KR101718296B1 - Process for production of polyurethane, and uses of polyurethane produced thereby - Google Patents

Abstract

An object of the present invention is to provide a process for producing a polyurethane and a polyurethane urea having low adhesiveness and high peelability when producing a polyurethane urea with a polyether polyol, a polyisocyanate compound and a chain extender. The present invention provides a polyurethane resin composition comprising (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) Which is produced in the presence of an aprotic polar solvent in the production of a polyurethane.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polyurethane and a use of the polyurethane obtained therefrom,

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

Polyurethane compounds and polyurethaneurea compounds have been applied in various fields. The polyurethane compound is mainly composed of a polyhydroxy compound such as a polyester polyol or a polyether polyol, an isocyanate compound and, if necessary, a chain extender, a foaming agent, a foaming agent and the like, and is made of a polyurethane based elastic fiber, a polyurethane- And the like. Particularly, a polyurethane urea structure fiber has a property of excellent elastic properties and elongation recovery property because a polyether polyol is used as a soft segment component and a polyamine compound having a high cohesive strength is used as a hard segment. However, since these polyurethane based elastic fibers are highly sticky to each other, they have poor releasability at the time of release and have a large frictional resistance. Therefore, the process of manufacturing the radiator, A thread break occurs in a device. Therefore, problems such as yarn breakage in the processing step are liable to occur. Therefore, in order to lower the frictional resistance of the apparatus and the yarn in the working process, there are a method of adding a solid metal soap, an oil-soluble polymer, a higher fatty acid, an amino-modified silicone or the like as an emulsion, or a method of adding talc, silica, colloidal alumina Or titanium oxide, or a method of introducing silicone diol or silicone diamine into a part of the polyurethane main chain, and the like (for example, Patent Document 1).

However, even in this method, a sufficient anti-sticking effect is not obtained, or when the smooth agent causes significant wear to the radiator, the spinning wheel, the knee or the guide, or the oligomer in the fiber extracted by the emulsion component during the regular knitting process, There is a problem that a solid or a high viscosity component is separated into a solid or a paste and adheres to a large amount of the fibers to cause product contamination or clogging of a machine or an apparatus, For this reason, there has been a demand for a process for producing polyurethane which has low adhesiveness and high releasability (or peelability between polyurethanes) at the time of release without using such an emulsion or smoothing agent.

On the other hand, as an example of using a polyhydroxy hydrocarbon polymer having a hydroxyl group in a raw material of polyurethane, there is a use of a urethane-based resin as a modifier for improving the adhesiveness of a polyolefin resin material (Patent Document 2) Studies have been made to improve the durability of polyurethane based elastic fibers by mixing polyurethane with tetramethylene glycol (Patent Document 3). However, in the method described in Patent Document 3, since the hydrophobicity of the high molecular polyol is excessively high, there is a problem that the compatibility with the polyether polyol is poor, the gel is formed at the time of producing the polyurethane, and is not uniformly dispersed at the time of producing the yarn or the film. It is known that a stretch fabric or swimsuit made of fibers made of polyurethane produced by the method described in Patent Document 3 is excellent in chlorine-resistant, hot water resistance, light resistance, and the like, and a polyhydroxy hydrocarbon polymer having a hydroxyl group is used as a raw material To reduce the tackiness of the polyurethane and to lower the tackiness of molded products such as films made of polyurethane or elastic fibers and to improve the peelability. The polyurethane based elastic fibers described in Patent Document 3 are exemplified by polyhydric alcohols and polyvalent amines as chain extender, but they are elastic fibers obtained by melt spinning using a substantially polyhydric alcohol as a chain extender. By this method, polyvalent amines There has been a problem that it is difficult to form a so-called polyurethane-urea structure by homogeneous fibers or films due to the occurrence of an adverse reaction such as gelation or three-dimensional crosslinking at the time of chain extension reaction.

On the other hand, for the purpose of improving the physical properties of the polyurethane elastic fibers, studies have been made to improve the raw material components of the polyurethane. For example, as an example of using a polyester polyol, a glycol constituent component having a polyhydric alcohol having a hydrocarbon group as a side chain as an essential component and a hydrophobic polyester polyol formed of a carboxylic acid constituent component having a dimer acid as an essential component (Patent Document 4). However, even when these polyester polyols were used, no polyurethane still exhibiting sufficient peelability was obtained.

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

SUMMARY OF THE INVENTION In view of the above problems, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a polyurethane resin composition which is excellent in polyurethane elastic fibers, films, and high performance polyurethane applications It is still another object of the present invention to provide a method for producing polyurethane and polyurethane urea that is very useful and has low adhesiveness and high peelability, and a novel polyester polyol useful for producing polyurethaneurea.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that, in producing polyurethane, a polyether polyol and a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, And a polyester polyol having a constant oxygen content, more preferably by mixing the polyester polyol with a polyether polyol and reacting the polyisocyanate compound and the chain extender under the coexistence of a solvent to obtain a polyurethane and a poly It has been found that the adhesiveness of the urethane urea can be reduced, and the releasability and the property at the time of release can be improved, thereby completing the present invention.

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

[1] A process for producing a polyhydroxy hydrocarbon polymer, which comprises: (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (A) a polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular end and (b) a polyether polyol, (a) a polyol having at least one hydroxyl group at the molecular end, Wherein the reaction is carried out in the presence of 0.01 to 50.00% by weight of a hydroxy-hydrocarbon polymer in the presence of a solvent selected from the group consisting of an amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylsulfoxide By weight of the polyurethane.

[2] The process for producing a polyurethane according to [1], wherein the polyhydroxy hydrocarbon polymer (a) having at least one hydroxyl group at the molecular end thereof has a number average molecular weight of 500 to 5000.

[3] Preferably, the polyhydroxyhydrocarbon polymer (a) having at least one hydroxyl group at the molecular end thereof has an average number of hydroxyl groups per molecule of 1.5 to 2.7. The polyhydroxyhydrocarbon polymer according to [1] or [2] ≪ / RTI >

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

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

[6] Preferably, in any one of [1] to [5], wherein the main skeleton of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end (a) is hydrogenated polybutadiene ≪ / RTI >

Preferably, the polyhydroxy hydrocarbon polymer (a) having at least one hydroxyl group at the molecular end is a polyhydroxy hydrocarbon polymer (A) and an ester group-containing compound or a carboxyl group-containing compound (B) The process for producing a polyurethane according to any one of [1] to [6], wherein the polyester polyol is a polyester polyol.

[8] Preferably, the polyester polyol is a polyester polyol wherein the (A) and the (B) form at least one ester bond and the oxygen content of the polyester polyol is 2.0% by mass or more and 13.5% Wherein the polyurethane is a polyurethane.

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

[10] Preferably, the polyester polyol according to any one of [7] to [9], wherein the polyester polyol is a block copolymer of the (B), (A) Wherein the polyurethane is produced by a method comprising the steps of:

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

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

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

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

[15] A polyurethane comprising (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) Wherein the weight ratio of the polyether polyol (b) in the polyurethane is 54 wt% to 99 wt%.

[16] A polyurethane molded article characterized by comprising the polyurethane according to the above [14] or [15].

(17) A polyurethane resin composition comprising (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and Wherein the polyurethane molded article has an atomic composition (oxygen atom / carbon atom) of 0.22 or less on the surface of the polyurethane molded article.

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

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

[20] A fiber characterized by 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 , And the content of oxygen in the polyester polyol is 2.0% by mass or more and 13.5% by mass or less.

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

[21] or [22], wherein the polyester polyol is a block copolymer of the (B) (A) (B) type in which the polyester polyol is formed from the above (A) The polyester polyol described.

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

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

Preferably, the polyester polyol is an (AB) _nA type block copolymer (provided that n is an integer of 1 or more) formed of the above (A) and (B) 24] or [25].

[27] Preferably, the polyester polyol according to any one of [21] to [26], wherein the polyester polyol has a number average molecular weight of 500 to 5,000.

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

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a polyurethane while maintaining constant compatibility with a polyether polyol, and it is possible to reduce the tackiness of the obtained polyurethane. Further, when the obtained polyurethane is molded, the peelability of the molded articles can be improved. Further, when the elastic fiber made of this polyurethane is used to form a medical or the like, cost reduction due to reduction in the amount of use of an emulsion or a smoothing agent, improvement in operating stability due to product fouling, , The frictional resistance is reduced, and driving power reduction can be expected.

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

<Polyurethane>

The polyurethane of the present invention is a polyurethane obtained by (a) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) And the like.

The polyurethane in the present invention means a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) . The weight ratio of (b) the polyether polyol in the polyurethane is not particularly limited, but it is usually from 54 to 99% by weight, preferably from 60 to 90% by weight, more preferably from 70 to 85% by weight % to be. The larger the ratio is, the more the flexibility of the obtained polyurethane tends to be improved. On the other hand, the smaller the ratio, the better the peelability of the obtained polyurethane.

