higher fatty acids, amino-modified polysiloxane, etc. There is a method of introducing talc, silica, colloidal alumina, or titanium oxide as an agent, and a method of introducing silicon diol or silicon diamine into a part of the polyurethane main chain (for example, Patent Document 1).

However, even in this method, there is a problem that a sufficient anti-adhesion effect cannot be obtained, or that the smoothing agent causes significant wear to the spinning machine, warping machine, knitting machine, or yarn guide, or the warping, warping In the weaving process, the oligomers in the fiber extracted by the oil component or the solid or high-viscosity components in the oil become solid or slurry and the separated substances adhere to the fiber in large quantities, contaminating the product or using it. The problem was not solved due to the clogging of machinery or equipment. Therefore, there is a demand for a method for producing polyurethane that has low adhesion even without using such an oil or smoothing agent, and has high unwinding properties (or peeling properties between polyurethanes) at the time of spinning, and high peeling properties. .

On the other hand, an example in which a polyhydroxy hydrocarbon-based polymer having a hydroxyl group is used as a raw material of polyurethane is used as a modifier of a urethane-based resin for improving the adhesiveness of a polyolefin resin material (Patent Document 2 ), or as a polymer polyol mixed with polytetramethylene glycol to produce polyurethane, trying to improve the durability of polyurethane-based elastic fibers (Patent Document 3). However, in the method described in Patent Document 3, the hydrophobicity of the polymer polyol is too high, the compatibility with the polyether polyol is deteriorated, gelation occurs when polyurethane is produced, or dispersion is not uniform when it is made into a yarn or a film. question. In addition, it is known that stretchable fabrics or swimwear made of polyurethane fibers produced by the method described in Patent Document 3 are excellent in chlorine resistance, hot water resistance, light resistance, etc., but the use of polyhydroxyl hydrocarbon-based polymers having hydroxyl groups As a raw material, the adhesiveness of polyurethane is lowered, and even the adhesiveness of molded articles such as films or elastic fibers made of polyurethane is lowered, and it is not used for the purpose of improving peelability. In addition, the polyurethane-based elastic fibers described in Patent Document 3 include polyols and polyamines as chain extenders, but are actually elastic fibers obtained by melt spinning using polyols as chain extenders. If this method is used to obtain a so-called polyurethane-urea structure using polyamines, abnormal reactions such as gelation or three-dimensional crosslinking are likely to occur during the chain extension reaction, and there is a problem that it is difficult to form a homogeneous fiber or film.

In addition, on the other hand, the following studies have been carried out to improve the raw material components of polyurethane for the purpose of improving various physical properties of polyurethane elastic fibers. For example, as an example of using a polyester polyol, a hydrophobic polyester polyol consisting of a diol constituent whose essential component is a polyol having a hydrocarbon group in a side chain and a carboxylic acid constituent whose essential constituent is a dimer acid is proposed. (Patent Document 4). However, even when these polyester polyols are used, polyurethane exhibiting sufficient releasability cannot be obtained.

Background technical literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 10-259577

Patent Document 2: Japanese Patent Application Laid-Open No. 6-158016

Patent Document 3: Japanese Patent Application Laid-Open No. 11-131325

Patent Document 4: Japanese Patent Laid-Open No. 2002-212273

Contents of the invention

The problem to be solved by the invention

The present invention is made in view of the above-mentioned problems, and an object of the present invention is to provide a method for producing polyurethane and polyurethane urea and a new polyester polyol useful for producing polyurethane urea, and to produce polyurethane from polyether polyol, polyisocyanate compound, and chain extender When used, polyurethane and polyurethane urea are extremely useful for high-functional polyurethane applications such as polyurethane elastic fibers, films, and clothing, and have low adhesion and high peelability.

means to solve the problem

The inventors of the present invention have conducted earnest research to solve the above-mentioned problems, and as a result, found that when producing polyurethane, it is preferable to have a specific structure and a certain Oxygen-containing polyester polyol, more preferably mixing the polyester polyol and polyether polyol, can reduce the adhesion of the obtained polyurethane and polyurethane urea by reacting with a polyisocyanate compound and a chain extender in the presence of a solvent , can improve the detachability and the unwinding property at the time of spinning, thus completing the present invention.

That is, the gist of the present invention lies in the following [1] to [29].

[1] A method for producing polyurethane, comprising (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) When the raw material of the chain extender undergoes polyaddition reaction to obtain polyurethane, (a) the polyhydroxyl hydrocarbon-based polymer having at least one hydroxyl group at the molecular end is compared with (a) the polyhydroxyl hydrocarbon-based polymer having at least one hydroxyl group at the molecular end and ( b) The total ratio of the polyether polyol is 0.01 to 50.00% by weight, and the polyether polyol is reacted in the coexistence of a solvent selected from an amide-based solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylsulfoxide.

[2] Preferably, the method for producing polyurethane according to the above [1], wherein the (a) polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal has a number average molecular weight of 500 to 5,000.

[3] Preferably, the method for producing polyurethane according to the above [1] or [2], wherein the average number of hydroxyl groups per molecule of the (a) polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal is 1.5-2.7.

[4] Preferably, the method for producing polyurethane according to any one of [1] to [3] above, wherein the (c) polyisocyanate compound is an aromatic polyisocyanate.

[5] Preferably, the method for producing polyurethane according to any one of the above [1] to [4], wherein the (d) chain extender is a polyamine compound.

[6] Preferably, the method for producing polyurethane according to any one of the above-mentioned [1] to [5], wherein the main skeleton of the (a) polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular end is Hydrogenated polybutadiene.

[7] Preferably, the method for producing polyurethane according to any one of the above-mentioned [1] to [6], wherein the (a) polyhydroxyl hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal is composed of (A ) A polyester polyol formed from a polyhydroxy hydrocarbon polymer and (B) an ester group-containing compound or a carboxyl group-containing compound.

[8] Preferably, the method for producing polyurethane according to the above [7], wherein in the polyester polyol, the (A) and the (B) form at least one ester bond, and the polyester The oxygen content in the polyol is 2.0% by mass or more and 13.5% by mass or less.

[9] Preferably, the method for producing polyurethane according to the above [7] or [8], wherein the (B) is a polylactone.

[10] Preferably, the method for producing polyurethane according to any one of the above [7] to [9], wherein the polyester polyol is formed from (A) and (B) ( B) Block copolymers of type (A) (B).

[11] Preferably, the method for producing polyurethane according to the above [7] or [8], wherein the (B) is a dicarboxylic acid.

[12] Preferably, the method for producing polyurethane according to the above [11], wherein the dicarboxylic acid has 2 or more carbon atoms and 15 or less carbon atoms.

[13] Preferably, the method for producing polyurethane according to the above [10] or [11], wherein the polyester polyol is (AB) _n A formed from the (A) and the (B) Type block copolymer (where n is an integer of 1 or more).

[14] A polyurethane produced by the method for producing polyurethane according to any one of [1] to [13].

[15] A polyurethane characterized by comprising (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender , the proportion by weight of (b) polyether polyol in the polyurethane is 54% by weight to 99% by weight.

[16] A polyurethane molded article comprising the polyurethane described in [14] or [15].

[17] A polyurethane molded article comprising (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) The chain extender is composed of polyurethane, and the atomic composition (oxygen atom/carbon atom) of the surface of the polyurethane molded article is 0.22 or less.

[18] Preferably, the polyurethane molded article according to the above [17], wherein the surface of the polyurethane molded article has a water contact angle of 80 degrees or more.

[19] A film comprising the polyurethane described in [14] or [15].

[20] A fiber comprising the polyurethane described in [14] or [15].

[21] A polyester polyol, characterized in that it is formed from (A) a polyhydroxy hydrocarbon polymer and (B) an ester group-containing compound or a carboxyl group-containing compound, and the (A) and the (B) form at least one ester bond, and the oxygen content in the polyester polyol is 2.0% by mass or more, 13.5% by mass or less.

[22] Preferably, the polyester polyol according to the above [21], wherein the (B) is a polylactone.

[23] Preferably, the polyester polyol described in [21] or [22] above is characterized in that the polyester polyol is (B) (A) formed from (A) and (B) ) Block copolymers of type (B).

[24] Preferably, the polyester polyol according to the above [21], wherein the (B) is a dicarboxylic acid.

[25] Preferably, the polyester polyol according to the above [24], wherein the dicarboxylic acid has 2 or more carbon atoms and 15 or less carbon atoms.

[26] Preferably, the polyester polyol according to the above [24] or [25], wherein the polyester polyol is (AB) _n A formed from the (A) and the (B) Type block copolymer (where n is an integer of 1 or more).

[27] Preferably, the polyester polyol according to any one of the above [21] to [26], wherein the number average molecular weight of the polyester polyol is 500 or more, 5000 or less.

[28] Preferably, the polyester polyol according to any one of the above [21] to [27], wherein the (A) polyhydroxy hydrocarbon polymer is a hydrogenated polydiene polyol.

[29] A polymer in which at least one of the hydroxyl groups constituting the polyester polyol according to any one of [21] to [28] forms a urethane bond.

Invention effect

According to the present invention, polyurethane can be produced while maintaining a constant compatibility with polyether polyol, and the adhesiveness of the obtained polyurethane can be reduced. In addition, when the obtained polyurethane is molded, the releasability between molded objects can be improved. In addition, when the elastic fiber made of polyurethane is used to form clothing, etc., cost reduction can be achieved by reducing the amount of oil or smoothing agent used, and stable operation can be achieved by reducing the frequency of product staining and clogging of machinery or equipment. Improvement of performance and reduction of frictional force can be expected to reduce driving power and the like.

Detailed ways

The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents. The specific content will be described below.

<Polyurethane>

The polyurethane of the present invention can be obtained by combining the (a) polyhydroxyl hydrocarbon polymer having at least one hydroxyl group at the molecular end of the present invention with (b) polyether polyol, (c) polyisocyanate compound and (d) chain extender. Use to get.

