KR20110099216A - Process for production of polyurethane, and uses of polyurethane produced thereby - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing polyurethanes and polyurethaneureas having low tackiness and high peelability when producing polyurethaneureas with polyetherpolyols, polyisocyanate compounds, and chain extenders. The present invention relates to a polyurethane comprising (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal of the molecule, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender. In the preparation, the present invention relates to a method for producing a polyurethane, which is prepared in the presence of an aprotic polar solvent.

Description

The manufacturing method of polyurethane and the use of the polyurethane obtained from the same {PROCESS FOR PRODUCTION OF POLYURETHANE, AND USES OF POLYURETHANE PRODUCED THEREBY}

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

Polyurethane compounds and polyurethaneurea compounds are applied in various fields. Polyurethane compounds are mainly produced from polyhydroxy compounds such as polyester polyols and polyether polyols, isocyanate compounds and, if necessary, chain extenders, foaming agents, foam stabilizers, and the like, and polyurethane-based elastic fibers and polyurethane-urea-based elastic fibers. It is often used for such uses. In particular, the fiber having a polyurethaneurea structure has excellent properties of elasticity and elongation recovery since a polyether polyol is used as the soft segment component and a polyamine compound having a high cohesion force is used as the hard segment. However, since these polyurethane-based elastic fibers have high adhesiveness between fibers, they are poor in releasing property at the time of release and have high frictional resistance, so that the yarns are in contact with the spinning process for spinning machines, warping machines, knitting machines and guides. Thread breaks occur on existing equipment. Therefore, a problem such as causing thread breakage in the machining step is likely to occur. Therefore, in order to reduce the frictional resistance of the apparatus and yarn of a processing process, solid metal soap, oil-soluble polymer, higher fatty acid, amino modified silicone, etc. are added as an oil agent, and talc, silica, colloidal alumina as a smoothing agent. Or a method of dispersing titanium oxide or the like, or further introducing silicon diol or silicon diamine into a part of the polyurethane main chain (for example, Patent Document 1).

However, even in this method, a sufficient anti-sticking effect is not obtained, or the smoothing agent causes significant wear on the spinning machine, the warping machine, the knitting machine or the guide, or the oligomers in the fibers extracted by the oil component in the warp and knitting process, or in the emulsion. The separation of solid or high-viscosity components into solid or paste forms a problem of sticking to fibers in large quantities and causing product fouling or clogging of machines or apparatuses, and the problem has not been solved. For this reason, even if it does not use such an oil agent and a smoothing agent, the adhesiveness is reduced, the peeling property (or the peelability of polyurethanes between polyurethanes) at the time of release is high, and the manufacturing method of the polyurethane which has high peelability has been calculated | required.

On the other hand, as an example of using a polyhydroxy hydrocarbon-based polymer having a hydroxyl group as a raw material of polyurethane, the use as a modifier of a urethane-based resin for improving the adhesiveness of the polyolefin resin material (Patent Document 2) and as a polymer polyol, In order to manufacture polyurethane by mixing with tetramethylene glycol, the examination which aims at the durability improvement of a polyurethane-type elastic fiber has been performed (patent document 3). However, in the method of patent document 3, since the hydrophobicity of a high molecular polyol is too high, compatibility with polyether polyol is bad, and there existed a problem that it did not gelatinize at the time of polyurethane manufacture or disperse | distribute uniformly at the time of manufacture of a yarn or a film. In addition, stretch fabrics and swimwear made of fibers made of polyurethane produced by the method described in Patent Document 3 are known to be excellent in chlorine resistance, hot water resistance, light resistance, and the like, but a polyhydroxyhydrocarbon polymer having a hydroxyl group is used as a raw material. It was not used for the purpose of lowering the adhesiveness of a polyurethane, lowering the adhesiveness of moldings, such as a film and elastic fiber which consist of polyurethane, and improving peelability. Moreover, although the polyhydric alcohol and polyhydric amines are illustrated as a chain extender, the polyurethane-type elastic fiber of patent document 3 is an elastic fiber obtained by the melt spinning method which used the real polyhydric alcohol as a chain extender, and a polyhydric amines are obtained by this method. In order to obtain a so-called polyurethaneurea structure to be used, an abnormal reaction such as gel or three-dimensional crosslinking occurs easily during the chain extension reaction, and there is a problem that it is difficult to mold into homogeneous fibers or films.

On the other hand, for the purpose of improving the overall physical properties of polyurethane elastic fibers, studies have been made to improve the raw material components of polyurethane. As an example of using a polyester polyol, for example, a hydrophobic polyester polyol formed of a glycol constituent having a polyhydric alcohol having a hydrocarbon group as a side chain and a carboxylic acid constituent having a dimer acid as an essential component It is proposed (patent document 4). However, even when these polyester polyols were used, polyurethanes still exhibiting sufficient peelability were not obtained.

Japanese Laid-Open Patent Publication No. 10-259577 Japanese Unexamined Patent Publication No. Hei 6-158016 Japanese Patent Application Laid-Open No. 11-131325 Japanese Unexamined Patent Publication No. 2002-212273

In view of the above problems, the present invention provides a polyether polyol, a polyisocyanate compound, and a high-strength polyurethane use such as a polyurethane elastic fiber, a film, and medical treatment when producing a polyurethane with a chain extender. It is an object to provide a novel polyesterpolyol which is very useful, and also has a low tackiness and a high peelability of polyurethanes and polyurethaneureas, and furthermore useful for producing polyurethaneureas.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, when manufacturing a polyurethane, the polyhydroxy polyol which has a polyether polyol and at least 1 hydroxyl group in a molecule terminal, Preferably, a specific structure And by using a polyester polyol having a constant oxygen content, more preferably the polyester polyol and polyether polyol are mixed and reacted with a polyisocyanate compound and a chain extender in the presence of a solvent to obtain a polyurethane and a poly The adhesiveness of urethane urea can be reduced, the peelability and the peelability at the time of release were found out, and the present invention was completed.

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

[1] A raw material of (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal of the molecule, (b) polyether polyol, (c) polyisocyanate compound, and (d) chain extender is subjected to addition polymerization reaction. In obtaining a polyurethane, a poly having at least one hydroxyl group at the end of (a) a molecule relative to the sum of (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the end of the molecule and (b) a polyether polyol Reaction in the presence of a hydroxy hydrocarbon-based polymer is 0.01 to 50.00% by weight and a solvent selected from the group consisting of an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide The manufacturing method of the polyurethane characterized by the above-mentioned.

[2] The method for producing the polyurethane according to [1], wherein the number average molecular weight of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) is preferably 500 to 5000.

[3] Preferably, the number of average hydroxyl groups per molecule of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) is 1.5 to 2.7. Method of producing polyurethanes.

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

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

[6] Preferably, any one of [1] to [5], wherein the main skeleton of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) is hydrogenated polybutadiene. The manufacturing method of the described polyurethane.

[7] Preferably, (a) the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal of the molecule is (A) a polyhydroxyhydrocarbon polymer and (B) an ester group-containing compound or a carboxyl group-containing compound. It is a polyester polyol formed, The manufacturing method of the polyurethane in any one of [1]-[6].

[8] Preferably, in the polyester polyol, (A) and (B) form at least one ester bond, and the oxygen content in the polyester polyol is 2.0% by mass or more and 13.5% by mass or less. The manufacturing method of the polyurethane as described in [7] characterized by the above-mentioned.

[9] The method for producing the polyurethane according to [7] or [8], in which (B) is preferably polylactone.

[10] Preferably, the polyester polyol is a block copolymer of type (B) (A) (B) formed from the above (A) and (B). The manufacturing method of the polyurethane in any one of them.

[11] The method for producing the polyurethane according to [7] or [8], in which (B) is preferably dicarboxylic acid.

[12] The method for producing the polyurethane according to [11], wherein the carbon number of the dicarboxylic acid is preferably 2 or more and 15 or less.

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

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

[15] A polyurethane comprising (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal of the molecule, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, The polyurethane (b), wherein the weight ratio of the polyether polyol (b) in the polyurethane is 54% by weight to 99% by weight.

[16] A polyurethane molded product comprising the polyurethane according to the above [14] or [15].

[17] a polyurethane comprising (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal of the molecule, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender A polyurethane molded body, wherein the polyurethane molded body has an atomic composition (oxygen atom / carbon atom) of 0.22 or less on the surface of the polyurethane molded body.

[18] The polyurethane molded product according to [17], wherein the water contact angle on the surface of the polyurethane molded product is preferably 80 degrees or more.

[19] A film comprising the polyurethane according to the above [14] or [15].

[20] A fiber comprising the polyurethane according to [14] or [15].

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

[22] The polyester polyol according to [21], wherein (B) is preferably polylactone.

[23] The method of [21] or [22], wherein the polyester polyol is a block copolymer of type (B) (A) (B) formed from the above (A) and (B). Described polyesterpolyols.

[24] The polyester polyol according to [21], wherein (B) is dicarboxylic acid.

[25] The polyester polyol according to [24], wherein the carbon number of the dicarboxylic acid is preferably 2 or more and 15 or less.

[26] Preferably, the polyester polyol is a block copolymer of type (AB) _n A formed from (A) and (B), wherein n is an integer of 1 or more. 24] or the polyester polyol as described in [25].

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

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

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

According to the present invention, a polyurethane can be produced while maintaining a constant compatibility with the polyether polyol, and the adhesiveness of the polyurethane obtained can be reduced. Moreover, when shape | molding the obtained polyurethane, the peelability of moldings can be improved. Furthermore, when molding medical care using the elastic fiber made of this polyurethane, it is possible to reduce operating costs by reducing the amount of use of emulsions and smoothing agents, and to improve operation stability by reducing product fouling and reducing the clogging frequency of machines and devices. As the frictional resistance is reduced, driving power reduction can be expected.

Description of the element | module described below is an example (representative example) of embodiment of this invention, and this invention is not limited to these content. Hereinafter, the detail is demonstrated.

<Polyurethane>

The polyurethane of the present invention comprises (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular terminal of the present invention, (b) polyether polyol, (c) polyisocyanate compound, and (d) chain extension. Obtained by use with agent.

The polyurethane in the present invention refers to (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular terminal, (b) polyether polyol, (c) polyisocyanate compound, and (d) chain extender. It is to include. Moreover, it is although it does not specifically limit as a weight ratio which (b) polyether polyol in a polyurethane occupies, Usually, it is 54 to 99 weight%, Preferably it is 60 to 90 weight%, More preferably, it is 70 to 85 weight % to be. As this ratio increases, the flexibility of the polyurethane obtained tends to improve, while the smaller, the peelability of the polyurethane obtained tends to improve.