In the polyurethane of the present invention, at least one of (a) the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, or (b) the hydroxyl group constituting the polyether polyol forms a urethane bond &Lt; / RTI &gt; (A) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, or (b) at least two hydroxyl groups constituting the polyether polyol having a urethane bond Is formed in the polymerization chain.

[Chemical Formula 1]

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

The content or position of the polymer in the polyurethane of the present invention is not particularly limited and may be any polymer having the above structure in the polymerization chain. Examples of the compound having the above structure include a polyurethane resin, a polyurethaneurea resin, and a prepolymer thereof.

(A) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol (c) a polyisocyanate compound, and (d) a chain extender Refers to a polymer compound having a urethane bond (-NHCOO-) in a repeating unit of a main chain, in which the repeating constituent unit of the main chain is derived from both of the compounds (a) and (b) , polyurethane as a polymer compound (a) derived from only the origin, (b) polyurethane as a polymeric compound derived only from the origin (b), or a mixture thereof. In addition, the unreacted (a), (b), (c), or (d) and the polymer compound may be mixed.

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

The ratio of each component is usually A to the polyurethane, (A) the total number of moles of the polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular end and (b) the hydroxyl group of the polyether polyol, and (c) (B) is usually in the range of 1:10 to 1: 1, preferably 1: 1 to 1: 1, and the molar ratio of the isocyanate group of the compound to the active hydrogen substituent (hydroxyl group and amino group) (BA) is 1: 5 to 1: 1.05, more preferably 1: 3 to 1: 1.1, further preferably 1: 2.5 to 1: 1.2, particularly preferably 1: C is usually 1: 0.1 to 1: 5, preferably 1: 0.8 to 1: 2, more preferably 1: 0.9 to 1: 1.5, further preferably 1: 0.95 to 1: 1.2, 1: 0.98 to 1: 1.1.

<(a) Polyhydroxyhydrocarbon polymer having at least one hydroxyl group at the molecular end>

The polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end in the present invention is typically a polymer having a hydrocarbon skeleton such as a conjugated diene such as butadiene, isoprene, chloroprene or the like as a repeating unit, Quot; polyester polyol &quot; These can be used in combination with a polyether polyol, and the polyurethane produced therefrom can improve the stickiness of the obtained polyurethane, the peelability of the polyurethane molded article, and the releasability at the time of release.

The polymer having a hydrocarbon skeleton as a repeating unit is preferably a polymer obtained by radically polymerizing 1,3-butadiene as hydrogen peroxide as a polymerization initiator, to thereby obtain a conjugated diene polymer having a hydroxyl group at the terminal directly, A conjugated diene polymer having a hydroxyl group at the terminal thereof is prepared by preparing a living polymer having an alkali metal bonded at its terminal using a polymerization catalyst and then reacting with a monoepoxy compound or formaldehyde, And the like. At that time, vinyl monomers such as styrene, acrylonitrile, methyl (meth) acrylate, and vinyl acetate may be copolymerized in an amount of 30% by weight or less in the conjugated diene.

Further, a polymer of isobutylene or isobutylene with a conjugated diene such as isoprene or 1,3-pentadiene is subjected to an oxidative decomposition treatment with ozone or the like, followed by a reduction treatment with lithium aluminum hydride or the like, , Hydrogenation of the obtained polymer by a conventional method and copolymerization of an alpha -olefin such as ethylene or propylene with a diene-based compound in the same manner as described above are subjected to the same oxidative decomposition and reduction treatment to obtain an isobutylene- And the like.

Of the polyhydroxy hydrocarbon polymers having at least one hydroxyl group at the molecular end of the present invention, preferred are polyhydroxy hydrocarbon polymers whose principal skeleton is hydrogenated polybutadiene, hydrogenated polyisoprene, and polyisobutylene It is more preferable that the main skeleton is hydrogenated polybutadiene in terms of availability and ease of handling.

The proportion of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end used in the present invention is preferably 0.01 weight% or more based on the total amount of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end and the polyether polyol % Or more. More preferably 0.03% by weight or more, still more preferably 0.05% by weight or more, particularly preferably 0.07% by weight or more, and most preferably 0.1% by weight. As this value becomes larger, the tackiness of the obtained polyurethane resin tends to be lowered. On the other hand, the upper limit is preferably 50.00% by weight or less. More preferably not more than 30.00% by weight, still more preferably not more than 25.00% by weight, particularly preferably not more than 15.00% by weight, most preferably not more than 10.00% by weight. The smaller the value is, the lower the tackiness of the obtained polyurethane resin, but tends to improve the elasticity property and elongation recovery property.

The polyhydroxy hydrocarbon polymer has a number average molecular weight of 500 to 5000, preferably 700 to 4000, more preferably 900 to 3500, and is liquid or wax-like at room temperature. If the number average molecular weight is too high, the viscosity of the polyether polyol, prepolymer or prepolymer solution becomes excessively high, which leads to deterioration of operability and productivity, or the physical properties of the resultant polyurethane polymer at low temperatures tend to deteriorate. When the amount is too low, the resultant polyurethane polymer tends to be hardened, resulting in insufficient flexibility, insufficient elasticity such as strength and elongation, or excessive residual deformation when elongation and recovery are repeated. The polyester polyol has at least two ester bonds and at least two hydroxyl groups in the molecule, and preferably both ends of the polyester polyol main chain are hydroxyl groups.

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

The number of ester bonds formed by the polyhydroxy hydrocarbon polymer (A) contained in one molecule of the polyester polyol of the present invention is usually one or more.

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

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

&Lt; (A) Polyhydroxyhydrocarbon polymer >

The polyhydroxyhydrocarbon polymer (A) 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 above hydrocarbon skeleton as a repeating unit is not particularly limited and may be a polymer having repeating units of hydrocarbons having substituents such as chlorine, fluorine, and bromine as an element other than carbon and hydrogen (Hereinafter, may be referred to as a hydrocarbon polymer), and more preferably an aliphatic hydrocarbon polymer, with a hydrocarbon as a repeating unit being preferably formed of carbon and hydrogen.

Examples of the hydrocarbon polymer in the present invention include a polymer having a cyclic hydrocarbon as a repeating unit or a polymer having a repeating unit of a hydrocarbon having a side chain in the molecule.

When the content of hydrocarbons having side chains in the molecule is large, a hydrocarbon polymer having a large content of hydrocarbons having side chains is preferable because the melting point of the hydrocarbon polymer is lowered and handling is facilitated.

The hydrocarbon polymer may be a homopolymer of one repeating unit or a copolymer containing two or more repeating units.

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

The polyhydroxy hydrocarbon polymer in the present invention is preferably butadiene, isobutylene, isoprene, chloroprene and the like in view of easy introduction of functional groups to the terminal of the polymer and easy control of the molecular weight. Of hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated polyisobutylene, and the like; more preferably hydrogenated polybutadiene, hydrogenated polyisoprene, and hydrogenated polyisobutylene; (Hereinafter, referred to as hydrogenated polydiene), more preferably hydrogenated polybutadiene, from the standpoint of ease of access and ease of handling.

The polyhydroxy hydrocarbon polymer in the present invention has at least two hydroxyl groups in the polymer. The number of the hydroxyl groups is not usually limited as long as it satisfies the following oxygen content, but is usually 2 or more and 6 or less, and preferably 3 or less. Although the position of the hydroxyl group is not particularly limited, it is preferable that the hydroxyl group is present at the molecular end, more preferably two or more at the molecular end, and more preferably both ends of the main chain of the 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, whereby a polyester having higher compatibility with the polyether polyol than the saturated hydrocarbon polymer A polyol can be obtained. Further, the polyurethane obtained by using such a polyester polyol exhibits high peelability.

The number average molecular weight of the polyhydroxy hydrocarbon polymer in the present invention is usually 100 or more, preferably 200 or more, more preferably 300 or more, and usually 5000 or less, preferably 4000 or less, more preferably 3000 or less to be. Below the lower limit value, there is a tendency that the resultant polyurethane polymer is hardened to cause lowering of flexibility, lowering of elastic performance such as strength and elongation, or excessive residual deformation when elongation and recovery are repeated. If the upper limit is exceeded, the viscosity of the polyether polyol, prepolymer or prepolymer solution becomes excessively high, resulting in deterioration of operability and productivity, and the physical properties of the resultant polyurethane polymer at low temperatures tend to be lowered.

The properties of the polyhydroxy hydrocarbon polymer in the present invention are not particularly limited, but are usually liquid or wax-like at room temperature.

<(B) Ester group-containing compound>

The ester group-containing compound used in the present invention is not particularly limited as long as it has an ester group, and usually includes a compound in which a repeating unit is polymerized via an ester bond, and preferably a poly Lt; / RTI &gt;

<Polylactone>

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

Specific examples of the lactone include ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone ,? -valerolactone,? -valerolactone, enantolactone, and the like, and these may be used alone or in combination of two or more. Of these, ε-caprolactone, δ-valerolactone and γ-valerolactone are preferable, and ε-caprolactone is more preferable in view of availability and high reactivity.