The polyurethane in the present invention contains (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender. In addition, the weight ratio of (b) polyether polyol in polyurethane is not particularly limited, but is usually 54 to 99% by weight, preferably 60 to 90% by weight, more preferably 70 to 85% by weight. The larger the ratio, the more the flexibility of the polyurethane obtained tends to be improved, while the smaller the ratio, the more the peelability of the polyurethane obtained tends to be improved.

The polyurethane of the present invention contains at least one of (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular end or (b) a polymer that forms a urethane bond of the hydroxyl group of a polyether polyol of the present invention. . Preferably, a polymer having the following partial structure, that is, a polymer having the following structure in the polymer chain, constitutes (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular end of the present invention or (b ) Two or more hydroxyl groups of the polyether polyol form a urethane bond.

[chemical 1]

(In the formula (I), HO-X-OH represents (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at a molecular end or (b) a polyether polyol of the present invention.)

The content or position of the polymer in the polyurethane of the present invention is not particularly limited as long as it is a polymer having the above-mentioned structure in the polymer chain. Compounds having the above structure include, for example, polyurethane resins, polyurethane urea resins, prepolymers thereof, and the like.

In addition, in the present invention, "urethane containing (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal, (b) polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender" It is a polymer compound having a urethane bond (-NHCOO-) in the repeating unit of the main chain, and the repeating constituent unit of the main chain is not only a compound derived from both (a) and (b), but may also be Polyurethane which is a polymer compound derived only from (a), polyurethane which is a polymer compound derived only from (b), and a mixture thereof. In addition, unreacted (a), (b), (c) or (d) may be mixed with the above polymer compound.

The term "urethane" in the present invention means polyurethane or polyurethane urea unless otherwise specified, and it has been known that these two resins have substantially the same physical properties. On the other hand, as a difference in structural characteristics, 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.

Usually, each composition ratio is relative to polyurethane, and the total number of moles of (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal and (b) a hydroxyl group of a polyether polyol is set to A, and (c) polyol When the number of moles of the isocyanate group of the isocyanate compound is set to B, and the number of moles of active hydrogen substituents (hydroxyl and amino groups) of the (d) chain extender is set to C, A:B is usually 1:10 to 1: The range of 1, preferably 1:5~1:1.05, more preferably 1:3~1:1.1, more preferably 1:2.5~1:1.2, especially preferably 1:2~1:1.2, and (B-A):C 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 1:1.1 .

<(a) Polyhydroxyl hydrocarbon-based polymer having at least one hydroxyl group at a molecular terminal>

In the present invention, the polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular end refers to a hydrocarbon skeleton such as a representative butadiene, isoprene, chloroprene, and other conjugated dienes. unit polymer or the polyester polyol described later. By mixing them with polyether polyols and using them to produce polyurethane, the adhesiveness of the obtained polyurethane, the release property of the polyurethane molded article, and the unwinding property at the time of spinning can be improved.

The polymer having a hydrocarbon skeleton as a repeating unit is preferably exemplified by polymers obtained, for example, by radically polymerizing 1,3-butadiene with hydrogen peroxide as a polymerization initiator to directly produce a copolymer having a hydroxyl group at the end. Conjugated diene-based polymers, or use an anionic polymerization catalyst to produce a living polymer whose terminal is bonded to an alkali metal, and then react a monoepoxide or formaldehyde to produce a conjugated diene-based polymer having a hydroxyl group at the terminal, A polymer obtained by hydrogenating the obtained conjugated diene polymer according to a conventional method. In this case, the above-mentioned conjugated diene may be copolymerized with vinyl monomers such as styrene, acrylonitrile, methyl (meth)acrylate, and vinyl acetate in an amount of 30% by weight or less.

In addition, for example, the polymers of isobutene or isobutene and isoprene, 1,3-pentadiene and other conjugated dienes are oxidatively decomposed with ozone, etc., followed by reduction treatment with lithium aluminum hydride, etc., to obtain Isobutylene-based polymers obtained by hydrogenating the obtained polymers by conventional methods, and similarly oxidatively decomposing copolymers of α-olefins such as ethylene and propylene and diene-based compounds, performing reduction treatment, and hydrogenating polymer etc.

Among the polyhydroxy hydrocarbon-based polymers having at least one hydroxyl group at the molecular end of the present invention, preferably, the main skeleton is a polyhydroxy hydrocarbon-based polymer of hydrogenated polybutadiene, hydrogenated polyisoprene, and polyisobutylene, because it is easy to obtain Or in consideration of operation, it is more preferable that the main skeleton is a polymer of hydrogenated polybutadiene.

The ratio of the polyhydroxyl hydrocarbon-based polymer having at least one hydroxyl group at the molecular end used in the present invention is preferably 0.01 wt. % or more than 0.01% by weight. More preferably 0.03% by weight or more, further preferably 0.05% by weight or more, particularly preferably 0.07% by weight or more, most preferably 0.1% by weight. The larger this numerical value is, the more the adhesiveness of the obtained polyurethane resin tends to decrease. On the other hand, the upper limit is preferably 50.00% by weight or less. More preferably 30.00 wt% or less, further preferably 25.00 wt% or less, particularly preferably 15.00 wt% or less, most preferably 10.00 wt% or less. The smaller the value, the lower the adhesiveness of the obtained polyurethane resin, but the elastic properties and stretch recovery tend to be improved.

The number average molecular weight of the polyhydroxy hydrocarbon polymer is 500-5000, preferably 700-4000, more preferably 900-3500, 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 tends to become too high, resulting in deterioration of workability or productivity, or deterioration of the physical properties of the resulting polyurethane polymer at low temperatures . If it is too low, the obtained urethane polymer tends to be hard and cannot obtain sufficient flexibility, or elastic properties such as strength and elongation are insufficient, or excessive residual deformation is left when stretching and recovery are repeated. . In addition, polyester polyol refers to a substance having at least 2 or more ester bonds and 2 or more hydroxyl groups in the molecule, and preferably both ends of the main chain of polyester polyol are hydroxyl groups.

The polyester polyol of the present invention is a polyester polyol formed from (A) a polyhydroxy hydrocarbon polymer and (B) an ester-group-containing compound or a carboxyl-containing compound described later, specifically (A) a polyhydroxy hydrocarbon polymer A polymer that forms at least one ester bond with (B) an ester group-containing compound or a carboxyl 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, one molecule (A) of polyhydroxyl hydrocarbon polymer may form a plurality of ester bonds at the end of the molecule, or a plurality of polyhydroxyl hydrocarbon polymers (A) may form ester bonds, and the ester bond contained in the polyester polyol molecule The total number of 2 or more.

Hereinafter, the requirements constituting the polyester polyol of the present invention will be described separately.

<(A) Polyhydroxyl Hydrocarbon Polymer>

The (A) polyhydroxy hydrocarbon polymer in the present invention refers to a polymer having a hydrocarbon skeleton as a repeating unit, and a polymer having at least two hydroxyl groups in the above-mentioned polymer.

There is no particular limitation on the polymer having the above-mentioned hydrocarbon skeleton as a repeating unit, and it may be a polymer having a hydrocarbon as a substituent with an element other than carbon and hydrogen, such as chlorine, fluorine, bromine, etc., as a repeating unit, but preferably A polymer comprising carbon and hydrogen as a repeating unit of hydrocarbon (hereinafter, may be referred to as a hydrocarbon polymer), more preferably an aliphatic hydrocarbon polymer.

The hydrocarbon polymer in the present invention includes, for example, 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.

Since the melting point of the hydrocarbon polymer is lowered and handling becomes easier when the content of the hydrocarbon having a side chain in the molecule is large, a hydrocarbon polymer having a large content of the hydrocarbon having a side chain is preferable.

The above-mentioned hydrocarbon polymer may be a self-polymer in which one repeating unit is polymerized, or a copolymer containing two or more repeating units.

The number of carbon atoms in the repeating unit of the above-mentioned hydrocarbon is not particularly limited, but is usually 2 or more, preferably 3 or more, usually 9 or less, preferably 6 or less.

Considering that it is easy to introduce functional groups into the end of the polymer and to easily control the molecular weight, the polyhydroxy hydrocarbon polymer in the present invention preferably contains polymers of conjugated dienes such as butadiene, isobutylene, isoprene, and chloroprene. , and more preferably hydrogenated polybutadiene, hydrogenated polyisoprene, and hydrogenated polyisobutylene, etc., which are obtained by polymerizing conjugated dienes alone and then hydrogenated (hereinafter, hydrogenated polydiene), are easy to obtain From the viewpoint of properties and ease of handling, hydrogenated polybutadiene is more preferred.

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

By forming at least one ester bond in the polyhydroxy hydrocarbon polymer (A) constituting the polyester polyol of the present invention, the hydrophobicity of the polyester polyol can be adjusted, and the compatibility with the polyether polyol can be obtained higher than that of the saturated hydrocarbon polymer. of polyester polyols. In addition, polyurethane obtained using such a polyester polyol exhibits high releasability.

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, usually 5000 or less, preferably 4000 or less, more preferably At or below 3000. If it is less than the above-mentioned lower limit, there is a tendency that the obtained polyurethane polymer becomes hard, resulting in a decrease in flexibility, or a decrease in elastic properties such as strength and elongation, or when repeated stretching and recovery, there is a tendency to leave excessive stretch. residual deformation. When the above upper limit is exceeded, the viscosity of the polyether polyol, the prepolymer, or the prepolymer solution tends to become too high, resulting in decreased workability and productivity, or decreased physical properties of the resulting polyurethane polymer at low temperatures.

The properties of the polyhydroxy hydrocarbon polymer in the present invention are not particularly limited, but usually, it is liquid or waxy at normal 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 generally includes compounds in which repeating units are polymerized through ester bonds, preferably polylactones obtained by ring-opening polymerization of lactones.

<Polylactone>

The polylactone in the present invention can be obtained by performing a known polymerization reaction using a lactone as a raw material.

