JP5397143B2 - Polyurethane and process for producing the same - Google Patents

Description

  The present invention relates to polyurethane, a method for producing the same, and uses thereof.

  Polyurethane and polyurethaneurea are applied in various fields. Among them, it is often used for applications such as polyurethane elastic fibers and polyurethane urea elastic fibers. In particular, fibers with a polyurethane urea structure use polyether polyol as the soft segment component and use a polyamine compound with high cohesive strength as the hard segment, so they have excellent elastic properties and stretch recovery properties. ing.

However, these polyurethane-based elastic fibers are poor in unwinding at the time of spinning because of high adhesiveness between the fibers. In addition, since the frictional resistance is high, problems such as yarn breakage are likely to occur in the spinning machine, warping machine, knitting machine, and equipment in the processing process of the guide, and the friction between the processing equipment and the thread. Reduce resistance. Conventional techniques for solving such problems include a method of adding solid metal soap, oil-soluble polymer, higher fatty acid, amino-modified silicone, etc. to polyurethane elastic fiber as an oil agent, talc, silica, colloidal alumina as a smoothing agent. In addition, a method of dispersing titanium oxide or the like in a polyurethane elastic fiber, and a method of introducing silicon diol or silicon diamine into a part of the polyurethane main chain have been studied (for example, Patent Document 1).
However, even with these methods, there are problems that a sufficient anti-adhesion effect cannot be obtained, and that the smoothing agent causes significant wear on the spinning machine, warping machine, knitting machine and guide. In addition, a large amount of oligomers in yarn extracted by oil components during warping and knitting processes, and solid or high-viscosity components separated in solid or paste form adhere to the product, resulting in product fouling And problems such as clogging of machines and instruments have not been solved. For this reason, there has been a demand for a method for producing a polyurethane that reduces adhesiveness and has high unwinding properties (or polyurethane peelability) at the time of spinning without using such an oil agent or a smoothing agent.

  On the other hand, many examples of using polysiloxane polyol or fluorinated polyol as a raw material for polyurethane have been reported so far. For example, as an example of using a polysiloxane polyol, a thermoplastic polyurethane having a high rebound resilience using a modified polysiloxane diol (Patent Document 2), a polyurethane elastic fiber having a soft and good wearing feeling using an ether-modified silicone (Patent document 3) etc. are mentioned. However, since the former uses a large amount of the modified polysiloxane diol with respect to other polyols, the flexibility of the polyurethane is insufficient. In the latter, since ether-modified silicone is added to the obtained polyurethane after the polyurethane is produced, the ether-modified silicone tends to fall off from the fiber surface. Furthermore, even when an attempt is made to mix and react the silicone with a polyol during the production of a polyurethane, there is a problem that the compatibility with other polyols is poor and it is difficult to form a homogeneous polyurethane. As an example of using a fluorinated polyol, a composition for water-repellent polyurethane comprising a fluorinated diol compound has been proposed (Patent Document 4). The polyurethane composition described in Patent Document 4 is excellent in compatibility and water repellency, and is a cured product having no tack or bleed, and can be used for various purposes for waterproofing or weather resistance. However, the fluorinated diol compound has a melting point. There was a problem that it was expensive and the handleability was poor in polyurethane formation.

Japanese Patent Laid-Open No. 10-259577 JP 2004-250683 A JP 2004-332126 A JP 7-316500 A

  In view of the above problems, the present invention provides a polyurethane having low adhesiveness and high peelability, and a method for producing the same, which are useful for high-performance polyurethane applications such as polyurethane elastic fibers and films and clothing when producing polyurethane. This is the issue.

  As a result of intensive studies to solve the above problems, the present inventors have found that, in producing polyurethane, a polysiloxane diol or fluorinated diol and an ester group-containing compound or a carboxyl group-containing compound have at least one ester bond. In order to complete the present invention, the polyester polyol to be formed is reacted with a polyether polyol, an isocyanate compound, and a chain extender to reduce the adhesiveness of the resulting polyurethane and improve the peelability of the polyurethane. It came.

That is, the first gist of the present invention is a polyester polyol in which (a) (i) a polysiloxane diol or a fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond. , the total weight of (b) polyether polyols, (c) an isocyanate compound, and (d) a reportage polyurethane obtained using a chain extender, wherein the polyester polyol (a) and the polyether polyol (b) On the other hand, the polyester polyol (a) is in a polyurethane having a content of 0.01 to 20% by weight .
According to a second aspect of the present invention, in the polyurethane, the polyester polyol (a) is 0.01 to 10% by weight with respect to the total weight of the polyester polyol (a) and the polyether polyol (b). It exists in polyurethane.

The third gist of the present invention resides in the polyurethane, wherein the polyester polyol (a) has a number average molecular weight of 500 or more and 5000 or less.
The fourth gist of the present invention resides in a polyurethane wherein the ester group-containing compound or the carboxyl group-containing compound (ii) is a polylactone.

The fifth gist of the present invention resides in the polyurethane, wherein the ester group-containing compound or the carboxyl group-containing compound (ii) is a dicarboxylic acid.
The sixth gist of the present invention resides in the polyurethane, wherein the isocyanate compound (c) is an aromatic polyisocyanate.
The seventh gist of the present invention resides in the polyurethane wherein the chain extender (d) is a polyamine compound.

The eighth gist of the present invention is a polyester polyol in which (a) (i) a polysiloxane diol or fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond, polyether polyol (b), isocyanate compound (c), and a chain extender (d) is a method for producing a reportage polyurethane obtain a polyurethane as a raw material, the polyester polyol (a) and the polyether polyol (b) The polyester polyol (a) is used in an amount of 0.01 to 20% by weight based on the total weight of the polyurethane .

The ninth gist of the present invention resides in a method for producing polyurethane, which comprises the step of obtaining a mixture of polyester polyol (a) and polyether polyol (b) in the method for producing polyurethane.
The tenth aspect of the present invention resides in a method for producing the polyurethane, the method comprising reacting the mixture with an isocyanate compound (c) to obtain a prepolymer having isocyanate at both ends.