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

&Lt; Polyester polyol formed from polyhydroxy hydrocarbon polymer and polylactone >

One preferred embodiment of the polyester ester polyol of the present invention is a polyester ester polyol of the present invention wherein at least one ester group is formed between the polyhydroxy hydrocarbon polymer and the following polylactone and preferably the hydroxyl group of one molecule of the polyhydroxy hydrocarbon polymer At least one of the terminal hydroxyl groups possessed by one molecule of the polyhydroxy hydrocarbon polymer has at least one terminal hydroxyl group and at least one terminal hydroxyl group of the polyhydroxy hydrocarbon polymer has at least one terminal hydroxyl group, And has an ester bond with the polylactone and has a plurality of ester bonds in one molecule as a total.

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

The degree of polymerization of (A) or (B) is not particularly limited, and may be determined in consideration of the molecular weight of the starting material so that the oxygen content and molecular weight in the polyester polyol are desired values.

It is possible to easily change the molecular weight and the oxygen content of the resulting polyester polyol by controlling the polymerization degree of the above (A) or (B) according to the physical properties of the desired polyurethane resin. The production method is not particularly limited, but it can be generally obtained by reacting the polyhydroxy hydrocarbon polymer with the lactone in a predetermined ratio in the presence of a catalyst such as tetraisopropyl titanate or tetrabutyl titanate.

<(B) Carboxy group-containing compound>

The carboxyl group-containing compound used in the present invention is not particularly limited as long as it has a carboxyl group, but usually a monocarboxylic acid compound, a dicarboxylic acid compound, a substituted carboxylic acid compound such as a hydroxy acid or an alkoxy acid, And is preferably a dicarboxylic acid compound.

<Dicarboxylic acid>

The dicarboxylic acid compound used in the present invention may be any of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. The aliphatic dicarboxylic acid is usually at least 2 carbon atoms, preferably at least 3, more preferably Preferably 4 or more, and usually 16 or less, preferably 15 or less, and more preferably 14 or less. Specific examples include malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonamethylene dicarboxylic acid, 1,10 Decamethylene dicarboxylic acid, 1,11-undecamethylene dicarboxylic acid, and 1,12-dodecamethylene dicarboxylic acid. Specific examples of the aromatic dicarboxylic acid include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, and phenanthric dicarboxylic acid. These may be used singly or as a mixture of two or more kinds. The anhydrides, alkyl esters or halogen substituents of the unsaturated bonds of these dicarboxylic acids may also be used. Of these, aliphatic dicarboxylic acids and more preferably malonic acid, succinic acid, adipic acid, pimeric acid, suberic acid, azelaic acid, and sebacic acid are preferable because they are easily available and have high thermal stability. More preferred are succinic acid and adipic acid.

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

&Lt; Polyester polyol formed from polyhydroxy hydrocarbon polymer and dicarboxylic acid >

The polyester polyol formed by the polyhydroxy hydrocarbon polymer and the dicarboxylic acid in the present invention usually contains at least one hydroxyl group each having two molecules of the polyhydroxy hydrocarbon polymer and one molecule of the dicarboxylic acid Is a polyester polyol which forms an ester bond between two carboxyl groups.

(AB) _nA type polyester polyol which is preferably formed of a polyhydroxy hydrocarbon polymer (A) and a dicarboxylic acid (B). (A) and (B) may be bonded via an ester bond, or may be made of a carboxylic acid derivative such as a carboxylic acid diester.

In general, n may be an integer of 1 or more, more preferably ABA-type polyester polyol having one molecule of a polyhydroxy hydrocarbon polymer bonded to both ends of a dicarboxylic acid corresponding to n = 1.

Generally, the molecular weight of the polyhydroxy hydrocarbon polymer which is generally available is as high as at least 1500 or more, and when the polyhydroxy hydrocarbon polymer reacts with both ends of the dicarboxylic acid to produce a polyester polyol, the molecular weight becomes 3000 or more. If the molecular weight of the polyester polyol is excessively high when the value of n is large, the viscosity of the prepolymer or prepolymer solution becomes excessively high, resulting in deterioration of operability and productivity during production of the polyurethane or deterioration of physical properties at low temperatures of the obtained polyurethane polymer This is because there is a tendency.

The polyester polyol of the present invention may have a structure other than the above structure in the molecule, and preferably a polyester polyol which does not contain any structure other than the above-mentioned moiety.

In the above description, (A) and (B) are described in detail as the constituent for forming an ester bond. However, the polyester polyol of the present invention is not limited to this, and if the obtained molecular structure is the same, , Or may be obtained by a reaction method.

<Oxygen content>

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

The content of oxygen in the polyester polyol of the present invention is 2.0 mass% or more and 13.5 mass% or less, preferably 2.2 mass% or more, more preferably 2.5 mass% or more, furthermore preferably 3.0 mass% or more , Preferably 13 mass% or less, more preferably 12 mass% or less, further preferably 11.0 mass%. Below the lower limit, compatibility with the polyether polyol and solubility in solvents are insufficient, and when the upper limit is exceeded, the tackiness of the obtained polyurethane resin increases, which is not preferable.

The proportion of the polyhydroxy hydrocarbon polymer in the polyester polyol of the present invention is not particularly limited but is usually 10.0 mass% or more, preferably 20.0 mass% or more, more preferably 30.0 mass% or more, More preferably 40.0% by mass or more, and particularly preferably 45.0% by mass. The greater the mass ratio of the polyhydroxy hydrocarbon polymer in the polyester polyol of the present invention, the lower the tackiness of the obtained polyurethane. On the other hand, the upper limit is not particularly limited, but is 99.5 mass% or less, preferably 99.0 mass% or less, more preferably 98.5 mass% or less, further preferably 98.2 mass% or less, particularly preferably 98.0 mass% Or less. The smaller the mass ratio is, the more the compatibility with the polyether polyol and the solubility in the polar solvent tend to be improved.

<Physical Properties of Polyester Polyol>

The number average molecular weight of the polyester polyol of the present invention can be adjusted depending on the type and amount 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, more preferably 5000 or less. The number average molecular weight means the average molecular weight per molecule. If the number average molecular weight exceeds the upper limit, the viscosity of the prepolymer or prepolymer solution becomes excessively high, resulting in deterioration of operability and productivity, and the physical properties of the resultant polyurethane polymer at low temperatures tend to be lowered. Below the lower limit, the obtained polyurethane polymer tends to be hardened, so that sufficient flexibility may not be obtained, elasticity such as strength and elongation may not be sufficient, or excessive residual strain tends to remain after repeated elongation and recovery have.

< (b) Polyether polyol >

The polyether polyol in the present invention is a hydroxy compound having at least one ether linkage in the main skeleton of the molecule. The repeating unit in the main skeleton may be either saturated hydrocarbon or unsaturated hydrocarbon. For example, Methyl-1,4-butanediol units, 1,3-propanediol units, 1,2-propylene glycol units, 2-methyl-1, 1,3-propanediol unit, 3-methyl-1,5-pentanediol unit, 1,2-ethylene glycol unit, 1,6-hexanediol unit, 1 , 7-heptanediol unit, 1,8-octanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit and 1,4-cyclohexanedimethanol unit.

Among them, polytetramethylene ether glycol, polytrimethylene ether glycol, copolymerized polyether polyol of 1 to 20 mol% of 3-methyltetrahydrofuran and tetrahydrofuran (for example, PTG-L1000 "," PTG-L2000 ", and" PTG-L3500 "manufactured by Hodogaya Chemical Co., Ltd.), or copolymerized polyether glycols of neopentyl glycol and tetrahydrofuran.

< (c) Polyisocyanate compound >

Examples of the polyisocyanate compound used in the present invention include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4 ' Aromatic diisocyanates such as-MDI, para-phenylenediisocyanate, 1,5-naphthalene diisocyanate, and tridymine diisocyanate, aliphatic diisocyanates having aromatic rings such as?,?,? ',? - tetramethyl xylylene diisocyanate and the like , Aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate and 1,6-hexamethylene diisocyanate, 1,4- Cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (I PDI), 4,4'-dicyclohexylmethane diisocyanate, and isopropylidene dicyclohexyl-4,4'-diisocyanate, and the like. These may be used alone or in combination of two or more.

In the present invention, aromatic polyisocyanates having particularly high reactivity are preferable, and particularly tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are preferable. The NCO group of the polyisocyanate may be partially modified with urethane, urea, buret, allophanate, carbodiimide, oxazolidone, amide, imide, etc. In addition, .

The amount of these polyisocyanate compounds to be used is (1) the sum of the hydroxyl groups of the polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end and the hydroxyl group of the polyether polyol, and Is usually 0.1 to 5 equivalents, preferably 0.8 to 2 equivalents, more preferably 0.9 to 1.5 equivalents, more preferably 0.95 to 1.2 equivalents, and most preferably 0.98 to 1.1 equivalents based on the equivalent .

If the amount of the polyisocyanate to be used is too large, unreacted isocyanate groups may cause an undesirable reaction and tend to make it difficult to obtain desired physical properties. When the amount is too small, the molecular weight of the polyurethane and polyurethaneurea is not sufficiently increased, Is not expressed.