Specific examples of lactones used include ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propane Lactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, enantholactone, etc., can be used alone or in combination of two or more. Among these, ε-caprolactone, δ-valerolactone, and γ-valerolactone are preferable, and ε-caprolactone is more preferable from the viewpoint of easy availability and high reactivity.

Hereinafter, a polyester polyol composed of a polyhydroxy hydrocarbon polymer and a polylactone will be described as an example of a polyester polyol composed of a polyhydroxy hydrocarbon polymer and an ester group-containing compound.

<Polyester polyol formed from polyhydric hydrocarbon polymer and polylactone>

In the polyester polyol of the present invention, one of the preferred modes is that one or more ester groups are formed between the above-mentioned polyhydroxy hydrocarbon polymer and the following polylactone, and it is preferable that one molecule of the polyhydroxy hydrocarbon polymer has At least one of the hydroxyl groups in the polylactone forms an ester bond between it and the polylactone, and there are multiple ester bonds in one molecule in total; more preferably, at least one of the terminal hydroxyl groups in one molecule of the polyhydroxy hydrocarbon polymer has an ester bond between it and the polylactone. An ester bond is formed with polylactone, and there are multiple ester bonds in one molecule in total.

There is no particular limitation on the copolymerization form of the above-mentioned polyhydroxy hydrocarbon polymer and polylactone, but it is preferably (B) (A) (B) type composed of (A) polyhydroxy hydrocarbon polymer part and (B) polylactone part Block copolymers of polyester polyols. (B) is a ring-opening polymer of lactone, 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 become desired values.

By adjusting the degree of polymerization of (A) or (B) according to desired physical properties of the polyurethane resin, the molecular weight or oxygen content of the polyester polyol to be produced can be easily changed. The production method is not particularly limited, and it can be obtained by reacting a polyhydroxy hydrocarbon polymer and a lactone at a predetermined ratio in the presence of a catalyst such as tetraisopropyl titanate or tetrabutyl titanate in the absence of a solvent.

<(B) Carboxyl group-containing compound>

The carboxyl group-containing compound used in the present invention is not particularly limited as long as it has a carboxyl group. Generally, examples include monocarboxylic acid compounds, dicarboxylic acid compounds, substituted carboxylic acid compounds such as hydroxy acids or alkoxy acids, and dicarboxylic acid compounds are preferred. Acid compounds.

<Dicarboxylic acid>

The dicarboxylic acid compound used in the present invention can be any of aliphatic dicarboxylic acid and aromatic dicarboxylic acid, and the carbon number of aliphatic dicarboxylic acid is usually 2 or more, preferably 3 or more , more preferably 4 or more, usually 16 or less, preferably 15 or less, more preferably 14 or less. Specific examples include malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9- Nonanedicarboxylic acid (1,9-nonamethylenedicarboxylic acid), 1,10-decylenedicarboxylic acid, 1,11-undecylenedicarboxylic acid, 1,12-dodecenedicarboxylic acid, and the like. In addition, the aromatic dicarboxylic acid specifically includes phthalic acid, isophthalic acid, terephthalic acid, naphthalenedioic acid, anthracenedioic acid, or phenanthrenedioic acid. These may be used alone or as a mixture of two or more. In addition, acid anhydrides, alkyl esters, or halogen-substituted products of unsaturated bonds of these dicarboxylic acids can also be used. Among them, from the viewpoint of easy access and high thermal stability, aliphatic dicarboxylic acids are preferred, more preferably malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and more preferably Succinic acid, adipic acid.

Hereinafter, a polyester polyol composed of a polyhydroxy hydrocarbon polymer and a dicarboxylic acid will be described as an example of a polyester polyol composed of a polyhydroxy hydrocarbon polymer and a carboxyl group-containing compound.

<Polyester polyol formed from polyhydroxy hydrocarbon polymer and dicarboxylic acid>

In the present invention, the polyester polyol formed from a polyhydroxy hydrocarbon polymer and a dicarboxylic acid is usually divided between at least one hydroxyl group contained in 2 molecules of the polyhydroxy hydrocarbon polymer and 2 carboxyl groups contained in 1 molecule of dicarboxylic acid. Polyester polyols that form ester bonds.

Preference is given to polyester polyols of the (AB) _nA type formed from a polyhydroxy hydrocarbon polymer (A) and a dicarboxylic acid (B). (A) and (B) may be bonded via an ester bond, and may be produced from a carboxylic acid derivative such as a carboxylic acid diester.

Usually, n is an integer of 1 or more, and more preferably corresponds to an ABA-type polyester polyol in which both ends of a dicarboxylic acid are bonded to one molecule of a polyhydroxy hydrocarbon polymer when n=1.

Generally, the molecular weight of polyhydroxyl hydrocarbon polymers that can be obtained is relatively large, at least 1500 or above. If the two ends of dicarboxylic acid react with polyhydroxyl hydrocarbon polymers to form polyester polyols, the molecular weight is 3000 or above. This is because when the n value becomes large, if the molecular weight of the polyester polyol becomes too large, the viscosity of the prepolymer or the prepolymer solution tends to be too high, and the workability or productivity at the time of producing polyurethane tends to decrease. Alternatively, the physical properties of the obtained polyurethane polymer are lowered at low temperatures.

The polyester polyol of the present invention may have a structure other than the above-mentioned structure in the molecule, but is preferably a polyester polyol that does not contain structures other than the above-mentioned parts.

In addition, the constituents (A) and (B) used to form ester bonds are described in detail in the above description, but the polyester polyol of the present invention is not limited thereto, as long as the obtained molecular structure is the same, it can be obtained by any raw material , The substance obtained by the reaction method.

<Oxygen content>

The oxygen content in the polyester polyol of the present invention refers to the oxygen content in 1 molecule of polyester polyol, and generally refers to the ratio of oxygen atoms contained in a molecule to the molecular weight of 1 molecule of polyester polyol. For example, when there are 10 oxygen atoms in a polyester polyol with a molecular weight of 2000, it is (10×16/2000)×100=8.0% by mass.

The oxygen content of the polyester polyol of the present invention is in the range 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 2.5% by mass Above, more preferably 3.0% by mass or more, preferably 13% by mass or less, more preferably 12% by mass or less, even more preferably 11.0% by mass. When it is less than the above-mentioned lower limit, the compatibility with polyether polyol or the solubility in a solvent is insufficient, and when it exceeds the above-mentioned upper limit, the adhesiveness of the obtained polyurethane-based 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, and generally, the mass ratio is 10.0% by mass or more, preferably 20.0% by mass or more, more preferably 30.0% by mass or more 30.0% by mass or more, more preferably 40.0% by mass or more, particularly preferably 45.0% by mass. The greater the mass ratio of the polyhydroxy hydrocarbon polymer in the polyester polyol of the present invention, the more the adhesiveness of the obtained polyurethane tends to decrease. On the other hand, the upper limit is not particularly limited, and is 99.5% by mass or less, preferably 99.0% by mass or less, more preferably 98.5% by mass or less, still more preferably 98.2% by mass or less or less, particularly preferably 98.0% by mass or less. The smaller the above-mentioned mass ratio, the more the compatibility with polyether polyol or the solubility in polar solvents tends to be improved.

<Physical properties of polyester polyol>

The number average molecular weight of the polyester polyol of this invention can be adjusted by the kind or quantity of (A) or (B) used. The number average molecular weight is usually 500 or more, preferably 600 or more, more preferably 800 or more, usually 10000 or less, preferably 7000 or less, more preferably 5000 or less. The number average molecular weight represents the average molecular weight per molecule. When the number-average molecular weight exceeds the above-mentioned upper limit, the viscosity of the prepolymer or the prepolymer solution tends to become too high, resulting in a decrease in workability or productivity, or a decrease in the physical properties of the obtained polyurethane polymer at low temperatures. If it is less than the above-mentioned lower limit, there is a tendency that the obtained polyurethane polymer may become hard and cannot obtain sufficient flexibility, or elastic properties such as strength and elongation may be insufficient, and excessive stretching and recovery may be left behind when stretching and recovery are repeated. residual deformation.

<(b) Polyether polyol>

The polyether polyol in the present invention is a hydroxyl compound having at least one or more ether bonds in the main skeleton in the molecule, and the repeating unit in the main skeleton can be any one of saturated hydrocarbon or unsaturated hydrocarbon, for example, 1,4-butanediol unit, 2-methyl-1,4-butanediol unit, 3-methyl-1,4-butanediol unit, 1,3-propanediol unit, 1,2-propanediol unit , 2-methyl-1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 3-methyl-1,5-pentanediol unit, 1,2-ethanediol unit , 1,6-hexanediol unit, 1,7-heptanediol unit, 1,8-octanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit, 1,4- Cyclohexanedimethanol units, etc.

Among them, among the polyol units constituting the polyether polyol, polytetramethylene ether glycol or polytrimethylene ether glycol, 1 to 20 mole % of 3-methyltetrahydrofuran and tetrahydrofuran are preferred. (For example, "PTG-L1000", "PTG-L2000", "PTG-L3500" manufactured by Hodoga Chemical Co., Ltd.), or copolyether diols of neopentyl glycol and tetrahydrofuran, etc.

<(c) Polyisocyanate compound>

The polyisocyanate compound used in the present invention is exemplified, for example, 2,4- or 2,6-benzylidene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), Aromatic diisocyanates such as 2,4'-MDI, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, benzylidine diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate Aliphatic diisocyanate having an aromatic ring, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene Aliphatic diisocyanates such as methyl diisocyanate and 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, methyl cyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3- Cycloaliphatics such as isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4′-dicyclohexylmethane diisocyanate, isopropylidene biscyclohexyl-4,4′-diisocyanate, etc. diisocyanates, etc. These may be used alone or in combination of two or more.

In the present invention, highly reactive aromatic polyisocyanates are particularly preferred, and benzallidene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferred. In addition, a part of the NCO group of polyisocyanate may be replaced by urethane, urea, biuret, allophanate, carbodiimide, oxazolidinone, amide, imine, etc., and further Accordingly, isomers other than the above are also contained in the polynuclear body.

