JP2008248137A - Polyurethane resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane resin composition excellent in elastic properties, such as a high fracture stretchability, small stress fluctuation with respect to deformation in expansion, small hysteresis loss of stress in expansion and contraction, small residual strain after expansion and contraction under normal, low and high temperature, excellent moisture permeability and dyeability. <P>SOLUTION: The polyurethane resin composition comprises a polyetherpolyol, as a constituting component, containing at least 50 mol% of 1,3-propanediol unit obtained by dehydration of polyol, and preferably having a specified content of the hard segments in the total polyurethane polymer in the polyurethane resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to the novel polyurethane and polyurethane urea resin composition of the present invention and a method for producing the same.

  Polyurethanes and polyurethaneureas are applied in various fields, but since they have a wide variety of uses, particularly improvements in elastic functions and the like are desired. Specifically, it is desired that the elastic function at room temperature is high breaking elongation, small stress fluctuation with respect to deformation strain, low hysteresis loss of stress during expansion and contraction, and elastic recovery at low temperatures. Improvement is desired.

For the purpose of improving these elastic functions, technical improvements such as suppressing the crystallinity of soft segments in polyurethane and polyurethane urea using various diols that are difficult to crystallize have been made. It has not yet reached.
An example of the technical improvement is poly (1,2-propylene ether) glycol. Poly (1,2-propylene ether) glycol is a low-cost polyether glycol that is difficult to crystallize because it has methyl groups in the repeating unit. However, polyurethane elastomers obtained from poly (1,2-propylene ether) glycol have the disadvantages of low strength and elongation, and their uses are limited. In addition, the polyurethane has a problem that the reactivity is low because the hydroxyl group of poly (1,2-propylene ether) glycol is secondary. Further, since poly (1,2-propylene ether) glycol has a very narrow molecular weight distribution, it is described that the poly (1,2-propylene ether) glycol has a bad influence on the performance of polyurethane and polyurethane urea elastomer due to the molecular weight distribution being too narrow. (Non-Patent Document 1)
On the other hand, using polytetramethylene ether glycol (PTMG) to reduce the hard segment content to less than 10% in order to develop the softness and elastic functions required by customers for elastic fiber applications at room temperature. Therefore, the durability at low temperature is not always sufficient.
Therefore, as a means for solving the above-described problems, it has been attempted to produce polyurethane or polyurethane urea from polytrimethylene ether glycol.

  For example, polyurethane and polyurethaneurea elastomer compositions derived from polyoxetane polymers have also been reported. However, polyoxetane compositions derived from this method are only an academic consideration because of the instability of monomers, the cost, and the lack of commercial availability in large quantities, and problems remain in the industry. (Non-patent document 2).

Recently, there have been reports of polyurethanes and polyurethane urea elastomer molded products that are polymerized in a solvent-free manner using polytrimethylene ether glycol produced by the dehydration condensation reaction of 1,3-propanediol. Yes. (Patent Document 1)
S. D. Senecar "New Ultra-Low Monopolls with Unique High-Performance Characteristics", Polyethane Expo '96, 305-313 Conjeevavaram et al. Polymer Science, Polymer Chemistry Edition, 28, 429-444 (1985) JP 2005-535744 A

  According to the study by the present inventors, when using a polyether polyol obtained from oxetane described in Non-Patent Document 2, dimethyl sulfoxide which is not industrially available and is used as a solvent. In polyurethane urea, the solubility of polyurethane urea is not sufficient, so the molecular weight cannot be increased to achieve sufficient performance as an elastomer, or the removal of the solvent is difficult due to the high boiling point. Problems such as inapplicability with the polyether polyol obtained by the reaction became clear.

  Moreover, even if it is going to implement polyurethane and a polyurethane urea formation reaction using the manufacturing method which does not use the solvent currently disclosed by patent document 1, reaction cannot be controlled depending on the kind of isocyanate or amine, and homogeneous polyurethane and polyurethane urea are Problems such as inability to obtain occurred, and problems such as difficulty in forming into fibers and films became apparent. Specifically, by examining this technical content, although it is suitable for the production of a polyurethane comprising a combination of a relatively low-reactivity polyisocyanate or a relatively low-reactivity polyamine or polyol, a highly reactive aroma. In combination with aliphatic isocyanates and aliphatic amines, it was revealed that the reaction cannot proceed uniformly in the process of polyurethane polymerization, and polyurethane having sufficient physical properties cannot be obtained. Therefore, it is difficult to apply in the production of fibers, films, artificial leather, high-performance elastomers and the like.