In the polyurethane of the present invention, at least one of the hydroxyl group constituting the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) of the present invention or (b) the polyether polyol forms a urethane bond. Polymers present. Preferably, a polymer having the following partial structure, that is, a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the terminal of (a) the molecule of the present invention, or (b) at least two hydroxyl groups constituting the polyether polyol are urethane bonds. It is a polymer which has the following structure which formed the following in a polymerization chain.

[Formula 1]

(In Formula (I), HO-X-OH represents the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group in the (a) molecule terminal of this invention, or (b) polyether polyol.)

Content and position in particular of the said polymer in the polyurethane of this invention are not restrict | limited, What is necessary is just a polymer which has the said structure in a polymerization chain. As a compound containing the said structure, a polyurethane resin, a polyurethane urea resin, those prepolymers, etc. are mentioned, for example.

Moreover, in this invention, "(a) the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group in a molecule terminal, (b) polyether polyol (c) polyisocyanate compound, and (d) chain extender is included. Polyurethane to be referred to "means a polymer compound having a urethane bond (-NHCOO-) in a repeating unit of a main chain, and the repeating structural unit of the main chain is derived from both compounds of (a) and (b) Polyurethane as a high molecular compound derived only from (a), Polyurethane as a high molecular compound derived only from (b), and those mixed together may be sufficient. Moreover, unreacted (a), (b), (c), or (d) and the said high molecular compound may be mixed.

Polyurethane as used in the present invention refers to a polyurethane or polyurethane urea unless otherwise specified, and it is conventionally known that these two types of resins have almost the same physical properties. On the other hand, the difference in the structural features is that polyurethane is produced using a short chain polyol as a chain extender, and polyurethaneurea is produced using a polyamine compound as a chain extender.

Each composition ratio is usually a number of moles of the sum of the hydroxyl groups of (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the terminal of the molecule and (b) a polyether polyol with respect to polyurethane. When the number of moles of the isocyanate group of the compound is B, the number of moles of the active hydrogen substituents (hydroxyl group and amino group) of the chain extender (C), A: B is usually in the range of 1:10 to 1: 1, preferably 1: 5 to 1: 1.05, more preferably 1: 3 to 1: 1.1, still more preferably 1: 2.5 to 1: 1.2, particularly preferably 1: 2 to 1: 1.2, and (BA): C is usually 1: 0.1-1: 5, preferably 1: 0.8-1: 2, more preferably 1: 0.9-1: 1.5, still more preferably 1: 0.95-1: 1.2, particularly preferably It is in the range of 1: 0.98 to 1: 1.1.

<(a) Polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group in a molecule terminal>

In the present invention, a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at a molecular terminal is typically a polymer having a hydrocarbon skeleton such as conjugated diene such as butadiene, isoprene, chloroprene as a repeating unit, or described later. The polyester polyol to say. These can be used by mixing with a polyether polyol, and using them to produce a polyurethane, and can improve the adhesiveness of the polyurethane obtained, the peelability of a polyurethane molding, and the degradability at the time of release.

The polymer having a hydrocarbon backbone as a repeating unit is preferably a conjugated diene-based polymer having a hydroxyl group directly at the terminal, for example, by radical polymerization of 1,3-butadiene with hydrogen peroxide as a polymerization initiator. A living polymer in which an alkali metal is bonded to the terminal is prepared using a polymerization catalyst, and then a monoepoxy compound, formaldehyde or the like is reacted to form a conjugated diene polymer having a hydroxyl group at the terminal, and the obtained conjugated diene polymer is a conventional method. The thing which hydrogenated was mentioned is mentioned. In this case, vinyl conjugates such as styrene, acrylonitrile, methyl (meth) acrylate and vinyl acetate may be copolymerized in the conjugated diene in an amount of 30% by weight or less.

The polymer of isobutylene or isobutylene and conjugated diene such as isoprene or 1,3-pentadiene is subjected to oxidative decomposition treatment with ozone or the like, followed by reduction treatment with lithium aluminum hydride or the like, and a hydroxyl group at the terminal. An isobutylene-based polymer having a polymer was obtained, and the obtained polymer was hydrogenated by a conventional method, and a copolymer of? -Olefins such as ethylene and propylene and a diene-based compound was oxidatively decomposed and reduced, and then hydrogenated. And the like.

Among the polyhydroxyhydrocarbon polymers having at least one hydroxyl group at the molecular terminal of the present invention, polyhydroxyhydrocarbon polymers whose main skeleton is preferably hydrogenated polybutadiene, hydrogenated polyisoprene, and polyisobutylene are preferable. In addition, from the availability and ease of handling, the main skeleton is more preferably hydrogenated polybutadiene.

As a ratio of the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group in the molecule terminal used by this invention, it is 0.01 weight with respect to the total amount of the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group in a molecule terminal, and a polyether polyol. It is preferable that it is% or more. More preferably it is 0.03 weight% or more, More preferably, it is 0.05 weight% or more, Especially preferably, it is 0.07 weight% or more, Most preferably 0.1 weight%. As this numerical value increases, there exists a tendency for the adhesiveness of the polyurethane resin obtained to fall. On the other hand, the upper limit is preferably 50.00% by weight or less. More preferably it is 30.00 weight% or less, More preferably, it is 25.00 weight% or less, Especially preferably, it is 15.00 weight% or less, Most preferably, it is 10.00 weight% or less. The smaller the value, the lower the adhesiveness of the resulting polyurethane resin, but tends to improve elasticity characteristics and stretch recovery.

The polyhydroxy hydrocarbon-based polymer has a number average molecular weight of 500 to 5000, preferably 700 to 4000, more preferably 900 to 3500 and is liquid or waxy at room temperature. When number average molecular weight is too high, the viscosity of a polyether polyol, a prepolymer, or a prepolymer solution will become high too much, and operability and productivity will worsen, or there exists a tendency for the physical property at low temperature of the obtained polyurethane polymer to worsen. When too low, the polyurethane polymer obtained will become hard and sufficient flexibility will not be obtained, elastic performance, such as strength and elongation, may not be enough, or it will tend to leave excessive residual deformation when elongation and recovery are repeated. The polyester polyol is one having at least two or more ester bonds and two or more hydroxyl groups in the molecule, and preferably both terminals of the polyester polyol main chain are hydroxyl groups.

The polyester polyol of this invention is a polyester polyol formed from (A) polyhydroxy hydrocarbon polymer mentioned later, and (B) ester group containing compound or carboxyl group containing compound, Specifically, (A) polyhydroxy hydrocarbon polymer (B) At least one ester bond is formed with ester group containing compound or carboxyl group containing compound.

The number of ester bonds which the (A) polyhydroxyhydrocarbon polymer contained in 1 molecule of polyester polyols of this invention forms is 1 or more normally.

Specifically, one molecule of (A) polyhydroxyhydrocarbon polymer may form a plurality of ester bonds at the molecular terminal, and a plurality of polyhydroxyhydrocarbon polymers (A) form an ester bond, and in one polyesterpolyol molecule The total number of ester bonds contained may be 2 or more.

Hereinafter, it describes and divides into the requirements which comprise the polyester polyol of this invention.

<(A) Polyhydroxy Hydrocarbon Polymer>

The (A) polyhydroxyhydrocarbon polymer in the present invention is a polymer having a hydrocarbon skeleton as a repeating unit, and has at least two hydroxyl groups in the polymer.

The polymer having the hydrocarbon skeleton as a repeating unit is not particularly limited, and a polymer having a hydrocarbon having a halogen other than an element other than carbon and hydrogen, for example, chlorine, fluorine and bromine as a substituent, as a repeating unit Although it may be sufficient, Preferably it is a polymer (Hereinafter, it may be called a hydrocarbon polymer) which used the hydrocarbon formed from carbon and hydrogen as a repeating unit, More preferably, it is an aliphatic hydrocarbon polymer.

As a hydrocarbon polymer in this invention, the polymer which uses a linear hydrocarbon as a repeating unit, or the polymer which makes a hydrocarbon which has a side chain in a molecule | numerator as a repeating unit is mentioned.

When there is much content of the hydrocarbon which has a side chain in a molecule | numerator, since the melting | fusing point of a hydrocarbon polymer becomes low and handling becomes easy, the hydrocarbon polymer which has many content of the hydrocarbon which has a side chain is preferable.

The said hydrocarbon polymer may be a homopolymer by one repeating unit, or the copolymer containing two or more repeating units may be sufficient as it.

Although carbon number in particular of the repeating unit of the said hydrocarbon is not restrict | limited, Usually, it is 2 or more, Preferably it is 3 or more, Usually 9 or less, Preferably it is 6 or less.

The polyhydroxyhydrocarbon polymer in the present invention is easy to introduce a functional group into the terminal of the polymer, and in terms of easy molecular weight control, butadiene, isobutylene, isoprene, chloroprene and the like; It is a polymer containing conjugated diene of, More preferably, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated polyisobutylene, etc .; Is a polymer (hereinafter, hydrogenated polydiene) that is hydrogenated after homopolymerization of conjugated dienes, and more preferably hydrogenated polybutadiene from the viewpoint of availability and ease of handling.

The polyhydroxy hydrocarbon polymer in the present invention has at least two hydroxyl groups in the polymer. Although the number of the said hydroxyl groups will not be normally limited if it is a range which satisfy | fills the following oxygen content, Usually, they are two or more and six or less, Preferably they are three or less. Although the position of a hydroxyl group is not specifically limited, It is preferable that a hydroxyl group exists in a molecular terminal, It is more preferable that two or more are in a molecular terminal, It is further more preferable that it exists in both ends of the principal chain of a hydrocarbon polymer.

The polyhydroxy hydrocarbon polymer (A) constituting the polyester polyol of the present invention forms at least one ester bond to adjust the hydrophobicity of the polyester polyol, thereby making the polyester having higher compatibility with the polyether polyol than the saturated hydrocarbon polymer. Polyols can be obtained. Moreover, the polyurethane obtained using such polyester polyol shows high peelability.

The number average molecular weight of the polyhydroxyhydrocarbon 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, and more preferably 3000 or less. to be. If it is less than the said lower limit, the polyurethane polymer obtained will become hard and it will fall of flexibility, the fall of elastic performance, such as strength and elongation, or it will tend to leave excessive residual strain, when elongation and recovery are repeated. If it exceeds the said upper limit, the viscosity of a polyether polyol, a prepolymer, or a prepolymer solution will become high too much, and operability and productivity will fall, or there exists a tendency for the physical property in the low temperature of the polyurethane polymer obtained to fall.