The amount of these polyisocyanate compounds used is based on the total of (a) the polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular end, (b) the hydroxyl group of the polyether polyol, and the total of the hydroxyl group and amino group of the chain extender1 The equivalent is usually 0.1 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 0.9 to 1.5 equivalents, further preferably 0.95 to 1.2 equivalents, and most preferably 0.98 to 1.1 equivalents.

If the amount of polyisocyanate used is too large, the unreacted isocyanate group reacts undesirably, and it tends to be difficult to obtain the desired physical properties. If it is too small, the molecular weight of polyurethane and polyurethane urea will not be sufficiently large, and the desired performance will be obtained. Tendency not to manifest.

<(d) Chain extender>

The chain extenders referred to in the present invention are mainly classified into compounds having 2 or more hydroxyl groups, compounds having 2 or more amino groups, and water. Among them, short-chain polyols are preferred for polyurethane applications, specifically compounds with 2 or more hydroxyl groups, and polyamine compounds are preferred for polyurethane urea applications, specifically compounds with 2 or more amino groups. Among them, in order to stably advance the reaction, it is preferable to reduce water as much as possible.

In addition, when the polyurethane resin of the present invention uses a compound having a molecular weight (number average molecular weight) of 500 or less as a chain extender, the rubber elasticity of the polyurethane elastomer can be improved, so it is more preferable in terms of physical properties.

Compounds having two or more hydroxyl groups include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, and 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 Alcohol, 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-octanediol, 1, Aliphatic diols such as 9-nonanediol, alicyclic diols such as bishydroxymethylcyclohexane, diols having an aromatic ring such as benzenedimethanol and bishydroxyethoxybenzene, and the like.

Compounds having two or more amino groups include, for example, aromatic compounds such as 2,4- or 2,6-toluenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, etc. Diamine, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propylenediamine, 2-methyl-1,5-pentanediamine Amine, 1,3-diaminopentane, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1 , 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine and other aliphatic diamines, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane Alkane (IPDA), 4,4'-bicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bis Alicyclic diamines such as aminomethylcyclohexane and the like. These chain extenders may be used alone or in combination of two or more. Among them, ethylenediamine, propylenediamine, 1,3-diaminopentane, and 2-methyl-1,5-pentanediamine are preferable in the present invention, and among them, ethylenediamine and propylenediamine are more preferable.

The amount of these chain extenders used is not particularly limited, and when the equivalent obtained by subtracting the equivalent of the polyisocyanate compound from the total hydroxyl equivalent of (a) and (b) is regarded as 1, it is usually 0.1 equivalent or more , 5.0 equivalents or less. It is preferably 0.8 equivalent or more, 2.0 equivalent or less, more preferably 0.9 equivalent or more, 1.5 equivalent or less. If the amount used is too large, the obtained polyurethane and polyurethane urea tend to be too hard, and the desired characteristics cannot be obtained, or it is difficult to dissolve in a solvent, and processing becomes difficult. If it is too small, the resulting polyurethane and urea tend to be too soft, Sufficient strength, elastic recovery performance, or elastic retention performance cannot be obtained, or high-temperature characteristics deteriorate.

When the polyurethane and polyurethane urea targeted by the present invention are used for high-performance polyurethane elastomers such as polyurethane elastic fiber and synthetic leather, the following combinations of raw materials are exemplified.

In addition, for the purpose of controlling the molecular weight of polyurethane, a chain terminator having one active hydrogen group may be used as needed. Examples of these chain terminators include aliphatic monoalcohols such as ethanol, propanol, butanol, and hexanol having a hydroxyl group, and aliphatic monoalcohols such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, and diethanolamine having an amino group. monoamine. 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 needed. Examples of these additives include "CYANOX 1790" (manufactured by CYANAMID), "IRGANOX 245", "IRGANOX 1010" (manufactured by Chiba Specialty Chemical Corporation), "Sumilizer GA-80" (manufactured by Sumitomo Chemical Corporation) or 2,6-Di Antioxidants such as butyl-4-methylphenol (BHT), "TINUVIN622LD", "TINUVIN765" (manufactured by Ciba Specialty Chemikaruzu Co., Ltd. above), "SANOLLS-2626", "SANOLLS-765" (above, Sankyo Co., Ltd.), light stabilizers such as “TINUVIN328” and “TINUVIN234” (manufactured by Chiba Specialty Chemical Chemicals Co., Ltd.), etc., silicon compounds such as dimethylsiloxane polyoxyalkylene copolymers , red phosphorus, organic phosphorus compounds, organic compounds containing phosphorus and halogens, organic compounds containing bromine or chlorine, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc., and reactive flame retardants, pigments and dyes such as titanium dioxide , colorants such as carbon black, hydrolysis inhibitors such as carbodiimide compounds, fillers such as glass fiber, carbon fiber, alumina, talc, graphite, melamine, gypsum powder, lubricants, oils, surface Active agents, other inorganic additives, organic solvents, etc.

<Manufacturing method of polyurethane>

Hereinafter, the method for producing the polyester polyol and polyurethane of the present invention will be described in detail.

<Manufacturing method of polyester polyol>

The polyester polyols of the present invention are produced using polyhydroxyl hydrocarbon polymers. The polyhydroxy hydrocarbon polymer itself is a known compound and can be produced by a generally used method. In addition, these commercially available compounds can also be used. Representative examples include polymers obtained by subjecting conjugated dienes such as butadiene, isoprene, and chloroprene, preferably 1,3-butadiene, to hydrogen peroxide as a polymerization initiator. Carry out free radical polymerization, thereby directly make the conjugated diene polymer that has hydroxyl group at the end, or use anionic polymerization catalyst, make the living polymer that the end is bonded with alkali metal, then by reacting monoepoxide or formaldehyde, etc., A conjugated diene polymer having a hydroxyl group at the terminal is produced, and the obtained conjugated diene polymer is hydrogenated according to a conventional method. In addition, at this time, the above-mentioned conjugated diene may be copolymerized with vinyl monomers such as styrene, acrylonitrile, methyl (meth)acrylate, and vinyl acetate in an amount of 30% by mass or less.

In addition, for example, a polymer of isobutylene or a polymer of isobutene and isoprene, 1,3-pentadiene, or the like is oxidatively decomposed by ozone or the like, followed by reduction treatment with lithium aluminum hydride or the like to obtain Isobutylene-based polymers having a hydroxyl group at the end are obtained by hydrogenating the polymer obtained by a conventional method, and a copolymer of an α-olefin such as ethylene and propylene and a diene-based compound is similarly oxidatively decomposed and subjected to a reduction treatment. Polymers after hydrogenation, etc.

The manufacture of the polyester polyol of the present invention can adopt the conventionally known esterification technology. For example, there are methods of reacting a polyhydric alcohol with a lactone or dicarboxylic acid under normal pressure, esterifying under reduced pressure, esterifying in the presence of an inert solvent such as toluene, and then allowing condensed water or A method of azeotropically removing the condensed alcohol and the solvent, taking it out of the reaction system, etc.

The reaction temperature of esterification is the range of 100-250 degreeC normally. Preferably it is 120-240 degreeC, More preferably, it is 140-230 degreeC, Especially preferably, it is the range of 150-220 degreeC. If the reaction temperature is too low, the esterification reaction will not proceed sufficiently, and if it is too high, the coloring of the product may increase.

The reaction is preferably performed under an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and can be carried out under normal pressure or reduced pressure according to the purpose. In the reaction of a polyhydric alcohol with a dicarboxylic acid or a dicarboxylic acid ester, since water or alcohol is produced during the reaction, an inert gas may be circulated in the reaction system in order to promote their detachment from the reaction system.

<catalyst>

The form of the esterification reaction is not particularly limited, and the esterification reaction can also be carried out in a system where there is no catalyst. Generally, in order to make the esterification reaction proceed smoothly, it can be used for esterification and transesterification. All catalysts, such as inorganic or organic acids; Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Chlorides, oxides, hydroxides, or fatty acid salts of metals such as Sn, Sb, or Pb, such as acetic acid, oxalic acid, caprylic acid, lauric acid, or naphthenic acid; sodium methoxide, sodium ethoxide, aluminum triisopropoxide, titanic acid Alcohols such as isopropyl ester or n-butyl titanate; phenols such as sodium phenate; or other organometallic compounds of metals such as Al, Ti, Zn, Sn, Zr, or Pb, and the like. Considering that it is easy to obtain, has low toxicity, and is widely used in esterification reactions, titanium-based catalysts such as isopropyl titanate or n-butyl titanate are most preferred. The amount of the catalyst used at this time is preferably 0.00001-5.0% by mass, more preferably 0.0001-2.0% by mass, and most preferably 0.001-1.0% by mass relative to the total amount of raw materials used to prepare the polyester diol. If the amount is too small, it will take an extremely long time to form the polyester polyol, and the product will be easily colored. On the other hand, when the amount of the catalyst used is too large, there is a possibility that an excessive reaction acceleration effect on the urethane reaction may be exhibited.

The esterification reaction is preferably performed under an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and can be carried out under normal pressure or reduced pressure according to the purpose. In the reaction of a polyhydric alcohol with a dicarboxylic acid or a dicarboxylic acid ester, since water or alcohol is produced during the reaction, an inert gas may be circulated in the reaction system in order to promote their detachment from the reaction system.

The esterification reaction time varies according to the amount of catalyst used, the reaction temperature, the substrate of the reaction, the desired physical properties of the resulting polyester polyol, etc., the lower limit is usually 0.5 hours, preferably 1 hour, and the upper limit is usually 30 hours, preferably 20 hours.

When a catalyst is used for the esterification reaction, the (titanium-based) catalyst used for the reaction remains in the obtained polyester polyol product. Since the removal of the above-mentioned catalysts is usually accompanied by a complicated process, the resulting polyester polyol generally does not separate the (titanium-based) catalyst, and most of them are directly used in the manufacture of polyurethane.