An eleventh aspect of the present invention is a polyester polyol in which (a) (i) a polysiloxane diol or fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond. And (b) a polyether polyol , wherein the polyester polyol (a) is 0.01 to 20 with respect to the total weight of the polyester polyol (a) and the polyether polyol (b). In a mixture characterized in that it is by weight .
The twelfth aspect of the present invention resides in a prepolymer obtained from the mixture and the isocyanate compound (c).
The thirteenth aspect of the present invention resides in a polyurethane molded product, a polyurethane film, or a polyurethane fiber comprising the polyurethane.

  According to the present invention, improvement in homogeneity and reduction in tackiness of the obtained polyurethane can be achieved. As a result, when elastic fibers using this polyurethane are used to warp clothing, etc., the amount used such as oil or smoothing agent Cost reduction due to reduction, improvement in operational stability due to reduced product fouling and clogging of machines and instruments, and reduction in frictional resistance can be expected.

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents. The details will be described below.
The present invention relates to (a) (i) a polysiloxane diol or fluorinated diol, (ii) a polyester polyol in which an ester group-containing compound or a carboxyl group-containing compound forms at least one ester bond, and (b) a polyether polyol. , (C) an isocyanate compound, and (d) a polyurethane obtained using a chain extender.
Hereafter, it explains in full detail for every component requirement.

(1) (a) Polyester polyol The polyester polyol (a) used in the present invention has at least two ester bonds and two or more hydroxyl groups in the molecule, and preferably has a polyester polyol main chain. Both ends are hydroxyl groups.

  The polyester polyol (a) used in the present invention is usually used by mixing with the polyether polyol (b), and by producing polyurethane using them, the resulting polyurethane has adhesiveness and the polyurethane molded product is peeled off. And unwinding properties during spinning can be improved.

In the polyester polyol (a) used in the present invention, either a polysiloxane diol or a fluorinated diol (i) described later and either an ester group-containing compound or a carboxyl group-containing compound (ii) have at least one ester bond. This refers to the polyester polyol to be formed (hereinafter sometimes simply referred to as polyester polyol (a)).
The number of ester bonds formed by the polysiloxane diol or fluorinated diol (i) contained in one molecule of the polyester polyol used in the present invention is usually 1 or more.
Specifically, the polysiloxane diol or fluorinated diol (i) may form a plurality of ester bonds at the molecular terminals, or the plurality of polysiloxane diols or fluorinated diol (i) may form an ester bond. The total number of ester bonds contained in one molecule of the polyester polyol may be 2 or more.
Hereinafter, the requirements for constituting the polyester polyol of the present invention will be described separately.

(1-1) Polysiloxane diol
The polysiloxane diol used in the present invention is a compound having a plurality of siloxane sites and two hydroxyl groups. Known polysiloxane diols can be used, those having hydroxyl groups introduced into the side chain of polysiloxane, those introduced at both ends of polysiloxane, those introduced only at one end of polysiloxane, one end of polysiloxane And those introduced into the side chain. Among these, in order to obtain a polyurethane of a block copolymer, a polysiloxane diol having hydroxyl groups introduced at both ends of the polysiloxane is preferable. Specific examples include polysiloxane diol having the following structure.

  The polysiloxane diol in the present invention has two or more siloxane bonds and two hydroxyl groups in the molecule.

The number average molecular weight of the polysiloxane diol is not particularly limited, but 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. It is.
When the number average molecular weight exceeds the upper limit, when a mixture of the polyester polyol (a) and the polyether polyol (b) (hereinafter sometimes referred to as a polyol mixture), a prepolymer, or a prepolymer solution is formed, the viscosity thereof is increased. It tends to be too high and the operability and productivity tend to be poor, and the properties of the resulting polyurethane polymer at low temperatures tend to be poor. If it is less than the lower limit, the obtained polyurethane polymer becomes hard and sufficient flexibility cannot be obtained, or the elastic performance such as strength and elongation is not sufficient, or excessive residual strain is generated when repeated elongation and recovery. There is a tendency to leave.
The properties of the polysiloxane diol used in the present invention are not particularly limited, but are liquid or waxy at room temperature.

(1-2) Fluorinated diol The fluorinated diol used in the present invention is a compound having a fluorocarbon skeleton represented by CxFy and two hydroxyl groups. x is 2 to 15, preferably 3 to 12, and y is either 2x or 2 (x-1), preferably 2x.
The structure of the fluorinated diol may be linear, branched or cyclic, but is preferably linear. When the main chain is not a so-called perfluoro structure having a structure other than CxFy, the resulting polyurethane may not have sufficient water repellency.
Specific examples of such fluorinated diol compounds include 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5. , 5,6,6-decafluoro-1,7-heptanediol, 2,2,3,3,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol 2,2,3,3,4,4,5,5,6,7,7,8,8,9,9-hexadecafluoro-1,10-decadiol and the like.

The number average molecular weight of the fluorinated diol is not particularly limited, but is usually 50 or more, preferably 80 or more, more preferably 100 or more, usually 4000 or less, preferably 3000 or less, more preferably 2000 or less. is there. When the number average molecular weight exceeds the upper limit, not only the melting point of the fluorinated diol is high and the handling property is deteriorated, but also the viscosity of the polyol mixture, the prepolymer and the prepolymer solution becomes too high, and the operability and productivity are poor. In some cases, the properties of the resulting polyurethane polymer at low temperatures tend to be poor. If the number average molecular weight is less than the lower limit, the resulting polyurethane polymer is hard and sufficient flexibility cannot be obtained, or the elastic performance such as strength and elongation is not sufficient, or when stretching and recovery are repeated. There is a tendency to leave excessive residual strain.
Although the property of the fluorinated diol used in the present invention is not particularly limited, it is solid, liquid or waxy at room temperature.

(2) 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 a compound in which repeating units are polymerized through an ester bond. Preferred is a polylactone obtained by ring-opening polymerization of a lactone.
(2-1) Polylactone As the lactone, ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethylcaprolactone, β-propiolactone, γ-butyrolactone, δ-valero Examples include lactone, γ-valerolactone, and enanthlactone. These may be used alone or in combination of two or more. Ε-caprolactone is most preferred because it is readily available and highly reactive.
Hereinafter, as a polyester polyol (a) formed of a polysiloxane diol or fluorinated diol (i) and an ester group-containing compound (ii), a polyester polyol formed of a polysiloxane diol or fluorinated diol and a polylactone is taken as an example. State.