  Accordingly, an object of the present invention is to provide a polyurethane and a polyurethane urea resin composition that are extremely useful for high-performance polyurethane elastomer applications such as polyurethane elastic fibers, synthetic / artificial leather, and TPU.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain 50 mol% or more of 1,3-propanediol units obtained by polyol dehydration condensation reaction, obtained by polyol dehydration condensation reaction. By using polyether polyol as a component, and by specifying the amount of hard segments with respect to the total weight of the polyurethane polymer in the polyurethane, especially high elongation at break, small stress fluctuations due to deformation during expansion, and low hysteresis loss of stress during expansion and contraction The present inventors have found a polyurethane resin composition having excellent elastic properties and exhibiting a small residual strain after stretching under normal temperature, low temperature and high temperature conditions, excellent moisture permeability, and excellent dyeability, thereby completing the present invention. .

That is, the first gist of the present invention is a polyurethane containing at least a polyether polyol unit containing 50 mol% or more of 1,3-propanediol unit, and the amount of the hard segment is based on the total weight of the polyurethane polymer. Thus, the polyurethane is characterized by containing more than 10% and less than 30%.
The second gist lies in the polyurethane described above, wherein the polyether polyol is obtained by a dehydration condensation reaction.

The third gist lies in the polyurethane described above, wherein the polyether polyol has a molecular weight distribution of 1.5 or more.
The fourth gist lies in a film formed by molding the polyurethane as described above.
The fifth gist lies in a fiber formed by molding any of the polyurethanes described above.

  The sixth gist lies in the fiber as described above, which is an elastic fiber.

According to the present invention, the novel polyurethane and polyurethane urea resin composition of the present invention is

Excellent elastic function, ie, high elongation at break, small stress fluctuation with respect to strain when stretched, small hysteresis loss of stress when stretched, small residual strain after stretching under low temperature condition, moisture permeability and dyeing And excellent mechanical properties. Therefore, polyurethane and polyurethane urea resin compositions that are extremely useful for high-functional polyurethane elastomer applications such as polyurethane and polyurethane urea elastic fibers, synthetic / artificial leather, and TPU are provided. Further, the prepolymer as an intermediate has a high dissolution rate in a polar solvent, and greatly contributes to enhancing the productivity of the corresponding resin.

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

The polyurethane in the present invention is a polyurethane containing at least a polyether polyol unit containing 50 mol% or more of 1,3-propanediol units, and the amount of the hard segment is 10% with respect to the total weight of the polyurethane polymer. It is contained at a ratio of larger and smaller than 30%.
Preferably, it is 11% to 25%, more preferably 12% to 22%, and particularly preferably 12% to 20%. When the amount of the hard segment is too large, the obtained polyurethane polymer does not exhibit sufficient flexibility and elastic performance, or when a solvent is used, it tends to be difficult to dissolve and processing becomes difficult. If the amount is too small, the urethane polymer tends to be too soft and difficult to process, and sufficient strength, elastic performance, and durability cannot be obtained at low temperatures.
In addition, the hard segment referred to in the present invention refers to P.I. J. et al. Based on Flory (Journal of American Chemical Society, Vol. 58, pages 1877-1885 (1936),

% HS = 100 (R-1) (Mdi + Mda) / [Mp + RMdi + (R-1) Mda + GcMc]
(Weight of amine + isocyanate bond) / (total weight of polyol + isocyanate + amine + terminal allyl group)
M = number average molecular weight
Gc = equivalent of terminal allyl group (number of moles of terminal allyl group per mole of polyether polyol)
R = number of moles of isocyanate / (number of moles of hydroxyl group of polyether polyol + number of moles of terminal allyl group)
p = polyether polyol
di = diisocyanate
da = diamine (molar average molecular weight)
c = terminal allyl group