< (d) Chain extender >

The chain extender referred to in the present invention is mainly classified into a compound having two or more hydroxyl groups, a compound having two or more amino groups, and water. Among these, a polyol compound is preferable for a polyurethane application, particularly a compound having two or more hydroxyl groups, and a polyamine compound for a polyurethaneurea application, specifically a compound having two or more amino groups. Among them, it is preferable to reduce the water as much as possible in order to stably carry out the reaction.

When the polyurethane resin of the present invention is used as a chain extender in combination with a compound having a molecular weight (number average molecular weight) of 500 or less, the rubber elasticity of the polyurethane elastomer is improved, and therefore, it is more preferable from the viewpoint of physical properties.

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, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2- Ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2 Pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl- Aliphatic glycols such as propanediol, 1,8-octanediol, 2-methyl-1,8-octanediol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, And glycols having aromatic rings such as hydroxyethoxybenzene.

Examples of the compound having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylene diamine, xylylene diamine and 4,4'-diphenylmethane diamine, ethylenediamine, 1,2- -Propylene diamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl- 1,5-pentanediamine, Aliphatic diamines such as 2,4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4'-diamine , 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, and the like. These chain extenders may be used alone or in combination of two or more. Among them, ethylenediamine, propylenediamine, 1,3-diaminopentane and 2-methyl-1,5-pentanediamine are preferable in the present invention, and among these, ethylenediamine and propylenediamine are more preferable.

The amount of these chain extenders to be used is not particularly limited, but is usually 0.1 equivalents or more and 5.0 equivalents or less, when the equivalence of the total hydroxyl groups equivalent of (a) and (b) minus the equivalents of the polyisocyanate compound is 1. Preferably 0.8 equivalents or more and 2.0 equivalents or less, more preferably 0.9 equivalents or more and 1.5 equivalents or less. If the amount is too large, the resultant polyurethane and polyurethane urea become excessively hard and the desired characteristics are not obtained or they are not easily dissolved in the solvent and tend to be difficult to process. When the amount is too small, the resulting polyurethane and polyurethaneurea tend to be excessively soft, The performance is not obtained or the high-temperature characteristics tend to deteriorate.

When the polyurethane and the polyurethane urea to be used in the present invention are used for high-performance polyurethane elastomers such as polyurethane elastic fibers and synthetic leather, the following examples are given as combinations of raw materials.

For the purpose of controlling the molecular weight of the polyurethane, a chain terminator having one active hydrogen group may be used, if necessary. Examples of the chain stopper include aliphatic monools having a hydroxyl group such as ethanol, propanol, butanol and hexanol, diethylamine having an amino group, aliphatic monoalcohols such as dibutylamine, n-butylamine, monoethanolamine and diethanolamine Amines are exemplified. These may be used alone or in combination of two or more.

<Other additives>

Other additives may be added to the polyurethane of the present invention, if necessary. These additives include CYANOX 1790 (manufactured by CYANAMID), IRGANOX 245, IRGANOX 1010 (manufactured by Chiba Specialty Chemicals) Antioxidants such as butyl-4-methylphenol (BHT), antioxidants such as TINUVIN622LD, TINUVIN765 (manufactured by Chiba Specialty Chemicals), SANOL LS-2626, SANOL LS- UV absorbers such as "TINUVIN 328" and "TINUVIN 234" (manufactured by Chiba Specialty Chemicals), silicone compounds such as dimethylsiloxane polyoxyalkylene copolymer, Phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like, and reactive flame retardants, pigments such as titanium dioxide, colorants such as dyes and carbon black, carbodiimide compounds Of 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 the present invention and the method for producing the polyurethane will be described in detail below.

<Production method of polyester polyol>

The polyester polyol of the present invention is produced by using a polyhydroxy hydrocarbon polymer. The polyhydroxyhydrocarbon polymer is a compound known per se and can be produced according to a commonly used method. These commercially available compounds may also be used. Typically, a conjugated diene polymer having a hydroxyl group at its terminal end is directly polymerized by radical polymerization of a conjugated diene such as butadiene, isoprene or chloroprene, preferably 1,3-butadiene, as hydrogen peroxide as a polymerization initiator, A conjugated diene polymer having a hydroxyl group at the terminal is prepared by reacting a monoepoxy compound or formaldehyde or the like with a living polymer in which an alkali metal is bonded at the terminal using a catalyst and then the resulting conjugated diene polymer is reacted by a conventional method And hydrogenated. At this time, vinyl monomers such as styrene, acrylonitrile, methyl (meth) acrylate, and vinyl acetate may be copolymerized in an amount of 30 mass% or less in the conjugated diene.

Further, a polymer of isobutylene or isobutylene and a conjugated diene such as isoprene or 1,3-pentadiene is subjected to an oxidative decomposition treatment with ozone or the like, followed by a reduction treatment with lithium aluminum hydride or the like, A polymer obtained by hydrogenation of a polymer obtained by a conventional method and a copolymer of an? -Olefin such as ethylene and propylene with a diene compound are subjected to the same oxidative decomposition and reduction treatment to obtain an isobutylene polymer having a hydroxyl group, And the like.

The production of the polyester polyol of the present invention may employ conventionally known esterification techniques. For example, a method of reacting a polyol with a lactone or a dicarboxylic acid under atmospheric pressure, a method of esterification under reduced pressure, an esterification in the presence of an inert solvent such as toluene, followed by azeotroping condensation water or condensed alcohol with a solvent, And the like.

The reaction temperature of the esterification is usually in the range of 100 to 250 캜. Preferably 120 to 240 占 폚, more preferably 140 to 230 占 폚, particularly preferably 150 to 220 占 폚. If the reaction temperature is too low, the esterification reaction does not proceed sufficiently. If the reaction temperature is excessively high, the product may be colored.

The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary and can be carried out under normal pressure or reduced pressure depending on the purpose. In the reaction such as a polyol and a dicarboxylic acid or a dicarboxylic acid ester, water or an alcohol is produced during the reaction, so that an inert gas may be circulated in the reaction system in order to accelerate the desorption thereof from the reaction system.

<Catalyst>

The type of the esterification reaction is not particularly limited, and an esterification reaction can be carried out in a system in which no catalyst exists. Usually, in order to facilitate the esterification reaction, an inorganic acid or an organic acid; Chloride, oxide, hydroxide of a metal 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 an organic metal compound other than metals such as Al, Ti, Zn, Sn, Zr or Pb, and the like. A titanium-based catalyst such as isopropyl titanate or n-butyl titanate is the most preferable since it is easily available and low in toxicity and widely used for the esterification reaction. The amount of the catalyst to be used at that time is preferably 0.00001 to 5.0 mass%, more preferably 0.0001 to 2.0 mass%, most preferably 0.001 to 1.0 mass% with respect to the total amount of the raw materials for preparing the polyester diol. When the amount is too small, it takes a very long time to form the polyester polyol, and the product tends to be colored. On the other hand, if the amount of the catalyst is excessively large, there is a possibility of exhibiting an excessive reaction promoting action for the polyurethane formation reaction.

The esterification reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary and can be carried out under normal pressure or reduced pressure depending on the purpose. In the reaction such as a polyol and a dicarboxylic acid or a dicarboxylic acid ester, water or an alcohol is produced during the reaction. Therefore, an inert gas may be circulated in the reaction system in order to accelerate their desorption from the reaction system.

The esterification reaction time varies depending on the amount of the catalyst used, the reaction temperature, the substrate to be reacted, the desired polyesterpolyol to be produced, the desired physical properties, etc. The lower limit is usually 0.5 hours, preferably 1 hour, Is 20 hours.

When a catalyst is used in the esterification reaction, the (titanium-based) catalyst used for the reaction remains in the resulting polyester polyol product. Since removal of the catalyst usually involves a troublesome process, the produced polyester polyol is generally used in the production of polyurethane as it is without separating the (titanium-based) catalyst in many cases.

However, it is preferable to deactivate the titanium catalyst in the polyester polyol in a case where the content of the catalyst is large or in some polyurethane applications. Examples of the deactivation method of the titanium catalyst in the polyester polyol include (1) a method in which the polyester polyol is contacted with water under heating; (2) a method of treating a polyester polyol with phosphorus compounds such as phosphoric acid, phosphoric acid ester, phosphorous acid and phosphorous acid ester. In the case of the method (1) in which the polyester polyol is brought into contact with water, for example, 1 mass% or more of water is added to the polyester polyol, and the mixture is heated at a temperature of 70 to 150 캜, preferably 90 to 130 캜, Heat for 3 hours. The inactivating treatment by heating at this time may be carried out under atmospheric pressure or under pressure. If the system is decompressed after the deactivation treatment, moisture used for deactivation can be smoothly removed from the polyester polyol.

<Production method of polyurethane>

(A) a polyhydroxy hydrocarbon polymer having at least one hydroxyl group at the molecular end, (b) a polyether polyol, (c) a polyisocyanate compound, and (d) The extenders are mainly used as raw materials for production.

In order to produce the polyurethane, a polyurethane can be generally produced in the presence of a solvent. In the present invention, the polyurethane is preferably produced in the coexistence of an aprotic polar solvent.