(3) Polyester polyol formed from polysiloxane diol or fluorinated diol and polylactone One of the preferred embodiments of the polyester ester polyol in the present invention is between the polysiloxane diol or fluorinated diol and the following polylactone. 1 or more ester groups are formed, and preferably at least one of the hydroxyl groups of one molecule of polysiloxane diol or fluorinated diol forms an ester bond with polylactone, and there are a plurality of groups in one molecule. More preferably, at least one of the terminal hydroxyl groups of one molecule of the polysiloxane diol or fluorinated diol forms an ester bond with the polylactone, and there are a plurality of them in one molecule in total. Esters It has a bond.

  The type of copolymerization of the polyester polyol formed by the polysiloxane diol or fluorinated diol moiety (referred to as (X)) and the lactone polyester moiety (referred to as (Y)) is not particularly limited, but preferably (Y ) (X) (Y) type polyester polyol, (Y) is a ring-opening polymer of lactone, and (X) and (Y) are bonded via an ester bond. By adjusting the degree of polymerization of the lactone according to the desired physical properties of the polyurethane resin, it is possible to easily change the molecular weight and oxygen content of the produced polyester polyol. Although the production method is not particularly limited, it is generally obtained by reacting polysiloxane diol or fluorinated diol with a lactone at a predetermined ratio in the presence of a catalyst such as tetraisopropyl titanate or tetrabutyl titanate in the absence of a solvent. Can do.

(4) Carboxyl group-containing compound The carboxy group-containing compound used in the present invention is not particularly limited as long as it has a carboxy group, but usually a monocarboxylic acid compound, a dicarboxylic acid compound, a hydroxy acid, etc. Examples thereof include substituted carboxylic acid compounds, and preferred are dicarboxylic acid compounds.

(4-1) Dicarboxylic acid The dicarboxylic acid compound used in the present invention may be either an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but the aliphatic dicarboxylic acid generally has 2 or more carbon atoms, preferably It is 3 or more, more preferably 4 or more, and usually 16 or less, preferably 15 or less, more preferably 14 or less. Specific examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,9-nonamethylenedicarboxylic acid. Examples include acid, 1,10-decamethylene dicarboxylic acid, 1,11-undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, and the like. Examples of the aromatic dicarboxylic acid include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid.
Needless to say, these dihydric acid compounds or various derivatives can be used as the dicarboxylic acid compound, and these may be used as a mixture of two or more. Examples of the derivatives include alkyl esters and halogen-substituted products of unsaturated bonds. Among these, malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and derivatives thereof are preferable because they are easily available and have high thermal stability. Succinic acid, adipic acid and the like The derivatives of are most preferred.

  Hereinafter, as a polyester polyol formed from a polysiloxane diol or a fluorinated diol and a carboxyl group-containing compound, a polyester polyol formed from a polysiloxane diol or a fluorinated diol and a dicarboxylic acid will be described as an example.

(5) Polyester polyol formed from polysiloxane diol or fluorinated diol and dicarboxylic acid The polyester polyol formed from polysiloxane diol or fluorinated diol and dicarboxylic acid in the present invention is usually polysiloxane diol or fluorinated diol. A polyester polyol in which two molecules each form an ester bond between at least one hydroxyl group each possessed and two carboxy groups contained in one molecule of dicarboxylic acid.

Preferably, it is an (XZX) _i- type polyester polyol formed from a polysiloxane diol or fluorinated diol moiety (X) and a dicarboxylic acid moiety (referred to as Z). (X) and (Z) should just be couple | bonded via the ester bond, and may be manufactured from carboxylic acid derivatives, such as carboxylic acid diester.
More preferably, it is an XZX type polyester polyol in which polysiloxane diol or fluorinated diol is bonded to both ends of dicarboxylic acid one molecule at a time, corresponding to the case of i = 1.
By adjusting the degree of polymerization of the polysiloxane diol or fluorinated diol according to the desired properties of the polyurethane resin, it is possible to easily change the molecular weight and oxygen content of the polyester polyol produced. For these esterifications, conventionally known esterification techniques can be employed.

The polyester polyol (a) used in the present invention may have a structure other than the above structure in the molecule, but preferably a polyester polyol containing no other structure other than the above site.
In the above description, (X) and (Y), and (X) and (Z) are described in detail as constituents for forming an ester bond, but the polyester polyol of the present invention is limited to this. Instead, any raw material and reaction method may be used as long as the molecular structures obtained are the same.

The ratio of the polysiloxane diol or fluorinated diol (i) site in the polyester polyol (a) used in the present invention is not particularly limited, but the polysiloxane diol site is usually 10% by weight or more. Yes, preferably 20% by weight or more, more preferably 30% by weight or more, still more preferably 40% by weight or more, and particularly preferably 50% by weight. As this value increases, the tackiness of the resulting polyurethane resin tends to decrease. On the other hand, the upper limit is usually 96% by weight or less, preferably 94% by weight or less, more preferably 92% by weight or less, still more preferably 90% by weight or less, and particularly preferably 88% by weight or less. The smaller this value is, the more the adhesive property of the resulting polyurethane resin increases, but the elastic properties and stretch recovery tend to improve.
The fluorinated diol moiety is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more, still more preferably 30% by weight or more, and particularly preferably 40% by weight. As this value increases, the tackiness of the resulting polyurethane resin tends to decrease. On the other hand, the upper limit is usually 95% by weight or less, preferably 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and particularly preferably 70% by weight or less. The smaller this value is, the more the adhesive property of the resulting polyurethane resin increases, but the elastic properties and stretch recovery tend to improve.