More specifically, the polyurethane of the present invention comprises (a) 1,3-propanediol units of 50
In addition to a polyether polyol containing at least mol% as a constituent component, (b) a polyisocyanate and (c) a chain extender are preferably included.
Each composition ratio is usually (a) the number of moles of the hydroxyl group of the polyether polyol containing 50 mol% or more of 1,3-propanediol units, and (b) the mole of the isocyanate group of the polyisocyanate compound. When the number is B and (c) the number of moles of active hydrogen substituents (hydroxyl group and amino group) of the chain extender 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: 4 to 1: 1.1, even more preferably 1: 3 to 1: 1.4, particularly preferably 1: 2.5. To 1: 1.6 and (B-A): C is usually from 1: 0.1 to 1: 5, preferably from 1: 0.8 to 1: 2, more preferably from 1: 0. .9 to 1: 1.5, more preferably 1: 0.95 to 1: 1.2, and particularly preferably 1: 0.98 to 1: 1.

<(A) Polyether polyol containing 50 mol% or more of 1,3-propanediol unit>
The polyether polyol used in the present invention is composed of 50 mol% or more of 1,3-propanediol-derived oxytrimethylene units (1,3-propanediol units) with respect to all polyol units constituting the polyether polyol. The polyether polyol being used is shown. Specifically, the oxytrimethylene unit is represented by the following chemical formula (1).

In the present invention, other polyol units are expressed in the same manner unless otherwise specified.
_{- (CH 2 CH 2 CH 2} O) - (1)
As a polyol unit which comprises the polyether polyol used by this invention, it is required that a 1, 3- propanediol unit is 50 mol% or more with respect to all the polyol units. Preferably it is 60 mol% or more, More preferably, it is 70 mol% or more, More preferably, it is 80 mol% or more, Most preferably, it is 100 mol%. When the 1,3-propanediol unit is less than 50 mol%, the viscosity of the polyol becomes too high and the operability tends to deteriorate, and the resulting polyurethane tends to hardly exhibit sufficient strength and elongation.

The polyether is more preferably a polyether polyol containing 50 mol% or more of 1,3-propanediol units obtained by a dehydration condensation reaction of polyol.
Other polyol units are not particularly limited. For example, 2-methyl-1,3-propanediol unit, 2,2-dimethyl-1,3-propanediol unit, 3-methyl-1,5-pentanediol unit 1,2-ethylene glycol unit, 1,6-hexanediol unit, 1,7-heptanediol unit, 1,8-octanediol unit, 1,9-nonanediol unit, 1,10-decanediol unit, , 4-cyclohexanedimethanol unit and the like.

  Among these, 3 to 20 mol% of 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or 3-methyl-1, among the polyol units constituting the polyether polyol, A copolymerized polytrimethylene ether glycol composed of 5-pentanediol is preferred. Furthermore, polytrimethylene ether glycol composed of all 1,3-propanediol units is most preferable.

  Polyols used as raw materials for polyether polyols are 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 3-methyl-1,5-pentane. 2 such as diol, ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol It is preferable to use a diol having a single primary hydroxyl group.

Usually, these polyols are used alone, but if desired, they can be used as a mixture of two or more polyols. In particular, it is preferable to use 1,3-propanediol alone.
In the present invention, the lower limit of the charged amount of 1,3-propanediol needs to be 50 mol% or more with respect to the total polyol of the raw material. More preferably, the lower limit is 60 mol% or more, particularly preferably 70 mol% or more, and the upper limit is usually 100 mol% or less. When this content is too small, desired physical properties may not be obtained with the obtained urethane, and it may take a long time to produce polyether polyol, or the yield may deteriorate.

  Moreover, the oligomer of the 2-9 mer obtained by the dehydration condensation reaction of the main diol can be used together with these diols. Furthermore, triol or higher polyols such as trimethylolethane, trimethylolpropane, and pentaerythritol, or oligomers of these polyols can be used in combination. However, even in these cases, it is preferable that 1,3-propanediol accounts for 50 mol% or more. Usually, except for those that generate 5- or 6-membered cyclic ethers by dehydration condensation reaction such as 1,4-butanediol and 1,5-pentanediol, the number of carbon atoms having 2 primary hydroxyl groups is 3 to 10 Or a mixture of this with other polyols in which the proportion of the other polyols is less than 50 mol% is subjected to the reaction. Preferably, selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 3-methyl-1,5-pentanediol A diol or a mixture of 1,3-propanediol and another polyol having a ratio of the other polyol of less than 50 mol% is subjected to the reaction. More preferably, 3 to 20 mol% of 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or 3-methyl-1, What copolymerized 5-pentanediol is good.