The amount of each compound to be used is not particularly limited, and the amounts described above may be used. Hereinafter, an example of a production method in the coexistence of an aprotic polar solvent is shown, but there is no particular limitation on the coexistence of the aprotic polar solvent.

The aprotic polar solvent in the present invention is not particularly limited, but from the viewpoint of solubility, in the aprotic polar solvent, amide solvent, N-methylpyrrolidone, N-ethylpyrrolidone, And a side-chain is preferably used. Specific examples of the amide-based solvent include N, N-dimethylacetamide, N, N-dimethylformamide, and a mixture of two or more thereof, particularly preferably dimethylformamide or dimethylacetamide.

An example of the production method is a method in which (a), (b), (c) and (d) (B) and (c) are reacted, and (a) is mixed and (d) the prepolymer is reacted with the prepolymer (d) (B) reacting (c) and (d), followed by mixing (a). Among them, the two-step method is a step of preparing an intermediate product sealed with both terminal isocyanates corresponding to the soft segment of the polyurethane by reacting the polyether polyol with one equivalent or more of the polyisocyanate in advance. It is easy to adjust the molecular weight of the soft segment and easily separate the soft segment and the hard segment by reacting with the chain extender after the preparation of the prepolymer, and the elastomer can exhibit its performance easily. Particularly, when the chain extender is a diamine, the reaction rate with the isocyanate group is significantly different from that of the hydroxyl group of the polyether polyol. Therefore, it is more preferable to perform polyurethane urea by the two-stage method (prepolymer method).

<Short Stage>

The one-step method is also referred to as a one-shot method, and is a method in which the reaction is carried out by injecting together (a), (b), (c) and (d). The amount of each compound to be used may be the amount described above.

The reaction is usually carried out at 0 to 250 ° C, depending on the amount of 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 becomes too slow, or the solubility of the raw material or the polymer is low, resulting in poor productivity. When the temperature is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be carried out while distilling under reduced pressure. A catalyst, a stabilizer and the like may be added to the reaction, if necessary. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid. 6-dibutyl-4-methylphenol, distearyliodipropionate, di-betanaphthylphenylenediamine, tri (dinonylphenyl) phosphite, and the like.

<Stage 2>

The two-step method is also called a prepolymer method. A prepolymer having a polyisocyanate component and a polyol component reacted in advance at a reaction equivalent ratio of 1.0 to 10.00 is prepared in advance, and then a polyisocyanate component or an active hydrogen compound component such as a polyhydric alcohol or an amine compound The reaction can be carried out in two steps. Particularly, a method of reacting a polyisocyanate compound having an equivalent amount or more with respect to the polyol component to prepare a two-terminal NCO prepolymer, and subsequently reacting with a single chain diol or diamine as a chain extender, is useful.

In the present invention, the two-step method can be carried out in the presence of a solvent, and is preferably carried out in the presence of an aprotic solvent. Specifically, an amide-based solvent, N-methylpyrrolidone, N-ethylpyrrolidone, Side solvents, and mixtures of two or more thereof.

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

In the case of synthesizing a prepolymer, (1) a prepolymer may be synthesized by directly reacting a polyisocyanate compound with a polyether polyol without using a solvent, and (2) a prepolymer is synthesized by the method of (2) (3) a polyisocyanate and a polyether glycol may be reacted using a solvent from the beginning. In the case of the compound (1), in the present invention, by reacting the chain extender with a solvent, by dissolving the chain extender in a solvent, or by introducing a prepolymer and a chain extender into the solvent at the same time, It is important to obtain it in a form coexisting with a solvent.

The reaction equivalent ratio of the NCO / active hydrogen group (polyol) is usually 1, preferably 1.05, and the upper limit is usually 10, preferably 5, more preferably 3. If the ratio is too small, the molecular weight of the obtained prepolymer becomes excessively large and the amount of the hard segment to be described below becomes low, so that sufficient stretchability tends not to be obtained. When the ratio is excessively large, the amount of the hard segment to be described later becomes high, There is a tendency not to be.

The amount of the chain extender 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 in relation to the equivalent of the NCO group contained in the prepolymer.

In addition, a monofunctional organic amine or alcohol may coexist in the reaction.

The chain extension reaction is usually carried out at 0 to 250 ° C, depending on the amount of 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 becomes too slow, or the solubility of the raw material or the polymer is low, resulting in poor productivity. If the temperature is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be carried out under reduced pressure while defoaming.

A catalyst, a stabilizer and the like may be added to the reaction, if necessary. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid. Examples of the stabilizer include 2,6- Dibutyl-4-methylphenol, distearyliodipropionate, di-betanaphthylphenylenediamine, tri (dinonylphenyl) phosphite, and the like. However, when the chain extender is one having a high reactivity such as a single chain aliphatic amine, it is preferable to carry out the addition without adding a catalyst.

<Physical Properties of Polyurethane>

The polyurethane obtained by the above production method is generally obtained in a state in which it is dissolved in a solution because the reaction is carried out in the presence of a solvent. The physical property is not limited to a state, either in a solution state or a solid state, .

The weight average molecular weight of the polyurethane varies depending on the application, and is usually from 10,000 to 1,000,000, preferably from 50,000 to 500,000, more preferably from 100,000 to 400,000 as the polyurethane polymerization solution, It is between 100,000 and 30,000. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, more preferably 1.8 to 3. As the fiber, film, and moisture-permeable resin molded article, the weight average molecular weight of the polyurethane is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 ~ 40 million. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, more preferably 1.8 to 3.

The polyurethane obtained by the above production method preferably contains the hard segment in an amount of 1 to 20% by weight, more preferably 3 to 15% by weight, and more preferably 3 to 15% by weight, based on the total weight of the polyurethane polymer By weight is 4 to 12% by weight, particularly preferably 5 to 10% by weight. If the amount of the hard segment is excessively large, the obtained polyurethane polymer does not exhibit sufficient flexibility and elastic performance, or when the solvent is used, it tends to be hard to melt and tends to be difficult to process. When the amount is too small, the urethane polymer is too soft, which makes processing difficult, and there is a tendency that sufficient strength and elasticity performance are not obtained.

The hard segment in the present invention is calculated by the following formula based on the total weight of the isocyanate and amine bonding portions based on PJ Flory, Journal of American Chemical Society, 58, 1877-1885 (1936) .

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

here,

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

Mdi = Number average molecular weight of diisocyanate

Mda = number average molecular weight of chain extender

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

The polyurethane solution obtained in the present invention has satisfactory storage stability such as less gelation, less change with time, and less thixotropy, so that the polyurethane solution is in good condition Do. The polyurethane concentration of the polyurethane solution is usually from 1 to 99% by weight, preferably from 5 to 90% by weight, more preferably from 10 to 70% by weight, and particularly preferably from 5 to 90% by weight based on the total weight of the solution dissolved in the solvent 15 to 50% by weight. When the amount of the polyurethane is too small, it is necessary to remove a large amount of solvent and the productivity tends to be low. When the amount is too large, the viscosity of the solution becomes too high, and the operability and workability tend to deteriorate.

The polyurethane solution is not particularly specified, but when it is stored for a long period of time, the polyurethane solution is preferably stored under an inert gas atmosphere such as nitrogen or argon at room temperature or below.

<Polyurethane molded article and its use>

After obtaining the polyurethane and the urethane prepolymer solution produced in the present invention and then molding them, a polyurethane molded article can be obtained.

The polyurethane molded article of the present invention may be any of the above-mentioned polyurethane or a molded article made of the polyurethane obtained by the above-mentioned production method, and is not particularly limited, but usually includes (a) polyhydroxyhydrocarbon having at least one hydroxyl group at the molecular end (B) a polyether polyol, (c) a polyisocyanate compound, and (d) a chain extender, wherein the atomic composition of the surface of the polyurethane molded article ) Is 0.22 or less.

Specifically, the atomic composition (oxygen atom / carbon atom) of the surface of the polyurethane molded body refers to the oxygen content of the surface of the polyurethane molded body when the surface of the molded article is measured by, for example, ESCA (Electron Spectroscopy for Chemical Analysis) or XPS (X-ray Photoelectron Spectroscopy) Represents the relative abundance ratio of an atom to a carbon atom.

The value of the atomic composition (oxygen atom / carbon atom) of the surface of the polyurethane molded article of the present invention is preferably 0.20 or less, more preferably 0.16 or less. The smaller this value is, the smaller the tackiness of the obtained molded article tends to be, and the peelability tends to be improved. Further, it is preferably 0.00 or more, more preferably 0.05 or more. The larger this value is, the greater the packing property when the obtained molded articles are overlapped. For example, when the molded body is sealed, the wound yarn is loosened and the shape is not easily disturbed.