(6) Physical properties of polyester polyol The number average molecular weight of the polyester polyol used in the present invention can be adjusted by the type and amount of the substrate used. The lower limit of the number average molecular weight is usually 300 or more, preferably 400 or more, more preferably 500 or more, and the upper limit is usually 8000 or less, preferably 6000 or less, more preferably 5000 or less. The number average molecular weight indicates an average molecular weight per molecule. When the number average molecular weight exceeds the upper limit, the viscosity of the prepolymer and the prepolymer solution becomes too high and the operability and productivity tend to deteriorate, or the properties of the resulting polyurethane polymer at low temperatures tend to deteriorate. If the number average molecular weight is less than the lower limit, the resulting polyurethane polymer is hard and sufficient flexibility cannot be obtained, or the elastic performance such as strength and elongation is not sufficient, or when stretching and recovery are repeated. There is a tendency to leave excessive residual strain.

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

  Among these, among the polyol units constituting the polyether polyol, polytetramethylene ether glycol, polytrimethylene ether glycol, 1 to 20 mol% of a copolymer polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya) Chemical-manufactured “PTG-L1000”, “PTG-L2000”, “PTG-L3500”, etc.) or a copolymerized polyether glycol of neopentyl glycol and tetrahydrofuran is preferred.

The amount of the polyether polyol (b) used is not particularly limited, but the amount of the polyester polyol (a) used is usually based on the total weight of the polyester polyol (a) and the polyether polyol (b). It is 0.01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight or more, still more preferably 0.07% by weight or more, and particularly preferably 0.1% by weight or more. There exists a tendency for the adhesiveness of the obtained polyurethane resin to fall, so that the usage-amount of polyester polyol (a) becomes large. The amount of the polyester polyol (a) used is usually 20% by weight or less, preferably 17% by weight or less, more preferably 15% by weight or less, still more preferably 12% by weight or less, and particularly preferably 10% by weight. % By weight or less. The smaller the amount of the polyester polyol (a) used, the greater the tackiness of the resulting polyurethane resin, but there is a tendency for the elastic properties and stretch recovery properties to improve.
Moreover, the smaller the amount of the polyester polyol (a) used, the better the compatibility with the polyether polyol (b), making it easier to produce a homogeneous and transparent film or yarn. In general, the addition of a silicone compound is effective for improving the tackiness of the polyurethane, but there is a problem that the compatibility with the polyether polyol (b) is poor and the polyurethane resin or the like becomes cloudy. In the present invention, a polyester polyol having high compatibility with the polyether polyol is mixed with the polyether polyol, and the polyol mixture is used as the polyurethane material. Therefore, homogeneous and transparent polyurethane resins can be produced.

<(C) Isocyanate compound>
The isocyanate compound (c) used in the present invention is not limited. For example, 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'- MDI, aromatic diisocyanates such as paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, aliphatic diisocyanates having an aromatic ring such as α, α, α ′, α′-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene Aliphatic diisocyanates such as diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4 Cyclohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4 ' -An alicyclic diisocyanate such as diisocyanate is exemplified. These may be used alone or in combination of two or more. In the present invention, a highly reactive aromatic polyisocyanate is particularly preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferable. In addition, a part of the NCO group of the isocyanate compound may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc., and the polynuclear substance contains isomers other than those described above. The thing which is included is also included.

The amount of these isocyanate compounds (c) used is usually based on the total of the hydroxyl groups of the polyester polyol (a) and the polyether polyol (b) and 1 equivalent of the total of the hydroxyl groups and amino groups of the chain extender (d). 0.1 equivalent to 5 equivalents, preferably 0.8 equivalents to 2 equivalents, more preferably 0.9 equivalents to 1.5 equivalents, still more preferably 0.95 equivalents to 1.2 equivalents, and most preferably 0. 98 equivalents to 1.1 equivalents.
If the amount of the isocyanate compound used is too large, the unreacted isocyanate group will react unfavorably and the desired physical properties tend to be difficult to obtain. If it is too small, the molecular weight of polyurethane and polyurethane urea will not be sufficiently increased. The desired performance tends not to be expressed.

<(D) Chain extender>
The chain extender (d) referred to in the present invention is mainly classified into a compound having two or more hydroxyl groups, a compound having two or more amino groups, and water. Of these, short-chain polyols, specifically compounds having two or more hydroxyl groups, are preferred for polyurethane applications, and polyamine compounds, specifically compounds having two or more amino groups, are preferred for polyurethane urea applications. In the chain extender (d), water is preferably reduced as much as possible in order to carry out the reaction stably.

In the polyurethane resin of the present invention, it is more preferable in view of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less in combination as the chain extender (d) because the rubber elasticity of the polyurethane elastomer is improved.
Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2 -Propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl -1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8 -Aliphatic glycols such as octanediol and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene.

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

The amount of these chain extenders (d) used is not particularly limited, but when the equivalent of subtracting the equivalent of the isocyanate compound from the total hydroxyl equivalent of the polyester polyol (a) and the polyether polyol (b) is 1, Usually, it is 0.1 equivalent or more and 5.0 equivalent or less. Preferably it is 0.8 equivalent or more and 2.0 equivalent or less, More preferably, it is 0.9 equivalent or more and 1.5 equivalent or less. When the amount of the chain extender (d) used is too large, the obtained polyurethane and polyurethane urea are too hard and the desired properties cannot be obtained, and the processing tends to be difficult to dissolve in the solvent and is too small. And, it is so soft that sufficient strength, elastic recovery performance and elastic holding performance cannot be obtained, and high temperature characteristics tend to be deteriorated.
For the purpose of controlling the molecular weight of polyurethane, a chain terminator having one active hydrogen group can be used as necessary. Examples of these chain terminators include aliphatic monools such as ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having an amino group. Is done. These may be used alone or in combination of two or more.

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

<Polyurethane>
The polyurethane of the present invention indicates polyurethane or polyurethane urea unless otherwise specified, and it has been conventionally known that these two types of resins have similar physical properties. On the other hand, as structural differences, polyurethane is a resin that forms a chain structure mainly by urethane bonds, and polyurethane urea is a resin that forms a chain structure mainly by urethane bonds and urea bonds. From the viewpoint of raw materials, polyurethane is produced using a short-chain polyol as a chain extender, and polyurethane urea is produced using a polyamine compound as a chain extender.
The polyurethane in the present invention is a polyester polyol in which (a) (i) a polysiloxane diol or fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond, (b ) A polyether polyol, (c) an isocyanate, and (d) a chain extender.