  Polyether polyols containing 50 mol% or more of 1,3-propanediol units based on the dehydration condensation reaction of polyols with respect to all polyol units are known polyether polyols, polyester polyols, You may blend and use with a polycarbonate polyol. The polyether polyol to be blended is not particularly limited, but polytetramethylene ether glycol (PTMG), a copolymer polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya Chemical PTG-L1000, PTG-L2000, PTG-L3500). And the like, and a copolymer polyether glycol of neopentyl glycol and tetrahydrofuran. When blending polyether polyols that do not contain 1,3-propanediol units as described above, polyether polyols that do not contain 1,3-propanediol units may not be produced by a dehydration condensation reaction. It only has to be manufactured by a known technique.

  The amount to be blended is not particularly limited, but the weight ratio of the polyether polyol containing 50 mol% or more of 1,3-propanediol units obtained by a dehydration condensation reaction of polyol and a known polyol is preferably 99: 1 to 1:99, preferably 95: 5 to 5:95, more preferably 90:10 to 10:90, and still more preferably 80:20 to 20:80.

A polyether polyol containing 50 mol% or more of 1,3-propanediol units obtained by polyol dehydration condensation reaction may be used by capping the terminal hydroxyl group with caprolactone to make an ABA type polyol. Moreover, you may use it, making the terminal cap by making oxiranes, such as ethylene oxide and propylene oxide, react.
<Method for producing polyether polyol>
The polyether polyol used as a raw material in the present invention must be prepared by using a polyol produced by a dehydration condensation reaction and containing 1,3-propanediol units in an amount of 50 mol% or more based on the total polyol units. Become.

  The production of the polyether polyol by the dehydration condensation reaction of the polyol used in the present invention can be carried out either batchwise or continuously. For example, in the case of a batch system, a raw material polyol and a catalyst acid may be charged into a reactor and reacted with stirring. A compound of a metal selected from the group consisting of alkali metals, bases, group 4 and group 13 may coexist with the acid catalyst. In the case of a continuous reaction, for example, a polyol and a catalyst as raw materials are continuously supplied from one end of a reaction apparatus or a flow-type reaction apparatus in which a large number of stirring tanks are connected in series, and the inside of the apparatus is moved in a piston flow or a manner close to this. And a method of continuously extracting the reaction solution from the other end can be used.

Regarding the temperature of the dehydration condensation reaction, the lower limit is usually 120 ° C. and the upper limit is usually 250 ° C., preferably the lower limit is 140 ° C. and the upper limit is 200 ° C., more preferably the lower limit is 150 ° C. and the upper limit is 190 ° C. is there. If this temperature is too high, coloring tends to deteriorate, and if it is too low, the reaction rate tends not to increase.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction pressure is arbitrary as long as the reaction system is maintained in a liquid phase, and is usually carried out under normal pressure. If desired, the reaction may be carried out under reduced pressure or an inert gas may be circulated through the reaction system in order to promote elimination of water produced by the reaction from the reaction system. Water vapor or an organic solvent may be used in place of the inert gas.

The reaction time varies depending on the amount of catalyst used, the reaction temperature and the desired yield and physical properties of the dehydration condensate to be produced, but the lower limit is usually 0.5 hours and the upper limit is usually 50 hours. Preferably, the lower limit is 1 The upper limit is 20 hours.
The reaction is usually carried out without a solvent, but a solvent can be used if desired. The solvent may be appropriately selected from organic solvents used in usual organic synthesis reactions in consideration of vapor pressure under reaction conditions, stability, solubility of raw materials and products, and the like.

  Separation and recovery of the produced polyether polyol from the reaction system can be performed by a conventional method. When an acid that acts as a heterogeneous catalyst is used, the suspended acid is first removed from the reaction solution by filtration or centrifugation. Next, the low-boiling oligomers and organic bases are removed by distillation or extraction with water or the like to obtain the target polyether polyol. When an acid that acts as a homogeneous catalyst is used, water is first added to the reaction solution to separate the polyether polyol layer and the aqueous layer containing the acid, organic base, oligomer, and the like. In addition, since a part of polyether polyol forms the acid and ester used as a catalyst, after adding water to a reaction liquid, it heats and hydrolyzes an ester and makes it separate into layers. At this time, when an organic solvent having an affinity for both the polyether polyol and water is used together with water, hydrolysis can be promoted. In addition, when the polyether polyol has a high viscosity and the operability of the layer separation is not good, it is also preferable to use an organic solvent that has an affinity for the polyether polyol and can be easily separated from the polyether polyol by distillation. The polyether polyol phase obtained by the layer separation is distilled to distill off the remaining water and organic solvent to obtain the target polyether polyol. In addition, when an acid remains in the polyether polyol phase obtained by the layer separation, the remaining acid is removed by washing with water or an alkaline aqueous solution or treating with a solid base such as calcium hydroxide. Then use for distillation.