Although the property of the polyhydroxy hydrocarbon polymer in this invention is not specifically limited, Usually, it is a liquid or wax form 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 usually include a compound in which a repeating unit is polymerized via an ester bond, and preferably a poly obtained by ring-opening polymerization of lactone. Lactone.

<Polylactone>

Polylactone in this invention is obtained by performing a well-known polymerization reaction using lactone as a raw material.

Specifically used lactones are ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone, γ-valerolactone, enantholactone, and the like, and these may be used alone or in combination of two or more thereof. Among them, ε-caprolactone, δ-valerolactone and γ-valerolactone are preferable from the viewpoint of being easily available and highly reactive, and more preferably ε-caprolactone.

Hereinafter, as a polyester polyol formed from a polyhydroxy hydrocarbon polymer and an ester group containing compound, the polyester polyol formed from a polyhydroxy hydrocarbon polymer and a polylactone is described as an example.

<Polyester polyol formed of polyhydroxy hydrocarbon polymer and polylactone>

In the polyester ester polyol of the present invention, one of the preferred embodiments is one or more ester groups formed between the polyhydroxy hydrocarbon polymer and the following polylactone, preferably a hydroxyl group of one molecule of the polyhydroxy hydrocarbon polymer. At least one of which forms an ester bond with polylactone, has a plurality of ester bond in one molecule as a total, More preferably, at least 1 of the terminal hydroxyl group which one molecule of a polyhydroxy hydrocarbon polymer has, An ester bond is formed between polylactone, and it has a some ester bond in 1 molecule as a total.

Although the copolymerization form of the said polyhydroxy hydrocarbon polymer and polylactone is not specifically limited, Preferably, (A) polyhydroxy hydrocarbon polymer site | part and (B) polylactone site | part are (B) (A) (B) It is the polyester polyol which comprises a block copolymer of a type | mold. (B) is a lactone ring-opening polymer, and (A) and (B) are bonded via an ester bond.

The polymerization degree of (A) or (B) is not specifically limited, What is necessary is just to consider and determine the molecular weight of a raw material so that the oxygen content and molecular weight in a polyester polyol may be a desired value.

According to the physical property of a desired polyurethane resin, it is possible to change the molecular weight and oxygen content of the polyester polyol produced | generated easily by adjusting the polymerization degree of said (A) or (B). Although a manufacturing method is not specifically limited, In general, it can obtain by making a polyhydroxy hydrocarbon polymer and a lactone react in predetermined ratio in the presence of a catalyst, such as a tetraisopropyl titanate or tetrabutyl titanate, without a solvent.

<(B) carboxyl group-containing compound>

Although the carboxyl group-containing compound used by this invention will not be specifically limited if it has a carboxyl group, Usually, monocarboxylic acid compounds, dicarboxylic acid compounds, substituted carboxylic acid compounds, such as hydroxy acid and alkoxy acid, etc. are mentioned. And dicarboxylic acid compounds.

<Dicarboxylic acid>

Although any of aliphatic dicarboxylic acid and aromatic dicarboxylic acid may be sufficient as the dicarboxylic acid compound used by this invention, As aliphatic dicarboxylic acid, it is C2 or more normally, Preferably it is three or more, More preferably Preferably it is four or more, and usually 16 or less, Preferably it is 15 or less, More preferably, it is 14 or less. Specifically, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimeric acid, suveric acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10 -Decamethylene dicarboxylic acid, 1,11- undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, etc. are mentioned. Moreover, orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracenedicarboxylic acid, or phenanthrene dicarboxylic acid etc. are mentioned specifically as aromatic dicarboxylic acid. These may be used as 1 type or as 2 or more types of mixtures. In addition, anhydrides of these dicarboxylic acids, alkyl esters or halogen substituents of unsaturated bonds may be used. Among them, from the viewpoint of easy availability and high thermal stability, aliphatic dicarboxylic acids, more preferably malonic acid, succinic acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, More preferably, it is succinic acid and adipic acid.

Hereinafter, as a polyester polyol formed from a polyhydroxy hydrocarbon polymer and a carboxyl group-containing compound, what is formed from a polyhydroxy hydrocarbon polymer and a dicarboxylic acid is described as an example.

<Polyester Polyol Formed from Polyhydroxyhydrocarbon Polymer and Dicarboxylic Acid>

The polyester polyol formed from the polyhydroxy hydrocarbon polymer and the dicarboxylic acid in the present invention usually includes at least one hydroxyl group and two dicarboxylic acid molecules each of the two polyhydroxy hydrocarbon polymers each has. And polyesterpolyols each forming an ester bond between two carboxyl groups.

Preferably, it is a polyester polyol of the type (AB) _n A formed from a polyhydroxy hydrocarbon polymer (A) and a dicarboxylic acid (B). (A) and (B) should just be couple | bonding through the ester bond, and may be manufactured with carboxylic acid derivatives, such as carboxylic acid diester.

Usually, n should just be an integer greater than or equal to 1, More preferably, it is ABA type polyester polyol in which the polyhydroxy hydrocarbon polymer couple | bonded one by one with the both ends of the dicarboxylic acid corresponded when said n = 1.

In general, the molecular weight of the polyhydroxyhydrocarbon polymers available is at least 1500 or higher, and when the polyhydroxyhydrocarbon polymer reacts at both terminals of the dicarboxylic acid to produce a polyester polyol, the molecular weight is 3000 or more. When the value of n becomes large, when the molecular weight of a polyester polyol becomes large too much, the viscosity of a prepolymer or a prepolymer solution will become high too much, and the operability and productivity at the time of polyurethane manufacture will fall, or the physical property at the low temperature of the polyurethane polymer obtained will fall. Because there is a tendency.

Although the polyester polyol of this invention may have structures other than the said structure in a molecule | numerator, Preferably the polyester polyol which does not contain other structures other than the said site | part is preferable.

In addition, in the above description, although (A) and (B) were described in detail as a structure for forming an ester bond, the polyester polyol of this invention is not limited to this, If the molecular structure obtained is the same, what kind of raw material May be obtained by a reaction method.

<Oxygen content>

Oxygen content in the polyester polyol of this invention means oxygen content in 1 molecule of polyester polyols, and means the ratio of the oxygen atom contained in the molecule with respect to the molecular weight of 1 molecule of polyester polyols normally. For example, when 10 oxygen atoms exist in the polyester polyol of molecular weight 2000, it becomes (10x16 / 2000) x100 = 8.0 mass%.

Oxygen content of the polyester polyol of this invention is 2.0 mass% or more, It is the range of 13.5 mass% or less, Preferably it is 2.2 mass% or more, More preferably, it is 2.5 mass% or more, More preferably, it is 3.0 mass% or more Preferably it is 13 mass% or less, More preferably, it is 12 mass% or less, More preferably, it is 11.0 mass%. If it is less than the said lower limit, compatibility with a polyether polyol and solubility to a solvent are inadequate, and if it exceeds the said upper limit, since the adhesiveness of the polyurethane resin obtained will increase, it is not preferable.

Although the ratio of the polyhydroxy hydrocarbon polymer in the polyester polyol of this invention is not specifically limited, Usually, it is 10.0 mass% or more as mass ratio, Preferably it is 20.0 mass% or more, More preferably, it is 30.0 mass% or more, More preferably, it is 40.0 mass% or more, Especially preferably, it is 45.0 mass%. The larger the mass ratio of the polyhydroxyhydrocarbon polymer in the polyester polyol of the present invention, the more the adhesiveness of the polyurethane obtained tends to be lowered. On the other hand, the upper limit is not particularly limited, but is 99.5% by mass or less, preferably 99.0% by mass or less, more preferably 98.5% by mass or less, still more preferably 98.2% by mass or less, particularly preferably 98.0% by mass. It is as follows. As the mass ratio becomes smaller, the compatibility with the polyether polyol and the solubility in polar solvents tend to be improved.

Physical Properties of Polyester Polyol

The number average molecular weight of the polyester polyol of this invention can be adjusted according to the kind and quantity of (A) or (B) to be used. The number average molecular weight is usually 500 or more, preferably 600 or more, more preferably 800 or more, and usually 10000 or less, preferably 7000 or less, and more preferably 5000 or less. A number average molecular weight shows the average molecular weight per molecule. When a number average molecular weight exceeds the said upper limit, the viscosity of a prepolymer and a prepolymer solution will become high too much, and operability and productivity will fall, or there exists a tendency for the physical property in the low temperature of the polyurethane polymer obtained to fall. Below the lower limit, the polyurethane polymer obtained may be hard and sufficient flexibility may not be obtained, or elastic performances such as strength and elongation may not be sufficient, or excessive residual strain may remain when elongation and recovery are repeated. have.

<(b) polyether polyol>

The polyether polyol in the present invention is a hydroxy compound having at least one or more ether bonds in the main skeleton in the molecule, and as the repeating unit in the main skeleton, any of saturated hydrocarbons and unsaturated hydrocarbons may be used. 1,4-butanediol unit, 2-methyl-1,4-butanediol unit, 3-methyl-1,4-butanediol unit, 1,3-propanediol unit, 1,2-propylene glycol unit, 2-methyl-1 , 3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 3-methyl-1,5-pentanediol unit, 1,2-ethylene glycol unit, 1,6-hexanediol unit, 1 , 7-heptane diol units, 1,8-octanediol units, 1,9-nonanediol units, 1,10-decanediol units, 1,4-cyclohexanedimethanol units, and the like.

Among these, polytetramethylene ether glycol, polytrimethylene ether glycol, and the copolymerization polyether polyol of 1-20 mol% of 3-methyl tetrahydrofuran and tetrahydrofuran among the polyol units which comprise a polyether polyol (for example, For example, "PTG-L1000", "PTG-L2000", "PTG-L3500", etc. by Hodogaya Chemical Co., Ltd., or the copolymer polyether glycol of neopentyl glycol and tetrahydrofuran are preferable.

<(c) polyisocyanate compound>

As the polyisocyanate compound used in the present invention, for example, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4 ' Aromatic diisocyanates, such as -MDI, paraphenylene diisocyanate, 1, 5- naphthalene diisocyanate, and tridine diisocyanate, aliphatic diisocyanate which has aromatic rings, such as (alpha), (alpha), (alpha), (alpha) '-tetramethyl xylylene diisocyanate. , Aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4- Cyclohexanediisocyanate, methylcyclohexanediisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanatemethyl-3,5,5-trimethylcyclohexane (I PDI), alicyclic diisocyanate, such as 4,4'- dicyclohexyl methane diisocyanate and isopropylidene dicyclohexyl-4,4'- diisoate, etc. are illustrated. These may be single use or 2 or more types together.