  As for each composition ratio, the total number of moles of the hydroxyl groups of the polyester polyol (a) and the polyether polyol (b) is usually A, the number of moles of the isocyanate groups of the isocyanate compound (c) is B, and chain extension. When the number of moles of active hydrogen substituents (hydroxyl group and amino group) in the agent (d) is C, A: B is usually in the range of 1:10 to 1: 1, preferably 1: 5 to 1: 1. 05, more preferably 1: 3 to 1: 1.1, still more preferably 1: 2.5 to 1: 1.2, particularly preferably 1: 2 to 1: 1.2, and (B-A ): C is usually 1: 0.1 to 1: 5, preferably 1: 0.8 to 1: 2, more preferably 1: 0.9 to 1: 1.5, and still more preferably 1: 0. It is in the range of 95 to 1: 1.2, particularly preferably 1: 0.98 to 1: 1.1.

(7) Production Method of Polyester Polyol (a) Production of the polyester polyol can employ a conventionally known esterification technique. For example, a method of reacting a diol with a lactone or a dicarboxylic acid under normal pressure, a method of esterifying under a reduced pressure, or esterification in the presence of an inert solvent such as toluene, and then condensing condensed water or a condensed alcohol with a solvent. There is a method of removing it from the reaction system by boiling.
The reaction temperature for esterification is usually in the range of 100 to 250 ° C. Preferably it is 120-240 degreeC, More preferably, it is 140-230 degreeC, Most preferably, it is the range of 150-220 degreeC. If the reaction temperature is too low, the esterification reaction does not proceed sufficiently, and if it is too high, the coloring of the product may increase.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary, and the reaction can be performed under normal pressure or reduced pressure depending on the purpose. In reactions such as diols and dicarboxylic acids or dicarboxylic acid esters, water and alcohol are produced during the reaction. In order to promote their elimination from the reaction system, an inert gas is passed through the reaction system. Also good.

(8) Catalyst Although it is possible to carry out the esterification reaction in a system in which no catalyst is present, usually an inorganic acid or an organic acid; Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Pb, Sn, Sb, Pb or other metal chloride, oxide, hydroxide or acetic acid, Shu Fatty acids such as acids, 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 Other organometallic compounds of metals such as Al, Ti, Zn, Sn, Zr or Pb , It can be carried out using any catalysts used for conventional esterification and for transesterification. A titanium-based catalyst such as isopropyl titanate or n-butyl titanate is most preferred because it is easily available and has low toxicity and is widely used in esterification reactions. The amount of the catalyst used in that case is preferably 0.00001 to 1.0% by weight, more preferably 0.0001 to 0.1% by weight, and more preferably 0.001 to 0.1% by weight based on the total amount of the raw materials for preparing the polyester diol. Most preferred is 01% by weight. If this amount is too small, it takes a very long time to form the polyester polyol, and the product tends to be colored. On the other hand, if the amount of the catalyst used is too large, there is a possibility of exhibiting an excessive reaction promoting action for the polyurethane reaction.

The reaction time varies depending on the amount of the catalyst used, the reaction temperature, the substrate to be reacted, the desired physical properties of the polyester polyol to be produced, etc., but is as follows. The lower limit is usually 0.5 hours, preferably 1 hour, and the upper limit is usually 30 hours, preferably 20 hours.
Since the removal of the titanium-based catalyst from the polyester polyol product usually involves complicated steps, the produced polyester polyol is generally often used as it is for the production of polyurethane without separating the titanium-based catalyst. However, it is preferable to deactivate the titanium catalyst in the polyester polyol when the content of the catalyst is large or depending on the use of the polyurethane. Examples of the method for deactivating the titanium-based catalyst in the polyester polyol include: (x) a method in which the polyester polyol is brought into contact with water under heating; (y) the polyester polyol in phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid. The method of processing with phosphorus compounds, such as acid ester, etc. can be mentioned. And when it is based on the method of said (x) made to contact with water, for example, 1 weight% or more of water is added to polyester polyol, and it is 70-150 degreeC, Preferably it is about 90-130 degreeC for about 1-3 hours. Heat it up. The deactivation treatment by heating at that time may be performed under normal pressure or under pressure, and when the system is depressurized after the deactivation treatment, the water used for deactivation can be smoothly removed from the polyester polyol. .

<Production method of polyurethane>
In the present invention, a polyurethane is produced by a polyester in which (a) (i) a polysiloxane diol or fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond. A polyol, (b) a polyether polyol, (c) an isocyanate compound, and (d) a chain extender are mainly used as raw materials for production.
In order to produce the polyurethane, all production methods generally used experimentally / industrially can be used, and the polyurethane can be produced in the absence of a solvent or in the presence of a solvent. In addition, as long as there is no restriction | limiting in particular in the usage-amount of each compound, what is necessary is just to use the said amount.
When a solvent is used in the polyurethane reaction, the solvent to be used is not particularly limited, but is selected from the group consisting of amide solvents, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide from the viewpoint of versatility and solubility. The solvent used is preferably used. Specific examples of the amide solvent include N, N-dimethylacetamide, N, N-dimethylformamide, and a mixture of two or more thereof, and dimethylformamide and dimethylacetamide are particularly preferable.

As an example of the production method, the method (a), the method (b), the method (c) and the method (d) are reacted together (hereinafter referred to as a one-step method). ), The mixture and the above (c) are reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer and the above (d) are reacted (hereinafter referred to as a two-stage method). (B) and (c) are reacted, and then (a) is mixed and reacted with (d), (b), (c), and (d) are reacted. Then, the method of mixing said (a) is mentioned. Among these, the two-stage method prepares an intermediate sealed with isocyanate at both ends corresponding to the soft segment of polyurethane by reacting polyether polyol (b) with one or more equivalents of isocyanate compound (c) in advance. It goes through a process. By preparing the prepolymer and then reacting it with the chain extender (d), it is easy to adjust the molecular weight of the soft segment part, and the phase separation between the soft segment and the hard segment is easy to be made, and the performance as an elastomer is exhibited. There are easy features. In particular, when the chain extender (d) is a diamine, since the reaction rate with the isocyanate group is greatly different from that of the hydroxyl group of the polyether polyol, it is more preferable to carry out the polyurethane urea formation by a two-stage method.