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

The water contact angle of the surface is obtained by dropping several μL of water droplets on the surface of the molded body and measuring the internal angle formed by the tangent of the droplet and the surface of the molded body within 10 seconds. The water contact angle value of the surface of the polyurethane molded article of the present invention is 80 degrees or more, preferably 83 or more, more preferably 86 or more. The larger this value is, the smaller the tackiness of the obtained molded article tends to be, and the peelability tends to be improved. Further, it is preferably 180 degrees or less, more preferably 150 degrees or less. The smaller the value, the higher the packing property when the obtained formed bodies are overlapped with each other. For example, in the case where the formed body is hollow, the wound yarn is loosened and the shape is not easily disturbed.

In addition, the polyurethane, urethane prepolymer solution and polyurethane molded article of the present invention can be used for various purposes because they exhibit various properties. It can be widely used, for example, in foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, materials for use, artificial leather and the like.

The polyurethane, the polyurethane urea, and the urethane prepolymer solution prepared in the present invention can be used in a cast polyurethane elastomer. Examples of the industrial products include conveyor belt idlers, guide rollers, and rollers such as rolls, rolls such as rolling rolls, paper rolls, office machines, pretension rolls, solid tires such as forklifts, automotive vehicle new trams, bogies, Pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liner, pump impeller, cyclone cone, cyclone liner and so on. It is also applied to OA belt, paper transfer roll, copying cleaning blade, snow flare, toothed belt, and surf roller.

The polyurethane and the urethane prepolymer solution thereof produced in the present invention are also used as a thermoplastic elastomer. For example, it can be used as a tube or a hose, a spiral tube, a fire hose or the like in a pneumatic apparatus, a coating apparatus, an analytical apparatus, a physicochemical apparatus, a metering pump, a water treatment apparatus, an industrial robot, In addition, it is used as a belt such as a round belt, a V belt, a flat belt, and the like, and is used for various transmission mechanisms, spinning machines, packing machines, printing machines and the like. Also, examples of the hill top and sole of a shoe, coupling parts, packing parts, pole joints, bush parts, gear parts, gear parts, sports goods, leisure goods, and watch belts can be exemplified. Examples of the automobile parts include an oil stopper, a gear box, a spacer, a chassis part, an internal product, and a tire chain replacement product. In addition, a film such as a keyboard film, an automobile film, a curl cord, a cable sheath, a bellows, a conveyance belt, a flexible container, a binder, a synthetic leather, a dipping product, an adhesive and the like can be illustrated.

The polyurethane and the urethane prepolymer solution produced in the present invention can be applied to a solvent-based two-pack type paint, and can be applied to wooden products such as musical instruments, alms, furniture, fancy plywood and sporting goods. In addition, tar epoxy urethane can be used for automobile repair.

The polyurethane and the urethane prepolymer solution prepared in the present invention can be used as components such as a moisture curing type one-pack type paint, a block isocyanate type solvent type paint, an alkyd resin type paint, a urethane-modified synthetic resin type paint and an ultraviolet ray curable type paint, Overprint varnishes such as coatings for plastic bumpers, strippable paints, coatings for magnetic tapes, floor tiles, flooring materials, paper, wood grain printing films, varnishes for wood, coil coats for high prices, optical fiber protection coatings, solder resists, A topcoat, a vapor-deposition base coat, a white coat for food can, and the like.

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

The polyurethane and urethane prepolymer solution prepared in the present invention can be used as a binder in the form of a magnetic recording medium such as a magnetic recording medium, an ink, a casting, a baked brick, a graft material, a microcapsule, a granular fertilizer, a granular pesticide, a polymer cement mortar, , Regenerated foam, glass fiber sizing, etc.

The polyurethane and the urethane prepolymer solution produced in the present invention can be used as shrink-proofing, spindle-making, water-repellent processing or the like as a component of a fiber processing agent.

The polyurethane, polyurethane urea, and urethane prepolymer solution prepared in the present invention can be used as a sealant and / or caulking, such as a concrete exposed wall, a driven joint, a chassis periphery, a wall PC joint, an ALC joint, Sealant for insulation, heat-insulating chassis sealant, automobile sealant, and the like.

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as a medical material and can be used as a blood-suited material such as a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, , Bags, surgical gloves, artificial kidney potting materials, and the like.

The polyurethane, urethane urea, and urethane prepolymer solution thereof produced in the present invention can be used as a raw material for a UV curable paint, an electron beam curable paint, a photosensitive resin composition for a flexographic printing plate, a photo-curable optical fiber coating composition or the like, Can be used.

Particularly, it is preferable that the polyurethane used in the film or the fiber is used for taking advantage of the elastic performance and the moisture-permeability characteristic of the polyurethane produced in the present invention. Specific examples of applications include medical, sanitary materials, artificial leather, It is preferably used for fibers.

The polyurethane produced in the present invention and its application examples using the urethane prepolymer solution have been described above, but the present invention is not limited to these applications.

The production method of the film and the fiber is described below, but the production method is not particularly limited.

<Production Method of Film>

The method of producing the film is not particularly limited, and a known method can be used. For example, as a method for producing a film, there is a wet film production method in which a polyurethane resin solution is applied to a support or release member and a solvent or other soluble substance is extracted in a coagulation bath, a method in which a polyurethane resin solution is applied to a support or a release member, And a dry film production method in which the solvent is dried by heating or under reduced pressure. The support used in the production of the dried film is not particularly limited, but polyethylene or polypropylene film, paper, cloth or the like coated with glass, metal, or peeling agent is used. The coating method is not particularly limited, and any known coating method such as a knife coater, a roll coater, a spin coater, and a gravure coater may be used. The drying temperature can be set arbitrarily according to the capability of the dryer, and it is necessary to select a temperature range in which insufficient drying or rapid desolvation does not occur. Preferably from room temperature to 300 캜, more preferably from 60 캜 to 200 캜.

<Physical Properties of Film>

The thickness of the film of the present invention is usually 10 to 1000 占 퐉, preferably 10 to 500 占 퐉, and more preferably 10 to 100 占 퐉. If the thickness of the film is too thick, sufficient moisture permeability tends not to be obtained. On the other hand, if it is too thin, pinholes tend to be generated, or the film tends to be easily blocked, making handling difficult. The film can be suitably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture permeable materials. The film may be applied to a support such as a cloth or a nonwoven fabric. In this case, it may be thinner than 10 탆.

The elongation at break is usually 100% or more, preferably 200% or more, more preferably 300% or more, further preferably 500% or more. The breaking strength is usually 5 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and further preferably 30 MPa or more.

The elastic retention ratio (Hr1 / Hr1) obtained by grasping the stress at 150% elongation at the first shrinkage relative to the stress at 150% elongation at the first elongation in the 300% elongation-shrinkage repeated test at 23 deg. H1) is usually 10% or more, preferably 20% or more, more preferably 30% or more, and even more preferably 40% or more. The elasticity retention ratio (Hr5 / H5), which is likewise grasped by the ratio of the stress at 150% elongation at the fifth stretch to the stress at the 150th elongation at the fifth stretch, is usually 30% or more, preferably 50 %, More preferably not less than 70%, still more preferably not less than 85%.

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

The second residual strain in the 300% elongation-shrinkage repeated test at 23 캜 is usually 40% or less, preferably 30% or less, more preferably 25% or less, particularly preferably 20% or less . The residual strain at the fifth time is generally 50% or less, preferably 35% or less, more preferably 30% or less, particularly preferably 25% or less.

In addition, the physical properties of the polyurethane film and the yarn have a very good correlation, and the physical properties obtained in the test of the film and the like also show the same tendency in the yarn (fiber).

<Use of polyurethane fiber>

The fiber using the polyurethane of the present invention can be used for a specific purpose such as a leg part of pants, pantyhose, stockings, diaper cover, paper diaper, sports clothes, underwear, socks, stretchable clothes excellent in fashionability, , Leotard, and the like. This is because it is excellent in elongation recovery property, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, processability and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless it exceeds the gist of the present invention. The analysis and measurement in the following Examples and Comparative Examples were based on the following methods.

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

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

&Lt; Molecular weight of polyurethane and polyurethane urea >

The molecular weight of the obtained polyurethane or polyurethane urea was determined by preparing a dimethylacetamide solution of polyurethane or polyurethane urea and measuring the molecular weight of the obtained polyurethane or polyurethaneurea using a GPC apparatus (product name: HLC-8220, column: TskgelGMH-XL, And the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Peel test method>

Two pieces of the obtained films were superimposed on each other, and a film having a sample length of 4 cm (each including an overlapping portion of 2.5 cm between the initial test length at the time of fixing a 1.5 cm-length tensile tester) and a width of 1 cm was obtained with a test strip rudder. The test piece was allowed to stand for 10 minutes under conditions of a temperature of 25 ° C and a relative humidity of 50% under a pressure of 200 g / cm 2, and then a tensile tester ("Rheometer NRM-2003J" manufactured by FUDOH) And the T-shaped peel strength was measured by pulling the test film at a speed of 300 mm / min.

<Film Properties>

The polyurethane or polyurethane urea test piece was formed into a monolayer shape having a width of 10 mm, a length of 100 mm and a thickness of about 50 占 퐉 and a tensile tester (product name: "Tensilon UTM-III-100" manufactured by Orientec Co., ] Was used to measure the tensile fracture strength, tensile elongation at break, tensile strength at 100% elongation and elongation at 300% at a temperature of 23 ° C (relative humidity of 55%) at a chuck distance of 50 mm and a tensile rate of 500 mm / Respectively.