In the present invention, particularly highly reactive aromatic polyisocyanates are preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferable. In addition, a part of the NCO group of the polyisocyanate may be modified with urethane, urea, biuret, allophanate, carbodiimide, oxazolidone, amide, imide, or the like, and the polynuclear body contains isomers other than the above. That includes doing.

The usage-amount of these polyisocyanate compounds is 1 in which the sum total of the hydroxyl group of (a) the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group at the terminal of a molecule, and (b) the polyether polyol, and the hydroxyl group and amino group of a chain extender. With respect to the equivalent weight, it is usually 0.1 equivalent-5 equivalents, preferably 0.8 equivalent-2 equivalents, more preferably 0.9 equivalent-1.5 equivalents, still more preferably 0.95 equivalent-1.2 equivalents, most preferably 0.98 equivalent-1.1 equivalents .

When the amount of the polyisocyanate used is too large, unreacted isocyanate groups tend to cause undesirable reactions, and the desired physical properties tend to be difficult to be obtained. When the amount of the polyisocyanate used is too small, the molecular weight of the polyurethane and the polyurethaneurea does not increase sufficiently, and the desired performance is achieved. This tends not to be expressed.

<(d) chain extender>

Chain extenders used in the present invention are mainly classified into compounds having two or more hydroxyl groups, compounds having two or more amino groups, and water. Among these, a short-chain polyol, specifically, the compound which has 2 or more hydroxyl groups is used for a polyurethane use, and the polyamine compound, specifically, the compound which has 2 or more amino groups is preferable for a polyurethaneurea use. Among these, it is preferable to reduce water as much as possible in order to carry out reaction stably.

Moreover, since the rubber elasticity of a polyurethane elastomer improves when the polyurethane resin of this invention uses a compound whose molecular weight (number average molecular weight) is 500 or less together as a chain extender, it is more preferable on a physical property.

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

As a compound which has two or more amino groups, For example, aromatic diamines, such as 2, 4- or 2, 6- tolylene diamine, xylylene diamine, and 4,4'- diphenylmethane diamine, ethylene diamine, 1,2 -Propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4'-diamine And alicyclic diamines such as 1,4-diaminocyclohexane and 1,3-bisaminomethylcyclohexane. These chain extenders may be used alone or in combination of two or more thereof. Among these, ethylenediamine, propylenediamine, 1,3-diaminopentane and 2-methyl-1,5-pentanediamine are preferable in the present invention, and among these, ethylenediamine and propylenediamine are more preferable.

Although the usage-amount of these chain extenders is not specifically limited, When equivalent to the equivalent of the sum total of the hydroxyl groups equivalent of (a) and (b) minus the equivalent of the polyisocyanate compound is 1, it is usually 0.1 equivalent or more and 5.0 equivalents or less. Preferably it is 0.8 equivalent or more, 2.0 equivalent or less, More preferably, it is 0.9 equivalent or more and 1.5 equivalent or less. When the amount is excessively large, the obtained polyurethane and polyurethaneurea are too hard to obtain desired properties, or they are not easily dissolved in a solvent, which makes processing difficult. When the amount is too small, excessively soft, sufficient strength and elastic recovery performance or elastic retention There is a tendency that performance is not obtained or high temperature characteristics deteriorate.

When using the polyurethane and polyurethane urea made into object in this invention for high performance polyurethane elastomer applications, such as a polyurethane elastic fiber and a synthetic leather, the following examples are mentioned as a combination of a raw material.

Moreover, the chain stopper which has one active hydrogen group can be used as needed for the purpose of controlling the molecular weight of a polyurethane. As these chain stoppers, aliphatic monools, such as ethanol, propanol, butanol, and hexanol which have a hydroxyl group, diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine, etc. which have an amino group Amines are exemplified. These may be single use or 2 or more types together.

<Other additives>

Moreover, you may add another additive to the polyurethane of this invention as needed in addition to the above. As these additives, "CYANOX1790" (made by CYANAMID company), "IRGANOX245", "IRGANOX1010" (above, Chiba Specialty Chemicals make), "Sumilizer GA-80" (made by Sumitomo Chemical Co., Ltd.), or 2,6-di Antioxidants such as butyl-4-methylphenol (BHT), `` TINUVIN622LD '', `` TINUVIN765 '' (above, Chiba Specialty Chemicals), `` SANOL LS-2626 '', `` SANOL LS-765 '' (above, Sankyo Light stabilizers such as Sa), ultraviolet absorbers such as `` TINUVIN328 '', `` TINUVIN234 '' (above, Chiba Specialty Chemicals Co., Ltd.), silicone compounds such as dimethylsiloxane polyoxyalkylene copolymers, red phosphorus, organic phosphorus compounds, Phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, addition of ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like, reactive flame retardants, pigments such as titanium dioxide, dyes, colorants such as carbon black, carbodiimide compounds and the like Of autumn There may be mentioned the decomposition agent, a short glass fiber, carbon fiber, alumina, talc, graphite, melamine, fillers such as clay, lubricants, emulsions, surfactants, other inorganic extenders, organic solvents and the like.

<Production Method of Polyurethane>

The polyester polyol of this invention and the manufacturing method of a polyurethane are explained in full detail below.

<Method for producing polyester polyol>

The polyester polyol of this invention is manufactured using a polyhydroxy hydrocarbon polymer. The polyhydroxyhydrocarbon polymer is a compound known per se, and can be produced in accordance with a commonly used method. Moreover, these commercially available compounds can also be used. Typically, conjugated dienes such as butadiene, isoprene and chloroprene, preferably 1,3-butadiene, are radically polymerized with hydrogen peroxide as a polymerization initiator to directly prepare a conjugated diene polymer having a hydroxyl group at the terminal or anionic polymerization. A living polymer in which an alkali metal is bonded to a terminal is prepared using a catalyst, and then a monoepoxy compound, formaldehyde or the like is reacted to form a conjugated diene polymer having a hydroxyl group at the terminal, and the obtained conjugated diene polymer is obtained by a conventional method. The hydrogenated thing is mentioned. In addition, vinylmonomers, such as styrene, an acrylonitrile, methyl (meth) acrylate, and vinyl acetate, may be copolymerized by the said conjugated diene in the quantity of 30 mass% or less.

The polymer of isobutylene or isobutylene and conjugated dienes such as isoprene and 1,3-pentadiene is subjected to oxidative decomposition treatment with ozone or the like, followed by reduction treatment with lithium aluminum hydride or the like, The isobutylene polymer which has a hydroxyl group was obtained, and the obtained polymer was hydrogenated by the conventional method, and the copolymer of alpha-olefins, such as ethylene and a propylene, and a diene type compound was similarly oxidatively decomposed and reduced, and hydrogenated Addition etc. are mentioned.

The conventionally well-known esterification technique can be employ | adopted for manufacture of the polyester polyol of this invention. For example, a method of reacting polyol and lactone or dicarboxylic acid under atmospheric pressure, esterification under reduced pressure, and esterification in the presence of an inert solvent such as toluene, followed by azeotropic condensation water or condensation alcohol and solvent, How to remove.

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 does not proceed sufficiently. If too high, the coloration of the product may increase.

It is preferable to perform reaction in inert gas atmosphere, such as nitrogen and argon. Reaction pressure is arbitrary and can be implemented under normal pressure or reduced pressure according to the objective. In reactions such as polyols and dicarboxylic acids or dicarboxylic acid esters, since water and alcohol are produced during the reaction, an inert gas may be passed through the reaction system in order to promote their desorption from the reaction system.

<Catalyst>

The type of the esterification reaction is not particularly limited, and it is also possible to perform the esterification reaction in a system in which no catalyst is present, but in general, in order to proceed with the esterification smoothly, inorganic acids or organic acids; Chlorides, oxides, hydroxides of metals such as Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Sn, Sb, or Pb Or fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid; Alcohols such as sodium methoxide, sodium ethoxide, aluminum triisopropoxide, isopropyl titanate or n-butyl titanate; Phenols such as sodium phenolate; Or all catalysts used for normal esterification and transesterification, such as organometallic compounds other than metals such as Al, Ti, Zn, Sn, Zr or Pb. Since it is easy to obtain and also low in toxicity, it is widely used for esterification, and titanium-based catalysts, such as isopropyl titanate or n-butyl titanate, are the most preferable. As for the usage-amount of the catalyst at that time, 0.00001-5.0 mass% is preferable with respect to the said total raw material for polyesterdiol preparation, 0.0001-2.0 mass% is more preferable, 0.001-1.0 mass% is the most preferable. If the amount is too small, it takes a very long time to form a polyester polyol, and the product is easily colored. On the other hand, when the amount of the catalyst used is too large, there is a possibility of exhibiting excessive reaction promoting action for the polyurethane reaction.

It is preferable to perform the said esterification reaction in inert gas atmosphere, such as nitrogen and argon. Reaction pressure is arbitrary and can be implemented under normal pressure or reduced pressure according to the objective. In a reaction such as polyol and dicarboxylic acid or dicarboxylic acid ester, water and alcohol are generated during the reaction, so that an inert gas may be passed through the reaction system in order to promote their desorption from the reaction system.

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

When a catalyst is used at the time of the said esterification reaction, the (titanium system) catalyst used for reaction remains in the obtained polyester polyol product. Since the removal of the catalyst usually involves a complicated process, the produced polyester polyol is generally used in the production of polyurethane as it is without separating the (titanium) catalyst.

However, it is preferable to deactivate the titanium catalyst in the polyester polyol depending on the case where the content of the catalyst is large or depending on the purpose of the polyurethane. As a deactivation method of the titanium catalyst in polyester polyol, For example, (1) the method of making polyester polyol contact with water under heating; (2) The method of processing polyester polyol with phosphorus compounds, such as phosphoric acid, phosphate ester, phosphorous acid, and phosphite ester, etc. are mentioned. And in the case of the method of said (1) which makes contact with water, 1 mass% or more of water is added to polyester polyol, for example, and it is 1- at the temperature of 70-150 degreeC, Preferably it is 90-130 degreeC. You may heat about 3 hours. The deactivation process by heating at that time may be performed under normal pressure, or may be performed under pressure, and if the system is made into reduced pressure after deactivation process, the water used for deactivation can be removed smoothly from polyester polyol.

<Production Method of Polyurethane>

In the present invention, in order to prepare a polyurethane, (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the terminal of the molecule, (b) polyether polyol, (c) polyisocyanate compound, and (d) chain An extender is mainly used as a raw material for manufacturing.

In order to prepare the polyurethane, it is generally possible to produce the polyurethane in the presence of a solvent. In the present invention, the polyurethane is preferably prepared in the presence of an aprotic polar solvent.