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

<Two-stage method>
The two-stage method is also called a prepolymer method. First, a polyester polyol (a) and a polyether polyol (b) are mixed to obtain a mixture, and then an isocyanate compound (c) and a polyol mixture are usually reacted in a reaction equivalent. It is also possible to produce a prepolymer reacted at a ratio = 1.0 to 10.00, and then react it in two steps by adding an active hydrogen compound component such as an isocyanate compound (c) or a polyhydric alcohol, an amine compound to this. it can. Particularly useful is a method in which an isocyanate compound (c) of an equivalent amount or more is reacted with a polyol mixture to form an NCO prepolymer at both ends, and a polyurethane is obtained by reacting a short chain diol or diamine as a chain extender. .
The two-stage method can be carried out without a solvent or in the presence of a solvent. When carried out in the presence of a solvent, from the viewpoint of versatility and solubility, amide solvents, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl sulfoxide are preferable. Specific examples of amide solvents include N, N-dimethyl. Acetamide and N, N-dimethylformamide are more preferable, and N, N-dimethylformamide and N, N-dimethylacetamide are particularly preferable.
When synthesizing the prepolymer, (1) first, the isocyanate compound (c) and the polyether polyol (b) are directly reacted without using a solvent to synthesize the prepolymer, and the prepolymer may be used as it is. The prepolymer may be synthesized by the method 1) and then dissolved in a solvent and used. (3) The isocyanate compound (c) may be reacted with polyether glycol using a solvent from the beginning. In the case of (1), in the present invention, when acting with the chain extender (d), the chain extender (d) is dissolved in a solvent, or the prepolymer and the chain extender (d) are simultaneously introduced into the solvent. It is important to obtain polyurethane in a form coexisting with a solvent by such a method.

As for the reaction equivalent ratio of NCO / active hydrogen group (polyol), the lower limit is usually 1, preferably 1.05, and the upper limit is usually 10, preferably 5, more preferably 3. If this ratio is too small, excessive isocyanate groups tend to adversely affect the physical properties of the polyurethane due to side reactions, and if it is too small, the molecular weight of the resulting polyurethane will not be sufficient, resulting in strength and thermal stability. Tend to cause problems.
The amount of chain extender (d) used is not particularly limited, but the lower limit is usually 0.1, preferably 0.8, and the upper limit is usually 5 with respect to the equivalent amount of NCO groups contained in the prepolymer. 0.0, preferably in the range of 2.0.
Further, a monofunctional organic amine or alcohol may coexist during the reaction.
In the chain extension reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the temperature is too low, the progress of the reaction is too slow, or the solubility of the raw materials and the polymer is low, so that the productivity is poor, and if it is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure.
Moreover, a catalyst, a stabilizer, etc. can also be added for reaction as needed. Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. Examples of the stabilizer include 2,6-dibutyl-4-methylphenol. , Distearyl thiodipropionate, di-betanaphthyl phenylenediamine, tri (dinonylphenyl) phosphite and the like. However, when the chain extender is highly reactive, such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.

<Physical properties of polyurethane>
Since the polyurethane obtained by the above production method is reacted in the presence of a solvent, it is generally obtained in a state dissolved in a solution, but is not limited in a solution state or a solid state.
The weight average molecular weight of the polyurethane varies depending on the use, but is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 100,000 to 300,000 as the polyurethane polymerization solution. is there. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, and more preferably 1.8 to 3. As a fiber, a film, and a moisture-permeable resin molding, the weight average molecular weight of polyurethane is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 to 40. It is ten thousand. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.7 to 3, and more preferably 1.8 to 3.
Further, the polyurethane obtained by the above production method preferably contains 1 to 20% by weight, more preferably 3 to 15% by weight, based on the total weight of the polyurethane polymer. More preferably, it is 4 to 12% by weight, and particularly preferably 5 to 10% by weight. When the amount of the hard segment is too large, the obtained polyurethane polymer does not exhibit sufficient flexibility and elastic performance, or when using a solvent, it tends to be difficult to dissolve and difficult to process. If the amount of hard segment is too small, the urethane polymer tends to be too soft and difficult to process, and sufficient strength and elastic performance tend not to be obtained.
In the present invention, the hard segment refers to P.I. J. et al. Based on Flory, Journal of American Chemical Society, 58, 1877-1885 (1936), the weight of isocyanate and amine bond portion relative to the total weight is calculated by the following formula.

Hard segment (%) = [(R−1) (Mdi + Mda) / {Mp + R · Mdi + (R−1) · Mda}] × 100
here,
R = number of moles of isocyanate / (number of moles of hydroxyl group of polyether polyol + number of moles of terminal allyl group)
Mdi = number average molecular weight of diisocyanate
Mda = number average molecular weight of diamine
Mp = number average molecular weight of polyether polyol
The polyurethane solution obtained in the present invention is less prone to gelation, has good storage stability such as small changes in viscosity over time, and has low thixotropy, which is convenient for processing into films, yarns, etc. . The polyurethane concentration of the polyurethane solution is usually 1 to 99% by weight, preferably 5 to 90% by weight, more preferably 10 to 70% by weight, particularly preferably 15 to 50% by weight, based on the total weight of the solution dissolved in the solvent. %. If the amount of polyurethane is too small, it is necessary to remove a large amount of solvent, which tends to reduce productivity, and if too much,
The viscosity of the solution is too high and the operability and workability tend to be poor.
The polyurethane solution is not particularly specified, but when it is stored for a long period of time, it is preferably stored in an inert gas atmosphere such as nitrogen or argon at room temperature or lower.

<Polyurethane moldings / uses>
The polyurethane and its urethane prepolymer solution produced in the present invention can express various properties and are widely used in foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, and the like. Can be used.
The polyurethane, polyurethane urea and urethane prepolymer solution produced in the present invention can be used for cast polyurethane elastomers. Examples include rolls such as rolling rolls, papermaking rolls, office equipment, pretension rolls, forklifts, solid tires for casters, vehicles, etc., casters, industrial products such as conveyor belt idlers, guide rolls, pulleys Steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. It is also applied to OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, and surface rollers.