&Lt; Surface atom composition >

The surface atomic composition was determined by ESCA (Electron Spectroscopy for Chemical Analysis) measurement. The measurement was carried out using an ESCA apparatus "PHI Model 5800" from ULVAC-PY Co., Ltd. The measurement conditions are as follows.

· Excitation X-ray: monochromatic AlKα line (1486.6 eV)

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

· Neutralization gun: used (for prevention of electrification)

· Input lens setting (Lens Area Mode): Minimum Area Mode

· Analysis mode (LENS MODE): 5 (Minimum area mode)

· Aperture number: 5

· For emission (angle formed by the center axis of the detector from the sample normal): 45 degrees

· PassEnergy: 23.5 eV

Charge shift correction: The binding energy of C1s peak of C-H bonding 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 corrected relative sensitivity coefficient of oxygen O1s peak) / (peak area of carbon C1s / peak corrected relative sensitivity coefficient of carbon C1s peak)

In addition, the area of each peak of oxygen O1s and carbon C1s was obtained by performing a smoothing process (9 points) using the Savitzky-Golay algorithm using 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 energy used in calculating the relative abundance ratio and the respective corrected relative sensitivity coefficients used in MultiPak Ver.8.2C software are as follows.

O1s: bonding energy = 532.5 eV,

Correlation relative sensitivity coefficient = 13.118

C1s: bonding energy = 285.0 eV,

Correction relative sensitivity coefficient = 5.220

As for the peak area of carbon C1s, the peak obtained from the shake up of the benzene ring obtained by linking the area obtained by connecting the minimum value near 280 eV and 290.5 eV by shirley and the minimum value near 290.5 eV and 293 eV by shirley was 291 To about 293 eV) was used.

<Water contact angle>

Using a DM-300 automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd., 1.5 to 2.0 [mu] l of water drop was dropped on the surface of the polyurethane film, and after 5 seconds, the internal angle formed by the tangent of the water drop and the surface of the formed body was measured. The same operation was repeated five times by changing the location of the film, and the average value of the obtained five points was determined as 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) preliminarily heated to 40 占 폚 and 142.5 parts by weight of a hydrogenated polybutadiene polyol manufactured by Mitsubishi Chemical Corporation Terah HA "number average molecular weight: 2187, average number of hydroxyl groups per molecule: 1.8) was added and mixed, and this mixture was used as a raw material for polyurethane production. The ratio of poly-HA to this mixture was 5% by weight. Thereafter, 31 parts by weight of 4,4'-diphenylmethane diisocyanate (hereinafter also abbreviated as "MDI") heated to 40 ° C was added. At this time, the reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) was 1.6. The flask was set in an oil bath at 45 ° C and the temperature of the oil bath was raised to 70 ° C over 1 hour while stirring with an anchor type stirring vane under a nitrogen atmosphere and then maintained at 70 ° C for 3 hours. The residual NCO group was reacted with an excessive amount of dibutylamine and then the remaining dibutylamine was titrated back with hydrochloric acid to confirm that the reaction rate of NCO exceeded 99%. Then, the oil bath was removed, and N, N- 271 parts of dimethylacetamide (hereinafter sometimes abbreviated as "DMAC", manufactured by Kanto Chemical Co., Ltd.) was added and dissolved by stirring at room temperature to prepare a polyurethane prepolymer solution.

Ethylenediamine (EDA) / diethylamine (DEA) = 89/11 (molar ratio) = 1.72 / 0.27 (weight ratio) used as a chain extender was cooled to 10 DEG C while 380 parts by weight of the polyurethane prepolymer solution was maintained. Of a 0.6% DMAC solution was prepared. The polyurethane prepolymer solution cooled and maintained at 10 캜 in the 0.6% DMAC solution was added with stirring at a high speed to obtain a polyurethane urea DMAC solution having a polymer concentration of 20%.

The solution was aged at 25 캜 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC, and the weight average molecular weight was 17.2 million and the molecular weight distribution was 2.4. The proportion of polytetramethylene ether glycol (b) in the obtained polyurethane was 78% by weight.

The polyurethaneurea solution thus obtained was cast on a glass plate and dried at 60 DEG C to obtain a colorless transparent film having a thickness of about 50 mu m. The thickness of the film was measured by a thickness measuring machine.

As a result of carrying out the peeling test of the film, the stress required for peeling was 5.7 g / cm and the peeling property was good. The obtained elastic film had the characteristics shown in Table 1. [ The surface atomic composition of the film was 0.089 and the water contact angle was 90 degrees. The results are shown in Table 1.

&Lt; Example 2 >

In Example 1, 148.5 parts by weight of a polytetramethylene ether glycol (number-average molecular weight 1968, calculated from the hydroxyl group value) of a starting material for polyurethane production, 148.5 parts by weight of "Polyter HA" (number average molecular weight: (The average number of bonds of hydroxyl groups per molecule: 1.8) was added and mixed (the ratio of the polyether HA in the mixture was 1% by weight) and ethylenediamine / diethylamine = 1.81 / 0.28 A prepolymer and a polyurethane-urea solution were obtained in the same manner as in Example 1.

The solution was aged at 25 캜 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC, and the weight average molecular weight was 20.2 million and the molecular weight distribution was 2.5. The proportion of polytetramethylene ether glycol (b) in the obtained polyurethane was 81% by weight.

A colorless transparent polyurethane urea film having a thickness of about 50 탆 was obtained from this polyurethaneurea solution.

As a result of carrying out the peeling test of the film, the stress required for peeling was 5.7 g / cm and the peeling property was good. The obtained elastic film had the characteristics shown in Table 1. [ The surface atomic composition of the film was 0.119, and the water contact angle was 89 degrees. The results are shown in Table 1.

&Lt; Example 3 >

In Example 2, 149.85 parts by weight of polytetramethylene ether glycol (number-average molecular weight of 1968, produced by Mitsubishi Chemical Corporation) calculated from the hydroxyl value of the raw material for polyurethane production and 149.85 parts by weight of "Polyter HA" (number average molecular weight: (The average number of bonds of hydroxyl groups per molecule: 1.8) was added and mixed (the ratio of the polyether HA in the mixture was 0.1 wt%) to obtain a prepolymer and a polyurethaneurea solution.

The solution was aged at 25 캜 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC. As a result, the weight average molecular weight was 19.8 million and the molecular weight distribution was 2.4. The proportion of polytetramethylene ether glycol (b) in the obtained polyurethane was 82% by weight.

A colorless transparent polyurethane urea film having a thickness of about 50 탆 was obtained from this polyurethaneurea solution.

As a result of carrying out the peeling test of the film, the stress required for peeling was 33 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 1. [ The surface atomic composition of this film was 0.194. The results are shown in Table 1.

<Example 4>

(Number-average molecular weight: 1968, produced by Mitsubishi Chemical Corporation), 105 parts by weight of polytetramethylene ether glycol (number average molecular weight: 1968, manufactured by Mitsubishi Chemical Corporation) Number: 1.8) was added and mixed (the proportion of the polyether HA in the mixture was 30% by weight) to obtain a prepolymer and a polyurethane urea solution.

The solution was aged at 25 캜 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC. As a result, the weight average molecular weight was 19.8 million and the molecular weight distribution was 2.4. The proportion of the polytetramethylene ether glycol (b) in the obtained polyurethane was 57% by weight.

A slightly clouded polyurethane urea film having a thickness of about 50 탆 was obtained from this polyurethaneurea solution.

As a result of carrying out the peeling test of the film, the stress required for peeling was 33 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 1. [

&Lt; Comparative Example 1 &

Except that "Polyether HA" was not used and 150 parts by weight of polytetramethylene ether glycol (number-average molecular weight 1968 produced from hydroxyl group value, produced by Mitsubishi Chemical Corporation) was used as raw material for polyurethane production in Example 1 To obtain a prepolymer and a polyurethane-urea solution.

The solution was aged at 25 占 폚 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC. As a result, the weight average molecular weight was 19.1 million and the molecular weight distribution was 2.6. The proportion of polytetramethylene ether glycol (b) in the obtained polyurethane was 78% by weight.

A colorless transparent polyurethane urea film having a thickness of about 50 탆 was obtained from this polyurethaneurea solution.

As a result of carrying out the peeling test of this film, the stress required for peeling was 50 g / cm, and the film was stretched by 12% with respect to the initial test length upon peeling. The obtained elastic film had the properties shown in Table 1. [ The surface atomic composition of the film was 0.239 and the water contact angle was 76 degrees. The results are shown in Table 1.

&Lt; Example 5 >

[Production of polyester polyol]

1.2 g of tetrabutyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g (20.0 mmols) of hydrogenated polybutadiene polyol GI-1000 (manufactured by Nippon Soda Co., Ltd., molecular weight of 1500) were placed in a 100- , 10 g (87.6 mmol) of epsilon -caprolactone (Across) was added. A reflux condenser and a nitrogen inlet tube were placed and the reaction vessel was immersed in an oil bath and heated to 190 DEG C for 30 minutes and reacted at 190 DEG C for 7 hours to obtain polyester polyol 1. [ Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 1.