In addition, as long as there is no restriction | limiting in particular, the usage-amount of each compound may use the quantity described above. Although an example of the manufacturing method in the coexistence of an aprotic polar solvent is shown below, if it exists in the coexistence of an aprotic polar solvent, it will not restrict | limit in particular.

The aprotic polar solvent in the present invention is not particularly limited, but from the viewpoint of solubility, also among the aprotic polar solvents, an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide A solvent selected from the group consisting of the side is preferably used. Specific examples of the amide solvent are N, N-dimethylacetamide, N, N-dimethylformamide, and mixtures of two or more thereof, and dimethylformamide or dimethylacetamide is particularly preferable.

As an example of a manufacturing method, the method (1 method) which makes (a), (b), (c) and (d) react together, or (a) and (b) is mixed first, the mixture and (c) ) To react a prepolymer of an isocyanate group at both ends, and then react the prepolymer with (d) (single method), (b) and (c), and then mix (a) with (d) And (b) (c) and (d), and then (a). Among them, the two-stage method is a step of preparing an intermediate sealed with both terminal isocyanates corresponding to the soft segment of polyurethane by reacting the polyether polyol with one or more equivalents of polyisocyanate in advance. By preparing the prepolymer once and then reacting with a chain extender, it is easy to adjust the molecular weight of the soft segment portion, it is easy to ensure phase separation of the soft segment and the hard segment, and there is a characteristic that it is easy to exhibit the performance as an elastomer. In particular, when the chain extender is a diamine, the reaction rate with the isocyanate group is significantly different compared to the hydroxyl group of the polyether polyol. Therefore, it is more preferable to perform the polyurethaneureaization in a two-stage method (prepolymer method).

<One way>

One-stage method is also called a one-shot method, and is a method of performing reaction by injecting (a), (b), (c) and (d) together. The amount of each compound used may be the amount described above.

Reaction usually reacts each component at 0-250 degreeC, and this temperature changes with quantity of a solvent, reactivity of the raw material used, reaction equipment, etc. If the temperature is too low, the progress of the reaction is too slow, or the productivity is poor because the solubility of the raw material or the polymer is low. If the temperature is too high, the side reaction or decomposition of the polyurethane resin occurs, which is not preferable. The reaction may be performed while degassing under reduced pressure. Moreover, reaction, you may add a catalyst, stabilizer, etc. as needed. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, octylic acid first tin, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, and the like. 6-dibutyl-4-methylphenol, distearyl thiodipropionate, di beta naphthyl phenylenediamine, tri (dinonylphenyl) phosphite, etc. are mentioned.

<Two steps>

The two-stage process is also called the prepolymer method, and prepares the prepolymer which previously reacted the polyisocyanate component and the polyol component in the reaction equivalence ratio = 1.0-10.00, and then to this, active hydrogen compound components, such as a polyisocyanate component or a polyhydric alcohol, an amine compound, etc. The reaction may be carried out in two stages of addition. In particular, a method of obtaining a polyurethane by reacting at least an equivalent polyisocyanate compound with a polyol component to form both terminal NCO prepolymers and subsequently reacting a short chain diol or diamine which is a chain extender is used.

In the present invention, the two-stage method can be carried out in a solvent coexistence, but it is preferable to carry out in an aprotic solvent coexistence, specifically, an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl sulfoxide A side solvent, and a mixture of two or more thereof.

In the present invention, among these solvents, when producing polyurethane, an aprotic polar solvent is preferable from the viewpoint of solubility. Among the aprotic polar solvents, an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide are preferable, and specific examples of the amide solvent include N, N-dimethylacetamide. , N, N-dimethylformamide is more preferable, and N, N-dimethylformamide or N, N-dimethylacetamide is particularly preferable.

When synthesizing the prepolymer, (1) a polyisocyanate compound and a polyetherpolyol may be directly reacted without first using a solvent to synthesize the prepolymer, and may be used as it is. (2) The prepolymer is synthesized by the method of (1). You may dissolve in a solvent and use it, (3) You may make polyisocyanate and polyether glycol react using a solvent from the beginning. In the case of (1), in the present invention, the polyurethane is prepared by a method such as dissolving the chain extender in a solvent or introducing a prepolymer and a chain extender into the solvent at the same time. It is important to obtain in the form of coexistence with the solvent.

As for the reaction equivalence ratio of NCO / active hydrogen group (polyol), a minimum is 1 normally, Preferably it is 1.05, and an upper limit is 10 normally, Preferably it is 5, More preferably, it is the range of 3. If the ratio is too small, the molecular weight of the resulting prepolymer becomes too large and the amount of hard segments to be described later decreases, so that there is a tendency for sufficient elasticity not to be obtained. If the ratio is too large, sufficient flexibility is not obtained by increasing the amount of hard segments to be described later. There is a tendency to not.

The amount of the chain extender used is not particularly limited, but the lower limit is usually 0.1, preferably 0.8, and the upper limit is usually 5.0, preferably 2.0, with respect to the equivalent of NCO groups included in the prepolymer.

Moreover, you may make monofunctional organic amine and alcohol coexist at the time of reaction.

The chain extension reaction usually reacts each component at 0 to 250 ° C, and the temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the temperature is too low, the progress of the reaction is too slow, or the productivity is poor because the solubility of the raw material or the polymer is low. If the temperature is too high, the side reaction or decomposition of the polyurethane resin occurs, which is not preferable. The reaction may be performed while degassing under reduced pressure.

Moreover, reaction, you may add a catalyst, stabilizer, etc. as needed. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, octylic acid tin, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, and the like. Dibutyl-4-methylphenol, distearylthiodipropionate, di-betanaphthylphenylenediamine, tri (dinonylphenyl) phosphite, and the like. However, when the chain extender is highly reactive, such as short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.

<Physical Properties of Polyurethane>

Since the polyurethane obtained by the above production method is reacted in the presence of a solvent, it is generally obtained in a state dissolved in a solution, but the physical value is not limited to the state as long as there is no particular limitation in the solution state or the solid state. .

Although the weight average molecular weight of a polyurethane differs according to a use, As a polyurethane polymerization solution, it is 10,000-1 million normally, Preferably it is 50,000-500,000, More preferably, it is 100,000-400,000, Especially preferably, 100,000 to 300,000. As molecular weight distribution, Mw / Mn = 1.5-3.5, Preferably it is 1.7-3, More preferably, it is 1.8-3. As a fiber, a film, and a moisture-permeable resin molded object, the weight average molecular weight of polyurethane is 10,000-1 million normally, Preferably it is 50,000-500,000, More preferably, it is 100,000-400,000, Especially preferably, it is 150,000 It is -400,000. As molecular weight distribution, Mw / Mn = 1.5-3.5, Preferably it is 1.7-3, More preferably, it is 1.8-3.

Moreover, it is preferable that the polyurethane obtained by the said manufacturing method contains 1-20 weight% of quantities of hard segments with respect to the total weight of a polyurethane polymer, More preferably, it is 3-15 weight%, More preferably Preferably it is 4-12 weight%, Especially preferably, it is 5-10 weight%. When the amount of this hard segment is too large, the polyurethane polymer obtained does not exhibit sufficient flexibility or elastic performance, or when a solvent is used, it tends to be difficult to melt and difficult to process. When too small, there exists a tendency for a urethane polymer to be too soft and to be difficult to process, or to obtain sufficient strength and elastic performance.

In addition, based on PJ Flory, Journal of American Chemical Society, 58, 1877-1885 (1936), the hard segment mentioned in this invention calculates the weight of an isocyanate and an amine coupling | bonding part with respect to a total weight by a following formula. .

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

here,

R = number of moles of isocyanate / (number of moles of hydroxyl groups of polyhydroxyhydrocarbon polymers having at least one hydroxyl group at the number of moles of the hydroxyl groups of the polyether polyol + molecule terminal)

Mdi = number average molecular weight of diisocyanate

Mda = number average molecular weight of the chain extender

Mp = average molecular weight of the number average molecular weight of the polyether polyol and the number average molecular weight of the polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular terminal

The polyurethane solution obtained in the present invention has a good storage stability because the gelation is less likely to proceed, the change in viscosity over time, the storage stability is good, and the thixotropy is small. Do. 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 based on the total weight of the solution dissolved in the solvent. 15 to 50% by weight. When the amount of polyurethane is too small, it is necessary to remove a large amount of solvent and the productivity tends to be low. When the amount of polyurethane is too large, the viscosity of the solution is too high and the operability or processability tends to be deteriorated.

Although it does not specifically designate a polyurethane solution, when storing over a long period of time, it is preferable to store it in inert gas atmosphere, such as nitrogen and argon, at normal temperature or below temperature.

<Polyurethane molded article and use thereof>

After obtaining the polyurethane manufactured by this invention and its urethane prepolymer solution, and shape | molding them, a polyurethane molded object can be obtained.

The polyurethane molded product of the present invention may be a molded product made of the polyurethane or the polyurethane obtained by the above-mentioned manufacturing method, and is not particularly limited, but is usually (a) a polyhydroxy hydrocarbon having at least one hydroxyl group at the terminal of the molecule. A polyurethane molded product comprising a polyurethane comprising a polymer, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, wherein the atomic composition on the surface of the polyurethane molded product (oxygen atom / carbon atom) ) Is 0.22 or less.

The atomic composition (oxygen atom / carbon atom) on the surface of a polyurethane molded body is specifically, oxygen, for example, when the molded body surface is measured by, for example, Electron Spectroscopy for Chemical Analysis (ESCA) or X-ray Photoelectron Spectroscopy (XPS). The relative abundance of atoms to carbon atoms is shown.

As a value of the atomic composition (oxygen atom / carbon atom) of the polyurethane molded object surface of this invention, Preferably it is 0.20 or less, More preferably, it is 0.16 or less. As this value becomes smaller, there is a tendency that the adhesiveness of the obtained molded product is reduced and the peelability is good. Moreover, Preferably it is 0.00 or more, More preferably, it is 0.05 or more. As this value increases, the packing property at the time of overlapping moldings obtained tends to become high. For example, when a molded body is a yarn, it becomes difficult to unwind and unshape the wound yarn.

In addition, as the polyurethane molded product of the present invention, in addition to having an atomic composition (oxygen atom / carbon atom) of 0.22 or less on the surface, it is preferable that the water contact angle of the surface is 80 degrees or more.