However, when the content of the catalyst is large or depending on the use of polyurethane, it is preferable to deactivate the titanium catalyst in the polyester polyol. Examples of deactivation methods for titanium-based catalysts in polyester polyols include (1) contacting polyester polyols with water under heating; Phosphorus compounds such as polyester polyols are treated, etc. In addition, when the method (1) of contacting with water is used, for example, 1% by mass or more of water is added to the polyester polyol, and at a temperature of 70 to 150°C, preferably 90 to 130°C, , heating for about 1 to 3 hours. At this time, the deactivation treatment by heating can be carried out under normal pressure or under increased pressure. If the system is decompressed after the deactivation treatment, the water used for deactivation can be smoothly removed from the polyester multi-component Alcohol removed.

<Manufacturing method of polyurethane>

In the present invention, when producing polyurethane, (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at a molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) are used as main raw materials for production. chain extender.

When producing the above-mentioned polyurethane, it is generally possible to produce the polyurethane under the condition that a solvent coexists. In the present invention, it is preferable to produce polyurethane in the coexistence of an aprotic polar solvent.

In addition, the usage-amount of each compound is not specifically limited, What is necessary is just to use the amount described above. An example of the production method in the coexistence of an aprotic polar solvent will be shown below, but there are no particular limitations as long as it is in the coexistence of an aprotic polar solvent.

The aprotic polar solvent in the present invention is not particularly limited, and from the viewpoint of solubility, it is preferable to use an aprotic polar solvent selected from amide-based solvents, N-methylpyrrolidone, N-ethylpyrrolidone, and diethylpyrrolidone. Methyl sulfoxide solvent. Specific examples of amide solvents are N,N-dimethylacetamide, N,N-dimethylformamide and mixtures of two or more thereof, particularly preferably dimethylformamide or dimethylacetamide. amides.

As an example of the production method, there is a method of reacting (a), (b), (c) and (d) together (one-step method), or first mixing (a) and (b), and making the mixture with (c ) reaction to prepare a prepolymer having isocyanate groups at both ends, and then, reacting the prepolymer with (d) (two-step method), reacting (b) with (c), and mixing with (a) , the method of reacting with (d), and the method of mixing with (a) after reacting (b) (c) (d). Among them, the two-step method is a process of preparing an intermediate blocked with isocyanate at both ends corresponding to a soft segment of polyurethane by reacting polyether polyol with 1 equivalent or more of polyisocyanate in advance. By preparing a prepolymer once and then reacting it with a chain extender, the molecular weight of the soft segment can be easily adjusted, the phase separation between the soft segment and the hard segment can be easily achieved, and the performance as an elastomer can be easily exhibited. feature. In particular, when the chain extender is a diamine, the reaction rate with the isocyanate group is significantly different from that of the hydroxyl group of the polyether polyol, so it is more preferable to implement polyurethane urea by the two-step method (prepolymer method).

<one-step method>

The one-step method is also called one-shot foaming (one-shot), and is a method of reacting by putting (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, and the temperature varies depending on the amount of solvent, reactivity of raw materials used, reaction equipment, and the like. If the temperature is too low, the progress of the reaction will be too slow, or the productivity will deteriorate due to the low solubility of the raw material or the polymer, and if the temperature is too high, side reactions or decomposition of the polyurethane resin will occur, which is not preferable. The reaction can be performed under reduced pressure while defoaming (defoaming). In addition, a catalyst, a stabilizer, etc. may be added to a reaction as needed. Catalysts include, for example, triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, etc., and stabilizers include, for example, 2,6-dibutyl-4- methylphenol, bis(octadecanoyl)thiodipropionate, di-β-naphthylphenylenediamine, tris(dinonylphenyl)phosphide, etc.

<two-step method>

The two-step method is also called the prepolymer method. Usually, it can also be reacted in two stages, that is, the polyisocyanate component and the polyol component are reacted at a reaction equivalent ratio of 1.0 to 10.00 to produce a prepolymer, and then , to which polyisocyanate components or active hydrogen compound components such as polyols and amine compounds are added. In particular, the method of reacting a polyisocyanate compound having an equivalent or more relative to the polyol component to prepare an NCO prepolymer at both ends, and then allowing a short-chain diol or diamine to act as a chain extender to obtain Polyurethane.

In the present invention, the two-step method can be carried out under the coexistence of solvents, but it is preferably carried out under the coexistence of aprotic solvents. Specific examples include amide solvents or N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide solvents and mixtures of two or more of them.

In the present invention, when producing polyurethane, an aprotic polar solvent is preferable among these solvents from the viewpoint of solubility. Further, among the aprotic polar solvents, amide solvents or N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl sulfoxide are preferred, and if specific examples of amide solvents are given, N, N-di Methylacetamide, N,N-dimethylformamide, particularly preferably N,N-dimethylformamide or N,N-dimethylacetamide.

When synthesizing the prepolymer, (1) it can be like this. First, the polyisocyanate compound and polyether polyol are directly reacted without using a solvent to synthesize the prepolymer, and it can be used directly; (2) the method of (1) can be used A prepolymer is synthesized and then dissolved in a solvent for use; (3) The solvent can be used to react polyisocyanate and polyether diol from the beginning. In the case of (1), in the present invention, it is important to make it react with the chain extender by dissolving the chain extender in the solvent, or introducing the prepolymer and the chain extender into the solvent at the same time to obtain Polyurethane in a form that coexists with a solvent.

The lower limit of the range of the reaction equivalent ratio of NCO/active hydrogen group (polyol) is usually 1, preferably 1.05, and the upper limit is usually 10, preferably 5, and more preferably 3. If this ratio is too small, the molecular weight of the obtained prepolymer becomes too large, and the amount of the hard segment described later becomes low, and sufficient stretchability tends not to be obtained. If it is too large, the hard segment described later The amount of segments becomes high, and sufficient flexibility tends not to be obtained.

The amount of the chain extender used is not particularly limited, but the lower limit of the range of the used amount is usually 0.1, preferably 0.8, and the upper limit is usually 5.0, preferably 2.0, based on the equivalent weight of the NCO groups contained in the prepolymer.

In addition, monofunctional organic amines or alcohols may coexist during the reaction.

In the chain extension reaction, each component is usually reacted at 0 to 250° C., and the temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, and the reaction equipment. If the temperature is too low, the progress of the reaction will be too slow, or the solubility of the raw material or the polymer will be low, so the productivity will be deteriorated. If the temperature is too high, side reactions will occur or the polyurethane resin will be decomposed, which is not preferable. The reaction can be carried out under reduced pressure while defoaming.

In addition, a catalyst, a stabilizer, etc. may be added to a reaction as needed. Catalysts include, for example, triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, etc., and stabilizers include, for example, 2,6-dibutyl-4- methylphenol, bis(octadecanoyl)thiodipropionate, di-β-naphthylphenylenediamine, tris(dinonylphenyl)phosphide, etc. However, when the chain extender is a highly reactive compound such as a short-chain aliphatic amine, it is preferably implemented without adding a catalyst.

<Physical properties of polyurethane>

The polyurethane obtained by the above-mentioned production method reacts in the presence of a solvent, so it is generally obtained in a state dissolved in a solution, but the physical property value is not limited to the state, and there are no particular restrictions on the solution state and the solid state.

The weight-average molecular weight of polyurethane varies depending on the application, and as a polyurethane polymerization solution, it is usually 10,000 to 1 million, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 100,000 to 300,000. As a molecular weight distribution, Mw/Mn=1.5-3.5, Preferably it is 1.7-3, More preferably, it is 1.8-3. As fibers, films, and moisture-permeable resin molded articles, the weight-average molecular weight of polyurethane is usually 10,000 to 1 million, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 to 400,000. As a molecular weight distribution, Mw/Mn=1.5-3.5, Preferably it is 1.7-3, More preferably, it is 1.8-3.

In addition, the polyurethane obtained by the above-mentioned production method preferably contains 1 to 20% by weight of the hard segment, more preferably 3 to 15% by weight, further preferably 4 to 12% by weight, and particularly preferably 5 to 10% by weight. When the amount of the hard segment is too large, the resulting polyurethane polymer tends not to exhibit sufficient flexibility or elastic properties, is difficult to dissolve when using a solvent, and processing becomes difficult. If the amount is too small, the urethane polymer tends to be too soft and difficult to process, or cannot obtain sufficient strength or elastic properties.

In addition, the so-called hard segment in the present invention is based on P.J. Flory, Journal of American Chemical Society, 58, 1877-1885 (1936), and the weight of the isocyanate and amine-bonding part relative to the total weight is calculated according to the following formula.

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

it's here,

R = number of moles of isocyanate/(number of moles of hydroxyl groups of polyether polyol + number of moles of hydroxyl groups of polyhydroxy hydrocarbon-based polymers having at least one hydroxyl group at the molecular end)

Mdi = number average molecular weight of diisocyanate

Mda = number average molecular weight of the chain extender

Mp=The average molecular weight of the number average molecular weight of polyether polyol and the number average molecular weight of polyhydroxyl hydrocarbon polymer having at least one hydroxyl group at the molecular end

The polyurethane solution obtained in the present invention has good storage stability, is not prone to gelation, has a small change in viscosity over time, and is easy to process into films, yarns, etc. because of its low thixotropy. 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, a large amount of solvent needs to be removed, and the productivity tends to decrease, and if it is too large, the viscosity of the solution becomes too high, and the operability and processability tend to be deteriorated.

The polyurethane solution is not particularly specified, but for long-term storage, it is preferably stored at normal temperature or lower under an inert gas atmosphere such as nitrogen or argon.

<Polyurethane molded article and its application>

After the polyurethane produced in the present invention and the urethane prepolymer solution are obtained, the polyurethane molded article 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 composed of the above-mentioned polyurethane or polyurethane obtained by the above-mentioned production method, and is usually characterized in that it is composed of (a) having at least one molecular terminal A polyurethane molded article composed of a polyhydroxy hydrocarbon-based polymer of hydroxyl group, (b) polyether polyol, (c) polyisocyanate compound, and (d) chain extender polyurethane, the atomic composition of the surface of the polyurethane molded article (oxygen atom / carbon atom) is 0.22 or less.