The obtained polyether polyol is usually stored in an inert gas atmosphere such as nitrogen or argon.
Moreover, you may reduce an unsaturated terminal as needed.
For example, polytrimethylene ether glycol and a copolymer thereof are a method in which an unsaturated terminal is converted into a hydroxyl group in the presence of a metal catalyst selected from the group of groups 4 to 12 of the periodic table.

Examples of the metal catalyst selected from the group of groups 4 to 12 of the periodic table include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, and rhodium. ,iridium,

Nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury and the like can be mentioned. The preferred metal catalyst is a metal catalyst selected from the group of groups 6 to 11, and specific examples thereof include chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium. , Platinum, copper, silver and gold. A more preferable metal catalyst is a metal catalyst selected from the group of groups 8 to 10, and specific examples thereof include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Particularly preferred metal catalysts are rhodium, palladium, ruthenium or platinum, and palladium is most suitable from the viewpoint of availability and price.

As the metal catalyst, an alloy form with one or more other metals, a salt form, a coordination compound form, and the like can be used. The metal catalyst can be supported on a carrier. Examples of the carrier include activated carbon, alumina, silica, zeolite, clay, activated clay and the like. The electronic state of the metal only needs to be present in the reaction system in a zero-valent state at the time of reaction. For example, a metal in the II-valent state can be selected as a catalyst when added to the reaction system. The amount of the metal catalyst supported on the carrier is not particularly limited, but is usually 0.1% or more and less than 50%, preferably 0.5% to 20%, more preferably 1% to 10%.

  Taking palladium as an example of the metal catalyst, examples of the metal catalyst include finely divided metal palladium, supported metal palladium catalyst such as palladium on carbon, palladium on alumina, palladium on silica, and the like. In addition, tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, palladium (II) chloride, palladium (II) bis (triphenylphosphine) chloride, bis (pentandionato) palladium (II), palladium (II) Bis (benzonitrile) and the like. The catalyst may be added separately, resulting in the formation of complexes and salts.

The catalyst is used in an amount sufficient to increase the rate of reduction of unsaturated end groups so that it can be measured. The catalyst concentration is preferred such that the reaction proceeds to a desired ratio in a time that can be used in industrialization, for example, 24 hours or less, preferably 10 hours or less, more preferably 5 hours or less.
The amount used when the metal catalyst is supported on a support and when used as a fine metal catalyst is appropriately selected according to the type of the catalyst. For example, in the case of a catalyst supporting 5% by weight of palladium, As a ratio of the dry base standard to the weight of the polytrimethylene ether glycol and its copolymer, the metal catalyst (excluding the support) is usually 0.0001 to 10% by weight, preferably 0.001 to 1% by weight, and more preferably 0.001. 005 to 0.25% by weight.

Metal catalysts can also be complex catalysts and metal salts such as tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, palladium (II) chloride, palladium (II) bis (triphenylphosphine) chloride, bis (pentanedio Nato) palladium (II), palladium (II) when used as bis (benzonitrile), etc., the amount used is appropriately selected according to the type, but based on the weight of polytrimethylene ether glycol and its copolymer Usually, it is 0.001% to 10% by weight, preferably 0.001 to 5% by weight, more preferably 0.005% to 1% by weight.

It is presumed that the reduction of unsaturated end groups (desaturation treatment) by the treatment of polyalkylene ether glycol in the presence of a metal catalyst in this method is performed as follows. That is, a double bond moves from the allyl end to the inside to form a 1-propenyl group end, which reacts with water to eliminate propionaldehyde and form a hydroxyl end. As water necessary for the desaturation treatment, water contained in the metal catalyst can be used. For example, palladium-supported activated carbon is generally marketed as a water-containing product of about 50%. However, more than the amount necessary to hydrolyze the 1-propenyl group ends (for example, polyalkylene ether group).