The water contact angle of this surface is obtained by dropping several µL of water droplets on the molded body surface and measuring the internal angle formed by the tangent of the droplets and the molded body surface within 10 seconds. As a value of the water contact angle on the surface of the polyurethane molded object of this invention, it is 80 degree | times or more, Preferably it is 83 or more, More preferably, it is 86 or more. As this value becomes larger, there is a tendency that the adhesiveness of the obtained molded product is reduced and the peelability is good. Moreover, Preferably it is 180 degrees or less, More preferably, it is 150 degrees or less. The smaller the value is, the more likely the packing property is when the molded products obtained are overlapped. For example, when the molded product is a thread, the wound is unwound and the shape is less likely to be disturbed.

In addition, the polyurethane, urethane prepolymer solution, and polyurethane molded product 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, flooring materials, sealants, medical materials, artificial leather and the like.

The polyurethane, polyurethane urea, and the urethane prepolymer solution produced in the present invention can be used for a cast polyurethane elastomer. For example, as industrial products, such as rolling rolls, paper rolls, office equipment, rolls such as pretension rolls, forklifts, solid-state tires such as automobile vehicle new trams, trolleys and carriages, casters, conveyor belt idlers, guide rolls, Pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, and the like. The present invention also applies to belts of OA machines, paper feed rolls, copy cleaning blades, snow blows, toothed belts, surf rollers, and the like.

The polyurethane and the urethane prepolymer solution produced in the present invention are also applied to the use as a thermoplastic elastomer. For example, it can be used as a tube, hoses, spiral tubes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical equipment, physicochemical equipment, metering pump, water treatment equipment, industrial robot, etc. used in the food and medical fields. Moreover, it is used as various belts, such as a round belt, a V belt, and a flat belt, and is used for various transmission mechanisms, spinning machines, packing machines, printing machines, and the like. In addition, heel tops, soles, couplings, packings, pole joints, bushes, gears, rolls, and other parts of shoes, sporting goods, leisure items, and belts for watches can be exemplified. Moreover, as an automotive part, an oil stopper, a gear box, a spacer, a chassis part, an interior product, a tire chain replacement product, etc. are mentioned. Moreover, films, such as a keyboard film and a film for automobiles, a curl cord, a cable sheath, a bellows, a conveyance belt, a flexible container, a binder, a synthetic leather, a dipping product, an adhesive agent, etc. can be illustrated.

The polyurethane and the urethane prepolymer solution produced in the present invention can be applied to use as a solvent-based two-component paint, and can be applied to wooden products such as musical instruments, Buddhist altars, furniture, cosmetic plywood, and sporting goods. Moreover, it can be used also for automobile repair as tar epoxy urethane.

The polyurethane and the urethane prepolymer solution produced in the present invention can be used as components such as moisture-curable one-component paints, blocked isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet curable paints, and the like. Paints for plastic bumpers, strippable paints, coatings for magnetic tape, floor tiles, flooring, paper, wood overprint varnishes, wood varnishes, high processing coil coats, fiber optic protective coatings, solder resists, metal printing It can be applied as a top coat, a base coat for vapor deposition, a white coat for food cans, and the like.

The polyurethane produced in the present invention and the urethane prepolymer solution thereof are applied to food packaging, shoes, shoes, magnetic tape binders, toilet paper, wood, structural members, and the like as adhesives, and also as components of low-temperature adhesives and hot melts. Can be used.

The polyurethane produced in the present invention and the urethane prepolymer solution thereof are binders, magnetic recording media, inks, castings, calcined bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortars, resin mortars, and rubber chip binders. It can be used for regeneration foam, glass fiber sizing, etc.

The polyurethane manufactured by this invention and its urethane prepolymer solution can be used as a component of a fiber processing agent, and can be used for preshrunk processing, spindle processing, water repellent processing, etc.

Polyurethane, polyurethaneurea, and the urethane preplier solution prepared in the present invention are, as sealant and / or caulking, concrete exposed walls, induced joints, periphery of chassis, wall PC joints, ALC joints, board joints, composite glass It can be used for sealant for automotive use, heat insulation chassis sealant, automotive sealant and the like.

The polyurethane and the urethane prepolymer solution produced in the present invention can be used as a medical material, and as a blood-compatible material, a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc. It can be used in bags, surgical gloves, artificial kidney potting materials, etc.

The polyurethane, polyurethane urea, and the urethane prepolymer solution produced in the present invention are used as raw materials such as UV curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating materials, etc. after modifying the ends. Can be used.

In particular, it is preferable to be used for a film or a fiber in utilizing the elastic performance and the moisture permeability characteristic of the polyurethane manufactured by this invention, As these specific uses, it is elastic for medical, hygiene material, artificial leather, and clothing. It is preferable to use for a fiber.

As mentioned above, although the usage example using the polyurethane manufactured by this invention and its urethane prepolymer solution was described, this invention is not limited to these uses.

Although the manufacturing method of a film and a fiber is described below, a manufacturing method is not restrict | limited in particular.

<Production method of the film>

The manufacturing method of a film does not have limitation in particular, A well-known method can be used. For example, as a manufacturing method of a film, a wet film manufacturing method which applies a polyurethane resin solution to a support body or a mold release material, extracts a solvent and other soluble substances in a coagulation bath, and apply | coats a polyurethane resin solution to a support body or a mold release material, The dry film manufacturing method which dries a solvent by heating or pressure reduction etc. is mentioned. Although the support body used at the time of dry film manufacture is not specifically limited, The paper, cloth, etc. which apply | coated polyethylene, a polypropylene film, glass, a metal, and a peeling material are used. The coating method is not particularly limited, but any known one such as a knife coater, roll coater, spin coater, gravure coater, or the like may be used. The drying temperature can be arbitrarily set according to the capacity of the dryer, but it is necessary to select a temperature range in which insufficient drying or rapid desolvent does not occur. Preferably it is room temperature-300 degreeC, More preferably, it is the range of 60 degreeC-200 degreeC.

<Film properties>

The thickness of the film of this invention is 10-1000 micrometers normally, Preferably it is 10-500 micrometers, More preferably, it is 10-100 micrometers. When the thickness of the film is too thick, sufficient moisture permeability tends not to be obtained, and when too thin, pin holes tend to occur or the film tends to block and tends to be difficult to handle. Moreover, this film can be used suitably for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. Moreover, what apply | coated the film to support bodies, such as cloth and a nonwoven fabric, may be sufficient. In this case, it may be thinner than 10 µm.

Elongation at break is usually at least 100%, preferably at least 200%, more preferably at least 300%, even more preferably at least 500%. The breaking strength is usually 5 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and still more preferably 30 MPa or more.

In the 300% elongation-shrinkage repeated test at 23 ° C., the elasticity retention ratio (Hr1 /) obtained by the ratio of the stress in the 150% elongation at the first contraction to the stress in the 150% elongation at the first elongation (Hr1 / H1) is usually at least 10%, preferably at least 20%, more preferably at least 30%, even more preferably at least 40%. Similarly, the elasticity retention rate (Hr5 / H5) to be understood as the ratio of the stress in the 150% elongation at the fifth contraction to the stress in the 150% elongation at the fifth stretch is usually 30% or more, preferably 50 % Or more, more preferably 70% or more, even more preferably 85% or more.

Moreover, in the 300% elongation-shrinkage repeated test at 23 degreeC, the elasticity retention rate grasped | ascertained by the ratio of the stress in 150% elongation at the time of 2nd extension with respect to the stress in 150% elongation at the time of 1st elongation ( H2 / H1) is usually at least 20%, preferably at least 40%, more preferably at least 50%, even more preferably at least 60%.

Further, the second residual strain 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 20% or less. . In addition, the residual strain in the fifth time is usually 50% or less, preferably 35% or less, more preferably 30% or less, particularly preferably 25% or less.

Moreover, the physical property of a polyurethane film and a yarn has a very favorable correlation, and the physical-property value obtained by the test of a film, etc. shows the same tendency also in a yarn (fiber).

<Use of polyurethane fiber>

The fiber using the polyurethane of the present invention is more specifically exemplified in use, such as leg portions of pants, panty and stockings, diaper covers, paper diapers, sports clothing, underwear, socks, stretch clothing and swimwear excellent in fashion. It is used suitably for uses, such as a leotard. This is because it is excellent in elongation recovery, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, workability and the like.

Example

Although an Example of this invention is demonstrated further more concretely below, this invention is not limited by these Examples, unless the summary is exceeded. In addition, the analysis and the measurement in the following examples and comparative examples were based on the following methods.

<Number average molecular weight of polyhydroxyhydrocarbon polymer and polyether polyol>

The number-average molecular weight of the polyhydroxyhydrocarbon polymer and the polyether polyol used in the present invention was determined from a hydroxyl value (KOH (mg) / g) measurement method by the acetylation method according to JIS K 1557-1: 2007. .

<Molecular Weight of Polyurethane and Polyurethane Urea>

The molecular weight of the obtained polyurethane or polyurethane urea prepared a dimethylacetamide solution of polyurethane or polyurethane urea, and produced a GPC device [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TskgelGMH-XL (2 pieces)) The number average molecular weight (Mn) and the weight average molecular weight (Mw) in standard polystyrene conversion were measured.

<Peel test method>

Two obtained films were laminated | stacked on each other, the film of 4 cm in length (each including the initial test length part and 2.5 cm overlapping part at the time of fixing a 1.5 cm length tensile tester) was obtained by the test piece puncher, and the film of width 1cm. The test piece was left to stand for 10 minutes under conditions of a temperature of 25 ° C. and a relative humidity of 50% while applying a pressure of 200 g / cm 2 to a portion where the film overlaps, and then used a tensile tester ("Rometer NRM-2003J" manufactured by FUDOH). And the T-film peel strength was measured by tensioning the test film at a rate of 300 mm / min.

<Film properties>

Polyurethane or polyurethaneurea test piece was made into a single-shaped shape having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm, and according to JIS K 6301, a tensile tester [manufactured by Orientec, product name "Tensilon UTM-III-100" ], Tensile strength at break at 23 ° C (55% relative humidity), tensile failure elongation, strength at 100% elongation and 300% elongation at a distance of 50 mm between the chuck and 500 mm / min. It was.

Surface Atom Composition

The surface atomic composition was determined by ESCA (Electron Spectroscopy for Chemical Analysis) measurement. The measurement was performed using Albak-Pi Co., Ltd. ESCA apparatus "PHI Model 5800". Measurement conditions are as follows.

X-ray here: monochromatic AlKα (1486.6 eV)

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

· Neutral gun: use (for antistatic)

Input Lens Setting (Lens Area Mode): Minimum Area Mode

LENS MODE: 5 (Minimum Area Mode)

Aperture Number: 5

Emission (angle formed by the central axis of the detector from the sample normal): 45 degrees

PassEnergy: 23.5 eV

Charge shift correction: The binding energy of the C1s peak of the C-H bond carbon was adjusted to 285.0 eV.