[Production of polyurethane urea]

123.9 parts by weight of polytetramethylene ether glycol (number average molecular weight of 1955, manufactured by Mitsubishi Chemical Corporation), which had been previously heated to 40 ° C, and 12.5 parts by weight of the polyester polyol 1 synthesized above And the mixture was used as a raw material for producing polyurethane. The ratio of the polyester polyol 1 to this mixture was 5% by weight. Thereafter, 26.8 parts by weight of 4,4'-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as &quot; MDI &quot;) heated to 40 ° C was added. At this time, the reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) was 1.6. The flask was set in an oil bath at 45 ° C and the temperature of the oil bath was raised to 70 ° C over 1 hour while stirring with an anchor type stirring vane under a nitrogen atmosphere and then maintained at 70 ° C for 3 hours. The residual NCO group was reacted with an excessive amount of dibutylamine and then the remaining dibutylamine was titrated back with hydrochloric acid to confirm that the reaction rate of NCO exceeded 99%. Then, the oil bath was removed, and N, N- 236 parts of dimethylacetamide (hereinafter sometimes abbreviated as "DMAC", manufactured by Kanto Chemical Co., Ltd.) was added and dissolved by stirring at room temperature to prepare a polyurethane prepolymer solution.

The polyurethane prepolymer solution was cooled to 10 캜 and maintained at 0.5 (ethylenediamine (EDA) / diethylamine (DEA) = 89/11 (molar ratio) = 1.66 / % DMAC solution was prepared. The polyurethane prepolymer solution cooled and maintained at 10 캜 in the 0.5% DMAC solution was added with stirring at a high speed to obtain a polyurethane urea DMAC solution having a polymer concentration of 20%.

The solution was aged at 25 占 폚 overnight, and then the weight average molecular weight and the molecular weight distribution were measured by GPC. As a result, the weight average molecular weight was 21.9 million and the molecular weight distribution was 2.7. The proportion of polytetramethylene ether glycol (b) in the obtained polyurethane was 78% by weight.

The polyurethaneurea solution thus obtained was cast on a glass plate and dried at 60 DEG C to obtain a colorless transparent film having a thickness of about 50 mu m. The thickness of the film was measured by a thickness measuring machine.

As a result of carrying out the peeling test of the film, the stress required for peeling was 4.4 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The film had a surface atomic composition of 0.097 and a water contact angle of 95 degrees. The results are shown in Table 3.

&Lt; Example 6 >

[Production of polyester polyol]

60 g (28.6 mmol) of GI-2000 (Nippon Soda Co., Ltd., molecular weight 2100) was used instead of GI-1000, the amount of tetrabutyl orthotitanate used was changed to 3.6 mg, the amount of used 竜 -caprolactone was changed to 12 g ol) was used in place of the polyester polyol 2 used in Example 5. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 2.

[Production of polyurethane urea]

A polyurethane-urea solution and a film were obtained in the same manner as in Example 5, with the amount of raw materials injected in the polyurethane production shown in Table 3. As a result of carrying out the peeling test of the film, the stress required for peeling was 6.7 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The surface atomic composition of the film was 0.094 and the water contact angle was 94 degrees. The results are shown in Table 3.

&Lt; Example 7 >

[Production of polyester polyol]

Except that 51.3 g (24.4 mmol) of GI-2000, 2.5 mg of tetrabutyl orthotitanate, and 22 g (193 mmol) of epsilon -caprolactone were used in place of polyester polyol 3 . Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 3.

[Production of polyurethane urea]

A polyurethane-urea solution and a film were obtained in the same manner as in Example 5, with the amount of raw material injected at the time of producing the polyurethane shown in Table 3. As a result of carrying out the peeling test of this film, the stress required for peeling was 3.6 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The surface atomic composition of the film was 0.100 and the water contact angle was 95 degrees. The results are shown in Table 3.

&Lt; Example 8 >

[Production of polyester polyol]

(Idemitsu Kosan, molecular weight 1,800) 60 g (27.9 mmol) of hydrogenated polyisoprene polyol was used instead of GI-1000, the amount of tetrabutyl orthotitanate used was changed to 3.6 mg, the amount of used 竜 -caprolactone was changed to 10 g (87.6 mmols) of polyester polyol 4 was prepared in the same manner as in Example 5. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 4.

[Production of polyurethane urea]

A polyurethane-urea solution and a film were obtained in the same manner as in Example 5, with the amount of raw material injected at the time of producing the polyurethane shown in Table 3. As a result of carrying out the peeling test of this film, the stress required for peeling was 4.5 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The surface atomic composition of the film was 0.154 and the water contact angle was 88 degrees. The results are shown in Table 3.

&Lt; Example 9 >

[Production of polyester polyol]

In a 100 ml four-neck round bottom flask equipped with a stirrer, 4.2 mg of tetrabutyl orthotitanate (Tokyo Kasei Kogyo), 66.0 g (44.0 mmols) of hydrogenated polybutadiene polyol GI-1000 (Nippon Soda Co., , 3.8 g (22.0 mmol) of dimethyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto. A reflux condenser and a nitrogen inlet tube were placed and the reaction vessel was immersed in an oil bath and heated to 190 DEG C for 30 minutes and reacted at 190 DEG C for 7 hours to obtain polyester polyol 5. [ During the reaction, the outflow portion was heated to 120 DEG C with a tape heater, and methanol produced by the reaction was distilled off accompanied with nitrogen. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 5.

[Production of polyurethane urea]

A polyurethane-urea solution and a film were obtained in the same manner as in Example 5, with the amount of raw material injected at the time of producing the polyurethane shown in Table 3. As a result of carrying out the peeling test of the film, the stress required for peeling was 10.8 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The film had a surface atomic composition of 0.072 and a water contact angle of 96 degrees. The results are shown in Table 3.

&Lt; Example 10 >

[Production of polyester polyol]

3.0 g (21.1 mmol) of dimethyl succinate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of adipic acid dimethyl, 63.4 g (42.3 mmol) of GI-1000 was used and 2.2 mg of tetrabutyl orthotitanate , Polyester polyol 6 was prepared in exactly the same manner as in Example 9. Table 2 also shows the theoretical molecular weight and the theoretical oxygen content of the polyester polyol 6.

[Production of polyurethane urea]

A polyurethane-urea solution and a film were obtained in the same manner as in Example 5, with the amount of raw material injected at the time of producing the polyurethane shown in Table 3. As a result of carrying out the peeling test of this film, the stress required for peeling was 13.0 g / cm and the peeling property was good. The obtained elastic film had the properties shown in Table 3. [ The surface atomic composition of the film was 0.083 and the water contact angle was 98 degrees. The results are shown in Table 3.

&Lt; Comparative Example 2 &

[Production of polyurethane urea]

A polyurethane urea solution containing no polyester polyol and a film were obtained in the same manner as in Example 5, with the amount of raw materials injected at the time of producing the polyurethane shown in Table 3. As a result of carrying out the peeling test of this film, the stress required for peeling was 66.3 g / cm, and the peeling property was bad. The obtained elastic film had the properties shown in Table 3. [ The surface atomic composition of the film was 0.239 and the water contact angle was 76 degrees. The results are shown in Table 3.

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2008-306247) filed on December 01, 2008 and Japanese Patent Application (Japanese Patent Application No. 2009-179463) filed on July 31, 2009, the contents of which are incorporated herein by reference Is introduced as a reference.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a polyurethane while maintaining constant compatibility with a polyether polyol, and it is possible to reduce the tackiness of the obtained polyurethane. Further, when the obtained polyurethane is molded, the peelability of the molded articles can be improved. Further, when the elastic fiber made of this polyurethane is used to form a medical or the like, it is possible to reduce the cost by reducing the amount of use of the emulsions or the smoothing agent, improve the operational stability by reducing the product contamination and the frequency of clogging of the machine or mechanism , The frictional resistance is reduced, and driving power reduction can be expected. Therefore, the industrial value of the present invention is remarkable.

Claims (9)

(A) a polyester polyol formed from a polyhydroxy hydrocarbon polymer and (B) a dicarboxylic acid, wherein the (A) and the (B) form at least one ester bond, Wherein the content of oxygen is 2.0 mass% or more and 13.5 mass% or less. The method according to claim 1,
Wherein the dicarboxylic acid has 2 to 15 carbon atoms. 3. The method according to claim 1 or 2,
Wherein the polyester polyol is a block copolymer of the (AB) _nA type (wherein n is an integer of 1 or more) formed of the above (A) and the above (B). 3. The method according to claim 1 or 2,
Wherein the number average molecular weight of the polyester polyol is not less than 500 and not more than 5,000. 3. The method according to claim 1 or 2,
Wherein the polyhydroxyhydrocarbon polymer (A) is a hydrogenated polydiene polyol. delete delete delete delete