The atomic composition (oxygen atom/carbon atom) of the surface of the polyurethane molding is specifically indicated, for example, by ESCA (electron spectroscopy for chemical analysis, Electron Spectroscopy for Chemical Analysis) or XPS (X-ray photoelectron spectroscopy, X-ray Photoelectron Spectroscopy) On the surface of a molded body, the relative abundance ratio of oxygen atoms to carbon atoms.

The value of the atomic composition (oxygen atom/carbon atom) of the surface of the polyurethane molded article of the present invention is preferably 0.20 or less, more preferably 0.16 or less. The smaller this value is, the lower the adhesiveness of the obtained molded article tends to be, and the better the peelability tends to be. In addition, it is preferably 0.00 or more, and more preferably 0.05 or more. The larger this value is, the better the packing property when the formed bodies are stacked on each other tends to be improved. For example, when the formed bodies are yarns, the wound yarns are less likely to be unwound and lose their shape.

In addition, the polyurethane molded article of the present invention preferably has an atomic composition (oxygen atom/carbon atom) of the surface of 0.22 or less and a water contact angle of the surface of 80 degrees or more.

The water contact angle of the surface is measured by dropping several μL of water on the surface of the molded article, and measuring the internal angle between the tangent of the droplet and the surface of the molded article within 10 seconds. The value of the water contact angle of the surface of the polyurethane molded article of the present invention is 80 degrees or more, preferably 83 or more, more preferably 86 or more. The larger this value is, the lower the adhesiveness of the obtained molded article tends to be, and the better the peelability tends to be. In addition, it is preferably 180 degrees or less, more preferably 150 degrees or less. The smaller this value is, the better the packing property when the formed bodies are stacked on each other tends to be improved. For example, when the formed bodies are yarns, the wound yarns are less likely to be unwound and lose their shape.

In addition, the polyurethane, urethane prepolymer solution, and polyurethane molded article of the present invention can be used in various applications because they exhibit various properties. For example, it can be widely used in foams, elastomers, paints, fibers, adhesives, bed materials, sealing materials, medical materials, artificial leather, etc.

The polyurethane, polyurethane urea and the urethane prepolymer solution produced in the present invention can be used for casting polyurethane elastomers. Examples include rolls such as pressure extension rolls, papermaking rolls, office equipment, and pre-stretch rolls; Casters, etc.; as industrial products, there are conveyor belt rollers, guide rollers, pulleys, steel pipe linings, rubber screens for ores, gears, connecting rings, liners, pump impellers, cyclone separator cones, cyclone separator linings, etc. In addition, it is also suitable for belts of OA (office supplies) equipment, paper feed rollers, cleaning plates for copying, snow blowers, toothed belts, scooters (surfrolar), etc.

The polyurethanes produced according to the invention and their urethane prepolymer solutions are also suitable for use as thermoplastic elastomers. For example, it can be used as pipes or hoses, spiral pipes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical instruments, physical and chemical equipment, quantitative pumps, water treatment equipment, industrial robots, etc. used in the food and medical fields. In addition, it can be made into round belts, V-shaped belts, flat belts and other belts for various transmission mechanisms, textile equipment, packaging equipment, printing equipment, etc. In addition, equipment parts such as heels and soles of footwear, connectors, seals, beam-column joints, bushes, gears, and rollers, sporting goods, leisure goods, and watch bands can be exemplified. Moreover, as auto parts, oil brakes, gearboxes, partitions, chassis parts, interior accessories, tire chain substitutes, etc. In addition, films such as keyboard films and automotive films, wire wrap (カールコード), cable sheaths, corrugated tubes, conveyor belts, flexible containers, adhesives, synthetic leather, dipping products, adhesives wait.

The polyurethane and its urethane prepolymer solution produced by the present invention can also be applied to solvent-based two-component coatings, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sporting goods. In addition, as tar epoxy polyurethane, it can also be used for car repair.

The polyurethane produced by the present invention and its urethane prepolymer solution can also be used as moisture-curing one-component coatings, blocked isocyanate-based solvent coatings, alkyd resin coatings, polyurethane modified synthetic resin coatings, and ultraviolet-curable coatings. As a component of coatings, it can be used as: coatings for plastic buffers, peelable coatings, coating agents for tapes, floor tiles, floor materials, paper, wood grain printing films, etc. Overprint varnishes, wood varnishes, coil coatings for high processing coatings, optical fiber protective coatings, solder resists, overcoats for metal printing, primers for vapor deposition, white coatings for food cans, etc.

The polyurethane of the present invention and its urethane prepolymer solution, as bonding agent, can be applied to food packaging, footwear, footwear, tape adhesive, cosmetic paper, wood, structural member etc., in addition, also can use Used as a component of low-temperature adhesives and hotmelt adhesives.

The polyurethane produced by the present invention and its urethane prepolymer solution, as a binder, can be used for magnetic recording media, inks, castings, sintered bricks, transplant materials, microcapsules, granular fertilizers, granular pesticides, polymers Cement mortar, resin mortar, rubber sheet adhesive, recycled foam, glass fiber correction, etc.

The polyurethane produced by the present invention and its urethane prepolymer solution can be used as a component of a fiber processing agent for shrink-proof processing, wrinkle-proof processing, water-repellent processing, and the like.

The polyurethane, polyurethane urea and its urethane prepolymer solution produced by the present invention can be used as a sealant and/or caulking agent for concrete interior walls, induction joints, window frames, wall PC joints, ALC Joints, panel joints, sealants for laminated glass, sealants for heat-insulating windows, sealants for automobiles, etc.

The polyurethane and its urethane prepolymer solution produced by the present invention can be used as medical materials, as materials suitable for blood, can be used for tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc., in addition, as disposable The raw materials used can be used for catheters, tubes, bags, surgical gloves, artificial kidney potting materials, etc.

The polyurethane, polyurethane urea and its urethane prepolymer solution produced by the present invention can be used as a photosensitive resin composition for UV-curable coatings, electron beam-curable coatings, and flexographic printing plates after terminal modification. Raw materials for photocurable optical fiber coating material compositions, etc.

In particular, the polyurethane produced by the present invention is preferably used for films or fibers in terms of exhibiting the characteristics of elasticity and moisture permeability, and for these specific applications, it is preferably used for medical, hygienic materials, artificial leather, and elastic fibers for clothing.

As mentioned above, although the application example which used the polyurethane produced by this invention and its urethane prepolymer solution was described, this invention is not limited to these applications.

The production methods of films and fibers are described below, but the production methods are not particularly limited.

<Manufacturing method of thin film>

The method for producing the thin film is not particularly limited, and known methods can be used. For example, the production method of the film is exemplified by the wet film production method, in which a polyurethane resin solution is coated on a support or a release material, and soluble substances such as solvents are extracted in a coagulation bath; and the dry film production method, in which the polyurethane resin The solution is coated on a support or a release material, and the solvent is dried by heating or reducing pressure. There are no particular limitations on the support used for drying to form a film, and paper or cloth coated with a polyethylene or polypropylene film, glass, metal, release material, or the like can be used. The method of coating is not particularly limited, and any of known methods such as a knife coater, a roll coater, a spin coater, and a gravure coater may be used. The drying temperature can be set arbitrarily according to the capacity of the dryer, and a temperature range needs to be selected so that insufficient drying or severe desolventization will not occur. It is preferably in the range of room temperature to 300°C, more preferably 60°C to 200°C.

<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. If the thickness of the film is too thick, sufficient moisture permeability tends not to be obtained, and if it is too thin, pinholes are likely to be formed, or the film tends to stick and it is difficult to handle. In addition, the film can be preferably used for medical adhesive films, hygienic materials, packaging materials, decorative films, other moisture-permeable materials, and the like. In addition, the film can also be coated on 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, 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, still more preferably 30 MPa or more.

Elasticity obtained from the ratio of the stress at 150% elongation at the first shrinkage to the stress at 150% elongation at the first elongation in a 300% elongation-shrinkage repeated test at 23°C The retention rate (Hr1/H1) is usually 10% or more, preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more. Similarly, the elastic retention (Hr5/H5) obtained from 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 30% or more, preferably 50% or more, more preferably 70% or more, further preferably 85% or more.

In addition, in the 300% elongation-shrinkage repeated test at 23°C, it is obtained from the ratio of the stress at 150% elongation at the second elongation to the stress at 150% elongation at the first elongation The elasticity retention ratio (H2/H1) of is usually 20% or more, preferably 40% or more, more preferably 50% or more, further preferably 60% or more.

In addition, the second residual deformation in the 300% elongation-shrinkage repeated test at 23°C is usually 40% or less, preferably 30% or less, more preferably 25% or less, Particularly preferably, it is 20% or less. In addition, the fifth residual deformation is usually 50% or less, preferably 35% or less, more preferably 30% or less, particularly preferably 25% or less.

In addition, polyurethane film has a very close relationship with the physical properties of yarn, and the physical property values obtained from film tests etc. show the same tendency even in yarn (fiber).

<Use of Polyurethane Fiber>

The fibers using the polyurethane of the present invention are preferably used for underpants, pantyhose, diaper covers, paper diapers, sportswear, underwear, socks, stretch garments excellent in fashion, Swimsuits, bodysuits, etc. This is because stretch recovery, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, processability and the like are excellent.

Example

Hereinafter, although the Example of this invention is demonstrated more concretely, this invention is not limited to these Examples unless the summary is exceeded. In addition, analysis and measurement in the following examples and comparative examples were performed according to the following methods.

<Number average molecular weight of polyhydroxyl hydrocarbon polymer and polyether polyol>

The number-average molecular weights of the polyhydroxy hydrocarbon-based polymers and polyether polyols used in the present invention are determined by a hydroxyl value (KOH (mg)/g) measurement method based on the acetylation method of JIS K1557-1:2007.