The relative abundance ratio of oxygen atoms to carbon atoms was calculated by the following equation.

Relative abundance 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 area of each peak of oxygen O1s and carbon C1s was calculated using the Savitzky-Golay algorithm (9 points) using the MultiPak Ver.8.2C software attached to the apparatus, and using the background curve of the shirley method. The oxygen O1s and carbon C1s peak binding energies used for the calculation of relative abundance and the corrected relative sensitivity coefficients used in the MultiPak Ver.8.2C software are as follows.

O1s: binding energy = around 532.5 eV

Correction relative sensitivity factor = 13.118

C1s: binding energy = around 285.0 eV

Correction relative sensitivity factor = 5.220

As for the peak area of carbon C1s, peaks derived from the shake up of the benzene ring obtained by connecting the minimum values around 280 eV and 290.5 eV by shirley and the minimum values near 290.5 eV and 293 eV by shirley (291 What added the area of (about -293 eV) was used.

<Water contact angle>

Using an automatic contact angle meter DM-300 manufactured by Kyowa Interface Science Co., Ltd., 1.5 to 2.0 µl of water droplets were dropped on the surface of the polyurethane film, and after 5 seconds, the angle formed by the tangent of the water droplets and the surface of the molded body was measured. The same operation was repeated 5 times, changing the place of a film, and the average value of the obtained 5 point value was made into the water contact angle.

&Lt; Example 1 >

142.5 parts by weight of polytetramethylene ether glycol (number average molecular weight 1968 calculated from hydroxyl value, manufactured by Mitsubishi Chemical Corporation) and a hydrogenated polybutadiene polyol manufactured by Mitsubishi Chemical Corporation (brand name "poly Ter HA "Number average molecular weight: 2187, Average number of bonds of the hydroxyl group per molecule: 1.8) 7.5 weight part was added, and this mixture was made into the raw material for polyurethane production. The ratio of polyter HA to this mixture was 5% by weight. Then, 31 weight part of 4,4'- diphenylmethane diisocyanate (it may abbreviate as "MDI" hereafter) heated at 40 degreeC was added. At this time, the reaction equivalence ratio of NCO / active hydrogen group (polyether polyol and chain extender) was 1.6. And this flask was set to 45 degreeC oil bath, the temperature of the oil bath was heated up to 70 degreeC over 1 hour, stirring by anchor-type stirring blades in nitrogen atmosphere, and it kept at 70 degreeC after that for 3 hours. After confirming that the reaction rate of NCO exceeded 99% by reacting the remaining NCO group with an excess of dibutylamine and then back titrating the remaining dibutylamine with hydrochloric acid, the oil bath was removed, and the flask was placed with N, N-. 271 parts of dimethylacetamide (Hereinafter, abbreviated as "DMAC". Kanto Chemical Co., Ltd. make) were added, and the polyurethane prepolymer solution was prepared by stirring and dissolving at room temperature.

Ethylenediamine (EDA) / diethylamine (DEA) = 89/11 (molar ratio) = 1.72 / 0.27 (weight ratio) used as a chain extender by holding 380 parts by weight of the polyurethane prepolymer solution at 10 캜 0.6% DMAC solution was prepared. The said polyurethane prepolymer solution cooled and maintained at 10 degreeC was added to this 0.6% DMAC solution, stirring at high speed, and the polyurethane urea DMAC solution of 20% of the polymer concentration was obtained.

After aging this solution overnight at 25 degreeC, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 17.2 million and molecular weight distribution was 2.4. Moreover, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78 weight%.

The polyurethaneurea solution thus obtained was cast on a glass plate, and dried at 60 ° C. to obtain a colorless transparent film having a thickness of about 50 μm. The thickness of the film was measured by a thickness meter.

As a result of performing the peeling test of this film, the stress required for peeling was 5.7 g / cm, and peelability was favorable. Moreover, the obtained elastic film was the characteristic as shown in Table 1. In addition, the surface atomic composition of this 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 weight part of polytetramethylene ether glycol (number average molecular weight 1968 computed from hydroxyl value, the product made by Mitsubishi Chemical Corporation) of the raw material for polyurethane manufacture, and "polyether HA" (number average molecular weight: 2187, 1 molecule) Average number of bonds of the hydroxyl group of sugar: 1.8) 1.5 parts by weight was added and mixed (the ratio of polyter HA in this mixture was 1% by weight), and ethylenediamine / diethylamine = 1.81 / 0.28 (weight ratio) A prepolymer and a polyurethaneurea solution were obtained in the same manner as in Example 1 except for the above.

After aging this solution overnight at 25 degreeC, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 20.2 million and molecular weight distribution was 2.5. Moreover, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 81 weight%.

From this polyurethaneurea solution, a colorless and transparent polyurethaneurea film having a thickness of about 50 μm was obtained.

As a result of performing the peeling test of this film, the stress required for peeling was 5.7 g / cm, and peelability was favorable. Moreover, the obtained elastic film was the characteristic as shown in Table 1. Moreover, the surface atomic composition of this 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 1968 calculated from hydroxyl value, manufactured by Mitsubishi Chemical Corporation) of the raw material for polyurethane production, and "polyter HA" (number average molecular weight: 2187, 1 molecule) The average bond number of the hydroxyl group of sugar: 1.8) 0.15 weight part was added and mixed (The ratio of polyter HA in this mixture is 0.1 weight%), it carried out similarly, and obtained the prepolymer and polyurethaneurea solution.

After aged this solution at 25 degreeC overnight, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 19.8 million, and molecular weight distribution was 2.4. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 82 weight%.

From this polyurethaneurea solution, a colorless and transparent polyurethaneurea film having a thickness of about 50 μm was obtained.

As a result of performing the peeling test of this film, the stress required for peeling was 33 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 1. In addition, the surface atomic composition of this film was 0.194. The results are shown in Table 1.

<Example 4>

Example 1 WHEREIN: 105 weight part of polytetramethylene ether glycol (number average molecular weight 1968 computed from the hydroxyl value, the product made by Mitsubishi Chemical Corporation), and an average bond of "polyether HA" (number average molecular weight: 2187, hydroxyl groups per molecule) Number: 1.8) A prepolymer and a polyurethaneurea solution were obtained in the same manner except for adding 45 parts by weight of the mixture (the ratio of polyter HA in this mixture was 30% by weight).

After aged this solution at 25 degreeC overnight, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 19.8 million, and molecular weight distribution was 2.4. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 57 weight%.

From this polyurethaneurea solution, a slightly turbid polyurethaneurea film having a thickness of about 50 μm was obtained.

As a result of performing the peeling test of this film, the stress required for peeling was 33 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 1.

Comparative Example 1

In Example 1, 150 parts by weight of polytetramethylene ether glycol (number average molecular weight 1968, manufactured by Mitsubishi Chemical Co., Ltd., calculated from hydroxyl groups) was used in the same manner without using "polyether HA", Prepolymer and polyurethaneurea solutions were obtained.

After aging this solution overnight at 25 degreeC, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 19.10,000 and molecular weight distribution was 2.6. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78 weight%.

From this polyurethaneurea solution, a colorless and transparent polyurethaneurea film having a thickness of about 50 μm was obtained.

As a result of performing the peeling test of this film, the stress required for peeling was 50 g / cm, and extending | stretching of 12% of film was seen with respect to the initial test length at the time of peeling. In addition, the obtained elastic film was the characteristic as shown in Table 1. Moreover, the surface atomic composition of this film was 0.239 and the water contact angle was 76 degrees. The results are shown in Table 1.

Example 5

[Production of Polyester Polyol]

1.2 mg of tetrabutyl ortho titanate (Tokyo Chemical Co., Ltd.), 30 g (20.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Co., Molecular Weight 1500) in a 100 ml four-neck round bottom flask equipped with a stirrer , 10 g (87.6 mmol) of ε-caprolactone (Across) was taken and weighed. A reflux tube and a nitrogen inlet tube were mounted, the reaction vessel was immersed in an oil bath, heated up to 190 ° C for 30 minutes, and reacted at 190 ° C for 7 h to obtain polyester polyol 1. In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 1 are also shown.

[Production of Polyurethane Urea]

6.52 parts by weight of polytetramethylene ether glycol (number average molecular weight 1955, manufactured by Mitsubishi Chemical Co., Ltd.), which was previously heated to 40 ° C. in a 1 L flask, and the polyester polyol 1 synthesized above. It added and mixed, and made this mixture the raw material for polyurethane manufacture. The ratio of polyesterpolyol 1 to this mixture was 5% by weight. Then, 26.8 weight part of 4,4'- diphenylmethane diisocyanate (it may abbreviate as "MDI" hereafter) heated at 40 degreeC was added. At this time, the reaction equivalence ratio of NCO / active hydrogen group (polyether polyol and chain extender) was 1.6. And this flask was set to 45 degreeC oil bath, the temperature of the oil bath was heated up to 70 degreeC over 1 hour, stirring by anchor-type stirring blades in nitrogen atmosphere, and it kept at 70 degreeC after that for 3 hours. After confirming that the reaction rate of NCO exceeded 99% by reacting the remaining NCO group with an excess of dibutylamine and then back titrating the remaining dibutylamine with hydrochloric acid, the oil bath was removed, and the flask was placed with N, N-. 236 parts of dimethylacetamide (it may abbreviate as "DMAC" hereafter. Product made by Kanto Chemical Co., Ltd.) were added, and the polyurethane prepolymer solution was prepared by stirring and dissolving at room temperature.

The polyurethane prepolymer solution was kept cooled to 10 ° C., while 0.5 of ethylenediamine (EDA) / diethylamine (DEA) = 89/11 (molar ratio) = 1.66 / 0.24 (weight ratio) used as a chain extender. A% DMAC solution was prepared. The said polyurethane prepolymer solution cooled and maintained at 10 degreeC was added to this 0.5% DMAC solution, stirring at high speed, and the polyurethaneurea DMAC solution of 20% of the polymer concentration was obtained.

After aged this solution at 25 degreeC overnight, when the weight average molecular weight and molecular weight distribution were measured by GPC, the weight average molecular weight was 21.90,000 and molecular weight distribution was 2.7. In addition, the ratio of (b) polytetramethylene ether glycol in the obtained polyurethane was 78 weight%.

The polyurethaneurea solution thus obtained was cast on a glass plate, and dried at 60 ° C. to obtain a colorless transparent film having a thickness of about 50 μm. The thickness of the film was measured by a thickness meter.

As a result of performing the peeling test of this film, the stress required for peeling was 4.4 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.097 and the water contact angle was 95 degrees. The results are shown in Table 3.