It is preferable that about 0.5% by weight, preferably 1% by weight, more preferably 10% by weight excess) of water is present in the reaction system. The amount of water in practical treatment is usually 1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the polyalkylene ether glycol.

  The upper limit of the desaturation temperature is selected from a temperature range lower than the decomposition temperature (T) of the polyalkylene ether glycol, and is usually T-20 ° C, preferably T-120 ° C, more preferably T-200 ° C. Is adopted. The lower limit of the desaturation temperature is usually 25 ° C, preferably 50 ° C. When the reaction temperature is high, it is possible to carry out the desaturation treatment under pressure.

  The desaturation treatment can be performed in the presence of a solvent. Examples of the solvent include methanol, ethanol, propanol, butanol, water, tetrahydrofuran, toluene, acetone and the like. The amount of the solvent is not particularly limited, but the upper limit is usually 10 times by weight, preferably 2 times by weight with respect to the polyalkylene ether glycol. The desaturation treatment may be either a batch type or a continuous type. Examples of the continuous type include a method in which a raw material such as polyalkylene ether glycol / water / solvent is continuously supplied to a column reactor filled with a metal catalyst.

  The catalyst for the desaturation treatment can be recycled after separation from the reaction solution after the reaction. As a separation method, in the case of a batch type, for example, a method of separating the catalyst by filtration, centrifugation or the like can be mentioned. It may also be effective to wash the catalyst used with a suitable solvent. Examples of the washing solvent include methanol, ethanol, propanol, butanol, tetrahydrofuran, ethyl ether, propyl ether, butyl ether, water, ethyl acetate, 1,3-propanediol, toluene, acetone and the like. In the case of a fixed bed reactor, the activity of the catalyst can be recovered to some extent by washing at an appropriate temperature using these solvents.

The reduction rate of the terminal unsaturated groups of the polyalkylene ether glycol by the above desaturation treatment is usually 20% or more, preferably 50 or more, and more preferably 75% or more.

<Physical properties of polyether polyol>
The number average molecular weight of the polyether polyol used in the present invention can be adjusted by the type and amount of catalyst used, and the lower limit is usually 80, preferably 600, more preferably 1000, and the upper limit is usually 10,000. Preferably it is 7000, More preferably, it is 5000.
The molecular weight distribution of the polyether polyol used in the present invention is usually 1.0 to 5.0, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and even more preferably 1. 5-2.2. If the molecular weight distribution is too small or too large, productivity is deteriorated during the production of the polyurethane, or the physical properties of the resulting polyurethane are unfavorable.

The Hazen color number of the polyether polyol is preferably closer to 0, and the upper limit is usually 500, preferably 400, more preferably 200, and most preferably 50.
The ratio of the terminal allyl group amount is usually 10%, preferably 5%, more preferably 1%, and still more preferably 0% with respect to the hydroxyl group. When the amount of terminal allyl groups is too large, the molecular weight of polyurethane and polyurethane urea cannot be sufficiently increased, and it tends to be difficult to obtain desired performance. If the amount is too small, the reaction rate may increase too much, and a gel or the like may be generated in the polyurethane and polyurethane urea reaction. However, when the amount is too small, a problem that the molecular weight is excessively increased can be avoided by allowing an appropriate amount of a monofunctional component to coexist in the reaction system by a conventional method.

<(B) Polyisocyanate compound>
Examples of the polyisocyanate compound used in the present invention include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-MDI, paraphenylene. Aromatic diisocyanates such as diisocyanate, 1,5-naphthalene diisocyanate and tolidine diisocyanate, aliphatic diisocyanates having aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and other aliphatic diisocyanates, 1,4-cyclo Xanthane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanatomethyl-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, aromatic polyisocyanates having high reactivity are particularly preferable, and tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are particularly preferable. Further, a part of the polyisocyanate NCO group may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc., and the polynuclear substance contains isomers other than the above. Some things are included.