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

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as components of moisture-curable one-component paints, block isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet curable paints, etc. For example, plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring materials, overprint varnishes such as paper and wood grain printing films, wood varnishes, coil coats for high processing, optical fiber protective coatings , Solder resist, metal printing top coat, vapor deposition base coat, food can white coat and the like.
The polyurethane and its urethane prepolymer solution produced in the present invention are applied as adhesives to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. It can also be used as a component of a melt.
The polyurethane and its urethane prepolymer solution produced in the present invention are magnetic recording medium, ink, casting, fired brick, graft material, microcapsule, granular fertilizer, granular agricultural chemical, polymer cement mortar, resin mortar, rubber chip binder. It can be used for recycled foam and glass fiber sizing.

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as a component of a fiber processing agent for shrink-proofing, anti-molding, water-repellent processing and the like.
The polyurethane, polyurethane urea and its urethane prepolymer solution produced in the present invention are used as a sealant caulking for concrete wall, induction joint, sash area, wall-type PC joint, ALC joint, board joint, composite glass Can be used for sealant, heat insulating sash sealant, automotive sealant, etc.
The polyurethane and its urethane prepolymer solution produced in the present invention can be used as medical materials, such as tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc. as blood compatible materials, and catheters as disposable materials. , Tubes, bags, surgical gloves, artificial kidney potting materials, etc.
The polyurethane, polyurethane urea, and urethane prepolymer solution produced in the present invention are modified with UV curable paint, electron beam curable paint, photosensitive resin composition for flexographic printing plate, photocurable It can be used as a raw material for the optical fiber coating material composition.
In particular, it is preferable to use the elastic performance and moisture permeability characteristics of the polyurethane produced by the present invention to be used for films and fibers. Specific examples of these applications include medical, hygiene materials, artificial leather, and clothing. It is preferable to use for these elastic fibers.
As mentioned above, although the usage example using the polyurethane manufactured by this invention and its urethane prepolymer solution was described, this invention is not limited to these uses.
Although the manufacturing method of a film and a fiber is described below, a manufacturing method is not necessarily restrict | limited.

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

<Physical properties of film>
Although the thickness of the film of this invention is not limited, Usually, 10-1000 micrometers, Preferably it is 10-500 micrometers, More preferably, it is 10-100 micrometers. If the film is too thick, sufficient moisture permeability tends not to be obtained, and if it is too thin, pinholes are likely to be formed or the film tends to be blocked and difficult to handle. Moreover, this film can be preferably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. The film may be applied to a support such as cloth or nonwoven fabric. In this case, it may be thinner than 10 μm.
The elongation at break is usually 100% or more, preferably 200% or more, more preferably 300% or more, and still more preferably 500% or more. The breaking strength is usually 5 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and further preferably 30 MPa or more.
The physical properties of the polyurethane film and the yarn have a very good correlation, and the physical properties obtained by the film test and the like show the same tendency in the yarn (fiber).

<Uses of polyurethane fibers>
The fiber using the polyurethane of the present invention is more specifically used for leg, panty / stocking, diaper cover, paper diaper, sports clothing, underwear, socks, fashionable stretch clothing, swimwear, It is preferably used for applications such as leotard. This is because it is excellent in stretch recovery, elasticity, hydrolysis resistance, light resistance, oxidation resistance, oil resistance, workability, and the like.
The excellent moisture permeability of this elastic fiber is characterized by being less stuffy and comfortable to wear when used in clothing. Moreover, the characteristic that the rate of fluctuation of stress is small or the modulus is small, for example, it can be passed through the sleeve with a small force when it is applied to the body as clothing, and it is very easy to remove even for small children and the elderly. It has the characteristics. In addition, because of the good fit and movement following ability, it can be used for sports clothing and more fashionable clothing. Further, since the elastic retention rate in the repeated extension test is high, the elastic performance is not easily impaired even after repeated use.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. The analysis and measurement in the following examples and comparative examples were based on the following methods.

<Number average molecular weight of polyether polyol>
The number average molecular weight of the polyether polyol used in the present invention was determined by a hydroxyl value (KOH (mg) / g) measurement method by an acetylation method based on JIS K1557-1: 2007.
<Molecular weight of polyurethane and polyurethane urea>
The molecular weight of the obtained polyurethane or polyurethane urea was prepared by preparing a dimethylacetamide solution of polyurethane or polyurethane urea and using a GPC apparatus [manufactured by Tosoh Corporation, product name “HLC-8220” (column: Tskel GMH-XL (two)]. 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 are overlapped, and a sample length of 4 cm (including an initial test length portion and a 2.5 cm overlap portion when fixed to a tensile tester having a length of 1.5 cm) and a width of 1 cm with a test piece punching machine. A film was obtained. The test piece was allowed to stand at a temperature of 25 ° C. and a relative humidity of 50% for 10 minutes in a state where a pressure of 200 g / cm 2 was applied, and then a tensile tester (FU
The T-type peel strength was measured by pulling the test film at a speed of 300 mm / min using a DOH “Rheometer NRM-2003J”).

<Physical properties of film>
The polyurethane or polyurethane urea test piece is a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm, and in accordance with JIS K6301, using a tensile tester (product name “Tensilon UTM-III-100” manufactured by Orientec Co., Ltd.). The tensile breaking strength at a temperature of 23 ° C. (relative humidity 55%), tensile breaking elongation, and strength at 100% elongation and 300% elongation were measured at a chuck distance of 50 mm and a tensile speed of 500 mm / min.

<Example 1>
<Production of polyester polyol 1>
In a 100 mL four-necked round bottom flask equipped with a stirrer, 4.2 mg of tetrabutyl orthotitanate (Tokyo Kasei Co., Ltd.), 62.5 g (34.5 mmol) of carbinol-modified silicone (KF-6001 manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group) Value 62) 10 g (87.6 mmol) of ε-caprolactone (Across) was measured. A reflux pipe and a nitrogen introduction pipe were attached, the reaction vessel was immersed in an oil bath, heated to 190 ° C. in 30 minutes, and reacted at 190 ° C. for 7 hours to obtain polyester polyol 1.