<Example 6>

[Production of Polyester Polyol]

Instead of GI-1000, 60 g (28.6 mmol) of GI-2000 (Nippon Soda Co., Molecular Weight 2100) was used, and 3.6 g of tetrabutyl ortho titanate was used and 12 g (105 mm) of ε-caprolactone. A polyester polyol 2 was produced in exactly the same manner as in Example 5 except for setting ol). In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 2 are also shown.

[Production of Polyurethane Urea]

The polyurethaneurea solution and the film were obtained like Example 5 by the raw material injection | pouring quantity of the polyurethane manufacture shown in Table 3. As a result of performing the peeling test of this film, the stress required for peeling was 6.7 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.094 and the water contact angle was 94 degrees. The results are shown in Table 3.

<Example 7>

[Production of Polyester Polyol]

Polyesterpolyol 3 in the same manner as in Example 6, except that 51.3 g (24.4 mmol) of GI-2000, 2.5 mg of tetrabutylortho titanate, and 22 g (193 mmol) of ε-caprolactone were used. Was prepared. In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 3 are also shown.

[Production of Polyurethane Urea]

The polyurethaneurea solution and the film were obtained like Example 5 by the raw material injection | pouring quantity at the time of polyurethane production shown in Table 3. As a result of performing the peeling test of this film, the stress required for peeling was 3.6 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.100 and the water contact angle was 95 degrees. The results are shown in Table 3.

<Example 8>

[Production of Polyester Polyol]

Instead of GI-1000, 60 g (27.9 mmol) of hydrogenated polyisoprene polyol Epol (Idemitsu Hexane, molecular weight 1800) was used, and 3.6 mg of tetrabutyl ortho titanate was used and 10 g of ε-caprolactone was used. Polyester polyol 4 was prepared in exactly the same manner as in Example 5 except that the concentration was (87.6 mmol). In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 4 are also shown.

[Production of Polyurethane Urea]

The polyurethaneurea solution and the film were obtained like Example 5 by the raw material injection | pouring quantity at the time of polyurethane production shown in Table 3. As a result of performing the peeling test of this film, the stress required for peeling was 4.5 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.154 and the water contact angle was 88 degrees. The results are shown in Table 3.

Example 9

[Production of Polyester Polyol]

In a 100 ml four-necked round bottom flask equipped with a stirrer, 4.2 mg of tetrabutyl ortho titanate (Tokyo Chemical Co., Ltd.), 66.0 g (44.0 mmol) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Co., Molecular Weight 1500) And 3.8 g (22.0 mmol) of dimethyl adipic acid (Tokyo Chemical Co., Ltd.) were attached and taken. A reflux tube and a nitrogen introduction tube were mounted, the reaction vessel was immersed in an oil bath, heated up to 190 ° C for 30 minutes, and reacted at 190 ° C for 7 h to obtain polyester polyol 5. During the reaction, the outlet portion was warmed to 120 ° C. with a tape heater, and methanol produced by the reaction was accompanied by nitrogen to distill off. In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 5 are also shown.

[Production of Polyurethane Urea]

The polyurethaneurea solution and the film were obtained like Example 5 by the raw material injection | pouring quantity at the time of polyurethane production shown in Table 3. As a result of performing the peeling test of this film, the stress required for peeling was 10.8 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.072 and the water contact angle was 96 degrees. The results are shown in Table 3.

<Example 10>

[Production of Polyester Polyol]

3.09 g (21.1 mmol) of dimethyl succinate (Tokyo Chemical Co., Ltd.) was used instead of dimethyl adipic acid, and the use of GI-1000 was 63.4 g (42.3 mmol) and the amount of tetrabutyl ortho titanate was 2.2 mg. A polyester polyol 6 was prepared in exactly the same manner as in Example 9 except for the above. In Table 2, the theoretical molecular weight and theoretical oxygen content of this polyester polyol 6 are also shown.

[Production of Polyurethane Urea]

The polyurethaneurea solution and the film were obtained like Example 5 by the raw material injection | pouring quantity at the time of polyurethane production shown in Table 3. As a result of performing the peeling test of this film, the stress required for peeling was 13.0 g / cm, and peelability was favorable. In addition, the obtained elastic film was the characteristic as shown in Table 3. In addition, the surface atomic composition of this film was 0.083 and the water contact angle was 98 degrees. The results are shown in Table 3.

Comparative Example 2

[Production of Polyurethane Urea]

In the raw material injection | pouring quantity at the time of polyurethane production shown in Table 3, it carried out similarly to Example 5, and obtained the polyurethaneurea solution and film which do not contain the polyester polyol. As a result of performing the peeling test of this film, the stress required for peeling was 66.3 g / cm, and peelability was bad. In addition, the obtained elastic film was the characteristic as shown in Table 3. Moreover, the surface atomic composition of this film was 0.239 and the water contact angle was 76 degrees. The results are shown in Table 3.

Although this invention was demonstrated in detail and with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2008-306247) for which it applied December 01, 2008, and the Japanese patent application (Japanese Patent Application No. 2009-179463) for which it applied for July 31, 2009, The content here Introduced by reference.

According to the present invention, a polyurethane can be produced while maintaining a constant compatibility with the polyether polyol, and the adhesiveness of the polyurethane obtained can be reduced. Moreover, when shape | molding the obtained polyurethane, the peelability of moldings can be improved. Furthermore, when the medical fiber and the like are molded using the elastic fiber made of this polyurethane, the operational stability is improved by reducing the cost by reducing the amount of use of the emulsion and the smoothing agent, and by reducing the product fouling and the clogging frequency of the machine or apparatus. As the frictional resistance is reduced, driving power reduction can be expected. Therefore, the industrial value of this invention is remarkable.

Claims (29)

The raw material of (a) a polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the terminal of the molecule, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender is subjected to addition polymerization reaction to obtain a polyurethane. In obtaining, (a) polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the molecular terminal and (b) polyhydroxypolyol having at least one hydroxyl group at the molecular terminal relative to the sum of the polyether polyols The proportion of the polymer is 0.01 to 50.00% by weight, and the reaction is carried out in the presence of an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and a solvent selected from the group consisting of dimethyl sulfoxide. Method of producing polyurethanes. The method of claim 1,
The number average molecular weight of the polyhydroxy hydrocarbon type polymer which has at least 1 hydroxyl group at the said (a) molecule terminal is 500-5000, The manufacturing method of the polyurethane characterized by the above-mentioned. The method according to claim 1 or 2,
The method for producing a polyurethane, wherein the average number of hydroxyl groups per molecule of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) is 1.5 to 2.7. The method according to any one of claims 1 to 3,
The method for producing a polyurethane, wherein the polyisocyanate compound (c) is an aromatic polyisocyanate. The method according to any one of claims 1 to 4,
And (d) the chain extender is a polyamine compound. 6. The method according to any one of claims 1 to 5,
The method for producing a polyurethane, wherein the main skeleton of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the terminal (a) is hydrogenated polybutadiene. The method according to any one of claims 1 to 6,
The polyhydroxy hydrocarbon-based polymer having at least one hydroxyl group at the terminal (a) is a polyester polyol formed from (A) a polyhydroxy hydrocarbon polymer and a (B) ester group-containing compound or carboxyl group-containing compound. The manufacturing method of the polyurethane characterized by the above-mentioned. The method of claim 7, wherein
(A) and (B) form said at least 1 ester bond, and the said polyester polyol is 2.0 mass% or more and 13.5 mass% or less, The polyurethane production characterized by the above-mentioned. Way. The method according to claim 7 or 8,
The said (B) is polylactone, The manufacturing method of the polyurethane characterized by the above-mentioned. The method according to any one of claims 7 to 9,
The said polyester polyol is a block copolymer of the (B) (A) (B) type formed from the said (A) and the said (B), The manufacturing method of the polyurethane characterized by the above-mentioned. The method according to claim 7 or 8,
Said (B) is dicarboxylic acid, The manufacturing method of the polyurethane characterized by the above-mentioned. The method of claim 11,
The carbon number of the said dicarboxylic acid is 2 or more and 15 or less, The manufacturing method of the polyurethane characterized by the above-mentioned. The method of claim 10 or 11,
The polyester polyol is a block copolymer of (AB) _n A type (wherein n is an integer of 1 or more) formed from the above (A) and (B), wherein the polyurethane is produced. A polyurethane produced by the method for producing a polyurethane according to any one of claims 1 to 13. A polyurethane comprising (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyetherpolyol, (c) a polyisocyanate compound, and (d) a chain extender, wherein the polyurethane (b) Polyurethane, characterized in that the weight ratio of the polyether polyol is 54% to 99% by weight. The polyurethane molded body which consists of the polyurethane of Claim 14 or 15. Polyurethane molded article consisting of a polyurethane comprising (a) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender A polyurethane molded body, wherein the atomic composition (oxygen atom / carbon atom) on the surface of the polyurethane molded body is 0.22 or less. The method of claim 17,
The polyurethane molded body characterized by the water contact angle of the said polyurethane molded body surface of 80 degree or more. It consists of the polyurethane of Claim 14 or 15, The film characterized by the above-mentioned. A fiber comprising the polyurethane according to claim 14 or 15. A polyester polyol formed from (A) a polyhydroxy hydrocarbon polymer and (B) an ester group-containing compound or a carboxyl group-containing compound, wherein (A) and (B) form at least one ester bond, and Oxygen content in a polyester polyol is 2.0 mass% or more and 13.5 mass% or less, The polyester polyol characterized by the above-mentioned. The method of claim 21,
Polyester polyol, characterized in that (B) is polylactone. The method of claim 21 or 22,
The polyester polyol is a block copolymer of the (B) (A) (B) type formed from the said (A) and the said (B). The method of claim 21,
(B) is a dicarboxylic acid, polyester polyol, characterized in that. The method of claim 24,
Carbon number of the said dicarboxylic acid is 2 or more and 15 or less, The polyester polyol characterized by the above-mentioned. The method of claim 24 or 25,
The polyester polyol is a block copolymer of (AB) _n A type (wherein n is an integer of 1 or more), wherein the polyester polyol is formed of the above (A) and (B). 27. The method of any of claims 21 to 26,
The polyester polyol whose number average molecular weights of the said polyester polyols are 500 or more and 5000 or less. The method according to any one of claims 21 to 27,
The polyester polyol, wherein the polyhydroxy hydrocarbon polymer (A) is a hydrogenated polydiene polyol. At least one of the hydroxyl groups which comprise the polyester polyol of any one of Claims 21-28 forms the urethane bond, The polymer characterized by the above-mentioned.