<Molecular weight of polyurethane and polyurethane urea>

The molecular weight of the obtained polyurethane or polyurethane urea was measured as follows. A dimethylacetamide solution of polyurethane or polyurethane urea was prepared using a GPC device [manufactured by Tosoh Corporation, product name "HLC-8220" (chromatographic column: TskgelGMH-XL (2 pieces) )], and measure the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of standard polystyrene.

<Peel test method>

The two obtained films were stacked, and a test piece punch was used to obtain a film with a sample length of 4 cm (including the initial test length of 1.5 cm when the tensile tester was fixed and the overlapping portion of 2.5 cm) and a width of 1 cm. . The test piece was left to stand for 10 minutes at a temperature of 25°C and a relative humidity of 50% under the condition of applying a pressure of 200 g/cm ² to the overlapped portion of the film, and then tested using a tensile tester (manufactured by FUDOH "レオメーターター") NRM-2003J"), by stretching the tested film at a speed of 300mm/min, the T-peel strength is measured.

<Film properties>

Make a polyurethane or polyurethane urea test piece into a rectangle with a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm. According to JISK6301, use a tensile testing machine [manufactured by Orientec Corporation, product name "Tensilon UTM-III-100"], in the chuck Under the conditions of 50mm distance between them and 500mm/min tensile speed, measure the tensile strength at break, tensile elongation at break, 100% elongation and 300% elongation at a temperature of 23°C (relative humidity 55%) strength.

<Surface atomic composition>

The surface atomic composition is determined by ESCA (Electron Spectroscopy for Chemical Analysis). The measurement was carried out using an ESCA apparatus "PHIModel 5800" of Albach-Fai Co., Ltd. The measurement conditions are as follows.

Excitation X-rays: monochromatic AlKα line (1486.6eV)

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

・Neutralization gun: Use (for preventing static electricity)

Input lens setting (LensAreaMode): MinimumAreaMode

・Analysis mode (LENSMODE): 5 (minimum area mode)

Aperture number: 5

For emission (the angle formed by the normal line of the sample and the central axis of the detector): 45 degrees

Pass Energy: 23.5eV

· Charge transfer correction: The bonding energy of the C1s peak of the C—H bonded carbon was adjusted to 285.0 eV.

The relative abundance ratio of oxygen atoms to carbon atoms is calculated from the following formula.

Relative existence ratio O/C=(peak area of oxygen O1s/peak correction relative sensitivity coefficient of oxygen O1s peak)/(peak area of carbon C1s/peak correction relative sensitivity coefficient of carbon C1s peak)

In addition, the peak areas of oxygen O1s and carbon C1s were obtained as follows, using the MultiPakVer.8.2C software attached to the device, performing smoothing processing (9 points) using the Savitzky-Golay algorithm, and obtaining using the background curve of the Shirley method. Oxygen O1s and carbon C1s peak bonding energies used to calculate the relative abundance ratio and their corrected relative sensitivity coefficients used in the MultiPakVer.8.2C software are shown below.

O1s: Bonding energy = around 532.5eV,

· Corrected relative sensitivity coefficient = 13.118

C1s: Bonding energy = around 285.0eV,

· Corrected relative sensitivity coefficient = 5.220

Regarding the peak area of carbon C1s, the area obtained by adding the following areas is used, that is, the area obtained by connecting the minimum values around 280eV and 290.5eV using shirley and the area obtained by connecting the minimum values around 290.5eV and 293eV using shirley from the benzene ring The area of the peak of the shakeup (around 291-293eV) is added.

<Water contact angle>

Using an automatic contact angle meter DM-300 manufactured by Kyowa Interface Science Co., Ltd., a 1.5-2.0 μL water drop was dropped on the surface of the polyurethane film, and after 5 seconds, the internal angle formed by the tangent of the water drop and the surface of the molded article was measured. The location of the film was changed, the same operation was repeated 5 times, and the average value of the obtained 5 points was used as the water contact angle.

<Example 1>

Into a flask with a capacity of 1 L, 142.5 parts by weight of polytetramethylene ether glycol (number average molecular weight calculated from the hydroxyl value: 1968, manufactured by Mitsubishi Chemical Corporation) and hydrogenated Polybutadiene polyol (trade name "Polyter HA" number average molecular weight: 2187, average number of bonded hydroxyl groups per molecule: 1.8) was 7.5 parts by weight, and this mixture was used as a raw material for polyurethane production. The ratio of "Polyter HA" to this mixture was 5% by weight. Then, 31 parts by weight of 4,4'-diphenylmethane diisocyanate (hereinafter, may be 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. Then, the flask was placed in a 45° C. oil bath, and the temperature of the oil bath was raised to 70° C. over 1 hour while stirring with an anchor-type stirring blade under a nitrogen atmosphere, and then kept at 70° C. for 3 hours. The residual NCO group was reacted with an excess amount of dibutylamine, and then, the residual dibutylamine was reverse titrated with hydrochloric acid. After confirming that the reaction rate of NCO exceeded 99%, the oil bath was removed, and N,N-dibutylamine was added to the flask. 271 parts of methyl acetamide (hereinafter, sometimes abbreviated as "DMAC"; manufactured by Kanto Chemical Co., Ltd.) were stirred and dissolved at room temperature to prepare a polyurethane prepolymer solution.

Cool 380 parts by weight of the above-mentioned polyurethane prepolymer solution to 10°C and keep the temperature. On the other hand, prepare ethylenediamine (EDA)/diethylamine (DEA)=89/11 (molar ratio )=1.72/0.27 (weight ratio) of 0.6% DMAC solution. The above polyurethane prepolymer solution cooled to and kept at 10° C. was added to the 0.6% DMAC solution while stirring at high speed to obtain a polyurethane urea DMAC solution with a polymer concentration of 20%.

After aging the solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 172,000, and the molecular weight distribution was 2.4. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.

The polyurethane urea solution thus obtained was cast on a glass plate and dried at 60° C. to obtain a colorless and transparent film with a thickness of about 50 μm. The thickness of the film was measured with a thickness measuring device.

The peeling test of this film showed that the stress required for peeling was 5.7 g/cm, and the peelability was good. In addition, the properties of the obtained elastic film are shown in Table 1. In addition, the surface atomic composition of the thin film was 0.089, and the water contact angle was 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 calculated from the hydroxyl value: 1968, manufactured by Mitsubishi Chemical Corporation), which is a raw material for polyurethane production, and "Polyter HA" (number-average molecular weight: 2187, the average number of bonded hydroxyl groups per molecule: 1.8) 1.5 parts by weight (the ratio of "Polyter HA" in this mixture is 1% by weight), and set to ethylenediamine/diethylamine=1.81/0.28 (weight ratio), except that, a prepolymer and a polyurethane urea solution were obtained in the same manner as in Example 1.

After aging the solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 202,000, and the molecular weight distribution was 2.5. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 81% by weight.

A colorless and transparent polyurethane urea film with a thickness of about 50 μm was obtained from the polyurethane urea solution.

The peeling test of this film showed that the stress required for peeling was 5.7 g/cm, and the peelability was good. In addition, the properties of the obtained elastic film are shown in Table 1. In addition, the surface atomic composition of the film was 0.119, and the water contact angle was 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 the hydroxyl value: 1968, manufactured by Mitsubishi Chemical Corporation), which is a raw material for polyurethane production, and "Polyter HA" (number-average molecular weight: 2187, the average bond number of hydroxyl groups per molecule: 1.8) 0.15 parts by weight (the ratio of "Polyter HA" in this mixture is 0.1% by weight), and a prepolymer was obtained in the same manner as in Example 2 and polyurethane urea solution.

After aging this solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 198,000, and the molecular weight distribution was 2.4. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 82% by weight.

A colorless and transparent polyurethane urea film with a thickness of about 50 μm was obtained from the polyurethane urea solution.

A peel test was performed on this film, and the stress required for peeling was 33 g/cm, showing good peelability. In addition, the properties of the obtained elastic film are shown in Table 1. In addition, the surface atomic composition of the thin 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 "Polyter HA" (number average molecular weight: 2187, per 1 molecule A prepolymer and a polyurethane urea solution were obtained in the same manner as in Example 1 except that the average number of bonded hydroxyl groups: 1.8) was 45 parts by weight (the ratio of "Polyter HA" in this mixture was 30% by weight).

After aging the solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 198,000, and the molecular weight distribution was 2.4. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 57% by weight.

From this polyurethane urea solution, a slightly cloudy polyurethane urea film with a thickness of about 50 μm was obtained.

A peel test was performed on this film, and the stress required for peeling was 33 g/cm, showing good peelability. In addition, the properties of the obtained elastic film are shown in Table 1.

<Comparative example 1>

In Example 1, "Polyter HA" was not used, and 150 parts by weight of polytetramethylene ether glycol (number-average molecular weight calculated from the hydroxyl value: 1968, manufactured by Mitsubishi Chemical Corporation) was used as a raw material for polyurethane production. , and obtained a prepolymer and a polyurethane urea solution in the same manner as in Example 1.

After aging the solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 191,000, and the molecular weight distribution was 2.6. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.

A colorless and transparent polyurethane urea film with a thickness of about 50 μm was obtained from the polyurethane urea solution.

The film was subjected to a peeling test. The stress required for peeling was 50 g/cm. When peeling, a film stretch of 12% relative to the initial test length was observed. In addition, the properties of the obtained elastic film are shown in Table 1. In addition, the surface atomic composition of the film was 0.239, and the water contact angle was 76 degrees. The results are shown in Table 1.

[Table 1]

<Example 5>

[Manufacture of polyester polyol]

Measure 1.2 mg of tetrabutyl orthotitanate (Tokyo Chemicals Corporation), 30 g (20.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Corporation, molecular weight 1500), 10 g (87.6 mmol) of ε-hexyl Lactone (Across) was added to a 100mL four-necked round-bottomed flask with a stirrer, a reflux tube and a nitrogen gas inlet tube were installed, the reaction vessel was immersed in an oil bath, and the temperature was raised to 190°C for 30 minutes to make it cool at 190°C. Reaction 7h, as polyester polyol 1. Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 1.