<Manufacture of polyurethane urea>
Polytetramethylene ether glycol (number average molecular weight 1955 calculated from hydroxyl value, 1955, manufactured by Mitsubishi Chemical Corporation) previously heated to 40 ° C. in a 1 L flask and 5 parts of the polyester polyol 1 synthesized above .71 parts by weight was added and mixed, and this mixture was used as a raw material for producing polyurethane. The ratio of polyester polyol 1 to this mixture was 5% by weight. Thereafter, 30.6 parts by weight of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as “MDI”) heated to 40 ° C. was added. The reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) at this time was 1.6. Then, this flask was set in a 45 ° C. oil bath, and the temperature of the oil bath was raised to 70 ° C. over 1 hour while stirring with a vertical stirring blade in a nitrogen atmosphere. Held for hours. After the residual NCO group was reacted with an excess amount of dibutylamine and then the residual dibutylamine was back titrated with hydrochloric acid to confirm that the NCO reaction rate exceeded 99%, the oil bath was removed, and N, A polyurethane prepolymer solution was prepared by adding 234 parts of N-dimethylacetamide (hereinafter sometimes abbreviated as “DMAC”; manufactured by Kanto Chemical Co., Inc.) and stirring and dissolving at room temperature.
The polyurethane prepolymer solution was cooled and held at 10 ° C., while a 0.5% DMAC solution of ethylenediamine (EDA) / diethylamine (DEA) = 88/12 (molar ratio) used as a chain extender was prepared. did. The polyurethane prepolymer solution cooled and held at 10 ° C. was added to this 0.5% DMAC solution while stirring at high speed to obtain a polyurethane urea DMAC solution having a polymer concentration of 20%.
This solution was aged overnight at 25 ° C., and then the weight average molecular weight and molecular weight distribution were measured by GPC. As a result, the weight average molecular weight was 194,000 and the molecular weight distribution was 2.5.
The polyurethaneurea solution thus obtained was cast on a glass plate and dried at 60 ° C. to obtain a colorless and transparent film having a thickness of about 50 μm. The thickness of the film was measured with a thickness meter.
When this film was peeled, the stress required for peeling was 0.6 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 2.

<Production of polyurethane urea 2>
Polyurethane urea 2 was produced in the same procedure as in Example 1, using 143.3 parts by weight of polytetramethylene ether glycol, 0.14 parts by weight of polyester polyol 1 synthesized in Example 1, and 29.0 parts by weight of MDI. .
After this solution was aged at 25 ° C. overnight, the weight average molecular weight and molecular weight distribution were measured by GPC. The weight average molecular weight was 303,000 and the molecular weight distribution was 2.5. When a film was produced from this polyurethane urea solution and subjected to a peel test, the stress required for the peel was 7.0 g / cm, and the peelability was good. Further, the obtained elastic film had characteristics as shown in Table 2.

<Comparative Example 1>
<Manufacture of polyurethane urea>
A polyurethane urea solution and a film containing no polyester polyol were obtained in the same manner as in Example 1 with the charging amounts shown in Table 2. When this film was peeled, the stress required for peeling was 66.3 g / cm, and the peelability was poor. Further, the obtained elastic film had characteristics as shown in Table 2.

  Improves the homogeneity of polyurethane and reduces the stickiness, and in the case of producing elastic fibers using this polyurethane, it reduces costs by reducing the amount of oil and smoothing agents used, product fouling and clogging of machinery and equipment It can be expected to improve operational stability by reducing frequency and drive power by reducing frictional resistance.

Claims (15)

(A) a polyester polyol in which (i) a polysiloxane diol or a fluorinated diol and (ii) an ester group-containing compound or a carboxyl group-containing compound form at least one ester bond, (b) a polyether polyol, (c) ) a Lupo polyurethane obtained using isocyanate compounds, and (d) is a chain extender,
The polyurethane, wherein the polyester polyol (a) is 0.01 to 20% by weight based on the total weight of the polyester polyol (a) and the polyether polyol (b).   The polyurethane according to claim 1, wherein the polyester polyol (a) is 0.01 to 10% by weight based on the total weight of the polyester polyol (a) and the polyether polyol (b). The polyurethane according to claim 1 or 2, wherein the polyester polyol (a) has a number average molecular weight of 500 or more and 5000 or less.   The polyurethane according to any one of claims 1 to 3, wherein the ester group-containing compound or the carboxyl group-containing compound (ii) is a polylactone.   The polyurethane according to any one of claims 1 to 3, wherein the ester group-containing compound or the carboxyl group-containing compound (ii) is a dicarboxylic acid.   The polyurethane according to any one of claims 1 to 5, wherein the isocyanate compound (c) is an aromatic polyisocyanate.   The polyurethane according to any one of claims 1 to 6, wherein the chain extender (d) is a polyamine compound. Polyester polyol, polyether polyol (b), isocyanate compound in which (a) (i) polysiloxane diol or fluorinated diol and (ii) ester group-containing compound or carboxyl group-containing compound form at least one ester bond (c), and a chain extender (d) is a method for producing a reportage polyurethane obtain a polyurethane as a raw material,
A method for producing a polyurethane, wherein the polyester polyol (a) is used in an amount of 0.01 to 20% by weight based on the total weight of the polyester polyol (a) and the polyether polyol (b).   The manufacturing method of the polyurethane of Claim 8 including the process of obtaining the mixture of polyester polyol (a) and polyether polyol (b).   The process according to claim 9, comprising a step of reacting the mixture with the isocyanate compound (c) to obtain a prepolymer having isocyanate at both ends. A polyester polyol in which (a) (i) a polysiloxane diol or fluorinated diol, (ii) an ester group-containing compound or a carboxyl group-containing compound forms at least one ester bond, and (b) a polyether polyol. A mixture containing
A mixture wherein the polyester polyol (a) is 0.01 to 20% by weight based on the total weight of the polyester polyol (a) and the polyether polyol (b).   The prepolymer obtained from the mixture of Claim 11, and an isocyanate compound (c).   The polyurethane molding which uses the polyurethane in any one of Claims 1-7.   The polyurethane film which uses the polyurethane in any one of Claims 1-7.   A polyurethane fiber comprising the polyurethane according to claim 1.