[Manufacture of polyurethane urea]

123.9 parts by weight of polytetramethylene ether glycol (number average molecular weight calculated from hydroxyl value: 1955, manufactured by Mitsubishi Chemical Corporation) and 6.52 parts by weight of the above-mentioned synthesis were added to a 1-L flask and mixed. The polyester polyol 1, the mixture is used as the raw material for the manufacture of polyurethane. The ratio of polyester polyol 1 to this mixture was 5% by weight. Then, 26.8 parts by weight of 4,4'-diphenylmethane diisocyanate (hereinafter, 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. Then, the flask was placed in a 45° C. oil bath, and the temperature of the oil bath was raised to 70° C. over 1 hour while stirring with an anchor-type stirring blade under a nitrogen atmosphere, and then kept at 70° C. for 3 hours. The residual NCO group was reacted with an excess amount of dibutylamine, and then, the residual dibutylamine was reverse titrated with hydrochloric acid. After confirming that the reaction rate of NCO exceeded 99%, the oil bath was removed, and N,N-dibutylamine was added to the flask. 236 parts of methyl acetamide (hereinafter, sometimes abbreviated as "DMAC"; manufactured by Kanto Chemical Co., Ltd.) were stirred and dissolved at room temperature to prepare a polyurethane prepolymer solution.

Cool the above polyurethane prepolymer solution to 10°C and maintain the temperature. On the other hand, prepare ethylenediamine (EDA)/diethylamine (DEA) = 89/11 (molar ratio) = 1.66 as a chain extender /0.24 (weight ratio) of 0.5% DMAC solution. The above-mentioned polyurethane prepolymer solution cooled and kept at 10° C. was added to the 0.5% DMAC solution while stirring at high speed to obtain a polyurethane urea DMAC solution with a polymer concentration of 20%.

After aging the solution overnight at 25° C., the weight average molecular weight and molecular weight distribution were measured by GPC, and the weight average molecular weight was 219,000, and the molecular weight distribution was 2.7. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78% by weight.

The polyurethane urea solution thus obtained was cast on a glass plate and dried at 60° C. to obtain a colorless and transparent film with a thickness of about 50 μm. The thickness of the film was measured with a thickness measuring device.

The peeling test of this film showed that the stress required for peeling was 4.4 g/cm, and the peelability was good. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the film was 0.097, and the water contact angle was 95 degrees. The results are shown in Table 3.

<Example 6>

[Manufacture of polyester polyol]

Use 60g (28.6mmol) of GI-2000 (Nippon Soda Corporation, molecular weight 2100) instead of GI-1000, set the amount of tetrabutyl orthotitanate to 3.6mg, and the amount of ε-caprolactone to 12g (105mmol) ), except that, polyester polyol 2 was produced in exactly the same manner as in Example 5. Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 2.

[Manufacture of polyurethane urea]

By the raw material charging amount of making polyurethane shown in table 3, obtain polyurethane urea solution and film in the same manner as embodiment 5. The peeling test of this film showed that the stress required for peeling was 6.7 g/cm, and the peelability was good. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the film was 0.094, and the water contact angle was 94 degrees. The results are shown in Table 3.

<Example 7>

[Manufacture of polyester polyol]

Polyester polyol was produced in the same manner as in Example 6, except that 51.3 g (24.4 mmol) of GI-2000, 2.5 mg of tetrabutyl orthotitanate, and 22 g (193 mmol) of ε-caprolactone were used. 3. Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 3.

[Manufacture of polyurethane urea]

The raw material charging amount when making polyurethane shown in table 3, obtain polyurethane urea solution and film in the same manner as embodiment 5. A peel test was performed on this film, and the stress required for peeling was 3.6 g/cm, showing good peelability. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the film was 0.100, and the water contact angle was 95 degrees. The results are shown in Table 3.

<Embodiment 8>

[Manufacture of polyester polyol]

Using 60g (27.9mmol) of "Epol" (Idemitsu Kosan, molecular weight 1800), which is a hydrogenated polyisoprene polyol, instead of GI-1000, the amount of tetrabutyl orthotitanate used was 3.6mg, and ε-hexyl Polyester polyol 4 was produced in exactly the same manner as in Example 5 except that the amount of lactone used was 10 g (87.6 mmol). Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 4.

[Manufacture of polyurethane urea]

The raw material charging amount when making polyurethane shown in table 3, obtain polyurethane urea solution and film in the same manner as embodiment 5. A peel test was performed on this film, and the stress required for peeling was 4.5 g/cm, and the peelability was good. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the film was 0.154, and the water contact angle was 88 degrees. The results are shown in Table 3.

<Example 9>

[Manufacture of polyester polyol]

Measure 4.2 mg of tetrabutyl orthotitanate (Tokyo Chemical Corporation), 66.0 g (44.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Corporation, molecular weight 1500), 3.8 g (22.0 mmol) of Dimethyl diacid (Tokyo Chemicals Co., Ltd.) was added to a 100 mL four-neck round bottom flask with a stirring bar. Install a reflux tube and a nitrogen gas introduction tube, immerse the reaction vessel in an oil bath, raise the temperature to 190° C. for 30 minutes, and react at 190° C. for 7 hours to obtain polyester polyol 5. During the reaction, the distillation part was heated to 120° C. with a belt heater, and the methanol generated by the reaction was distilled off with nitrogen. Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 5.

[Manufacture of polyurethane urea]

The raw material charging amount when making polyurethane shown in table 3, obtain polyurethane urea solution and film in the same manner as embodiment 5. The peeling test of this film showed that the stress required for peeling was 10.8 g/cm, and the peelability was good. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the thin film was 0.072, and the water contact angle was 96 degrees. The results are shown in Table 3.

[0089]

<Example 10>

[Manufacture of polyester polyol]

Use 3.09g (21.1mmol) of dimethyl succinate (Tokyo Chemical Industry Co., Ltd.) Except that it was 2.2 mg, polyester polyol 6 was produced in exactly the same manner as in Example 9. Table 2 also shows the theoretical molecular weight and theoretical oxygen content of the polyester polyol 6.

[Manufacture of polyurethane urea]

The raw material charging amount when making polyurethane shown in table 3, obtain polyurethane urea solution and film in the same manner as embodiment 5. The peeling test of this film showed that the stress required for peeling was 13.0 g/cm, and the peelability was good. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the thin film was 0.083, and the water contact angle was 98 degrees. The results are shown in Table 3.

<Comparative example 2>

[Manufacture of polyurethane urea]

The raw material charging amount when making by the polyurethane shown in table 3, obtain the polyurethane urea solution and the film that do not contain polyester polyol the same as embodiment 5. A peel test was carried out on this film, and the stress required for peeling was 66.3 g/cm, showing poor peelability. In addition, the characteristics of the obtained elastic film are shown in Table 3. In addition, the surface atomic composition of the film was 0.239, and the water contact angle was 76 degrees. The results are shown in Table 3.

[Table 2]

[table 3]

Although the present invention was described in detail and specific embodiments were also referred to, it will be apparent to those skilled in the art that various changes and modifications can be added without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application (Japanese Patent Application No. 2008-306247) filed on December 1, 2008 and Japanese Patent Application (Japanese Patent Application No. 2009-179463) filed on July 31, 2009, the contents of which are incorporated herein by reference.

Industrial availability

According to the present invention, polyurethane can be produced while maintaining a constant compatibility with polyether polyol, and the adhesiveness of the obtained polyurethane can be reduced. In addition, when the obtained polyurethane is molded, the releasability between molded objects can be improved. In addition, when the elastic fiber made of polyurethane is used to form clothing, etc., cost reduction can be achieved by reducing the amount of oil or smoothing agent used, and stable operation can be achieved by reducing the frequency of product staining and clogging of machinery or equipment. Improvement of performance and reduction of frictional force can be expected to reduce driving power and the like. Therefore, the industrial value of this invention is remarkable.

Claims (10)

1. a polyurethane, is characterized in that, contains (a) polyester polyol, (b) polyether polyol, (c) polyisocyanate compound and (d) chain extender, (b) polyether polyol in polyurethane The proportion by weight of alcohol is 54% by weight to 99% by weight. The polyester polyol is formed by (A) polyhydroxy hydrocarbon polymer and (B) ester group-containing compound or carboxyl group-containing compound. The (A) and Said (B) forms at least one ester bond, and the oxygen content in said polyester polyol is 2.0 mass % or more and 13.5 mass % or less. 2. A polyester polyol, characterized in that it is formed by (A) polyhydroxy hydrocarbon polymer and (B) ester-containing compound or carboxyl-containing compound, and said (A) and said (B) form at least one ester bond, and the oxygen content in the polyester polyol is not less than 2.0% by mass and not more than 13.5% by mass. 3. The polyester polyol according to claim 2, wherein said (B) is polylactone. 4. according to the polyester polyol of claim 2 or 3 record, it is characterized in that, described polyester polyol is formed by described (A) and described (B) (B) (A) (B) type block copolymers. 5. The polyester polyol according to claim 2, wherein said (B) is a dicarboxylic acid. 6 . The polyester polyol according to claim 5 , wherein the dicarboxylic acid has 2 or more and 15 or less carbon atoms. 7. according to the polyester polyol of claim 5 or 6 record, it is characterized in that, described polyester polyol is the block copolymerization of (AB) _n A type that is formed by described (A) and described (B) Object, wherein, n is an integer greater than 1. 8. The polyester polyol according to claim 2 or 3, wherein the polyester polyol has a number average molecular weight of 500 to 5000. 9. The polyester polyol according to claim 2 or 3, wherein the (A) polyhydroxy hydrocarbon polymer is a hydrogenated polydiene polyol. 10. A polymer characterized in that at least one of the hydroxyl groups constituting the polyester polyol according to claim 2 or 3 forms a urethane bond.