The amount of these polyisocyanate compounds used is usually 0.1 equivalent to 10 equivalents, preferably 0.8 equivalent to 1. equivalent to 1 equivalent of the hydroxyl group of the polyether polyol and 1 equivalent of the hydroxyl group and amino group of the chain extender. 5 equivalents, more preferably 0.9 equivalents to 1.05 equivalents.
If the amount of polyisocyanate used is too large, the unreacted isocyanate group will react unfavorably and the desired physical properties will tend to be difficult to obtain. If it is too small, the molecular weight of polyurethane and polyurethane urea will not be sufficiently large. The desired performance tends not to be expressed.

<(C) Chain extender>
The chain extender referred to in the present invention is mainly classified into a compound having two or more hydroxyl groups, a compound having two or more amino groups, and water. Of these, short-chain polyols, specifically compounds having two or more hydroxyl groups, are preferred for polyurethane applications, and polyamine compounds, specifically compounds having two or more amino groups, are preferred for polyurethane urea applications.

Among these, water is preferably reduced as much as possible in order to carry out the reaction stably.
In the polyurethane resin of the present invention, it is more preferable in view of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less as a chain extender because the rubber elasticity of the polyurethane elastomer is improved.

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

  Examples of the compound having two or more amino groups include 2,4- or 2,6-tolylenediamine, xylylenediamine, aromatic diamines such as 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'-dicyclohexylmethane Min (hydrogenated MDA), isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, alicyclic diamines such as 1,3-bis-aminomethyl cyclohexane.

Among these, ethylenediamine, propylenediamine, 1,3-diaminopentane, and 2-methyl-1,5-pentanediamine are preferable in the present invention. These chain extenders may be used alone or in combination of two or more. Although the usage-amount of these chain extenders is not specifically limited, It is 0.1 equivalent or more and 10 equivalent or less normally with respect to 1 equivalent of polyether polyols.

If the amount used is too large, the obtained polyurethane and polyurethane urea resin will be too hard and the desired properties will not be obtained, or it will be difficult to dissolve in the solvent and difficult to process, and if it is too small, it will be too soft and sufficient. Strength, elastic recovery performance and elastic holding performance tend not to be obtained, and high temperature characteristics tend to deteriorate.

  When the target polyurethane and polyurethane urea resin in the present invention are used for high-performance polyurethane elastomer applications such as polyurethane elastic fibers and synthetic leather, the following examples are given as combinations of raw materials. As one of the active hydrogen compound components, polyoxytrimethylene ether glycol having a molecular weight of 500 to 5000 of the above formula (1), as chain extender, ethylenediamine, propylenediamine, hexanediamine, xylylenediamine, 2-methyl, 1, Examples of polyisocyanate components such as 5-pentanediamine, 1,4-butanediol, and 1,3-propanediol include 4,4′-diphenylmethane diisocyanate and 2,4- or 2,6-tolylene diisocyanate.

For the purpose of controlling the molecular weight of the polyurethane resin, 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, monoethanolamine and diethanolamine having an amino group. These may be used alone or in combination of two or more.

<Other additives>
Furthermore, you may add another additive to the polyurethane resin of this invention as needed other than the above. As these additives, CYANOX 1790 (manufactured by Cyanamid Co., Ltd.), IRGANOX245, IRGANOX 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), or 2, Antioxidants such as 6-dibutyl-4-methylphenol (BHT), TINUVIN 622LD, TINUVIN 765 (manufactured by Ciba Specialty Chemicals Co., Ltd.), SANOL LS-2626, LS-765 (manufactured by Sankyo Co., Ltd.) Light stabilizers such as TINUVIN 328, TINUVIN 234 (manufactured by Ciba Specialty Chemicals Co., Ltd.), silicon compounds such as dimethylsiloxane polyoxyalkylene copolymer, red phosphorus, organic phosphorus Conversion Things, phosphorus and halogen-containing organic compound, a bromine or chlorine-containing organic compounds, An'nmoniumu polyphosphate, aluminum hydroxide, oxide antimony

Reactive flame retardants, pigments such as titanium dioxide, dyes, colorants such as carbon black, hydrolysis inhibitors such as carbodiimide compounds, short glass fibers, carbon fibers, alumina, talc, graphite, melamine, clay And fillers, lubricants, oils, surfactants, other inorganic extenders, organic solvents, and the like.

<Production method of polyurethane>
In order to produce the polyurethane resin of the present invention, (a) a polyether polyol containing 50 mol% or more of 1,3-propanediol units obtained by a dehydration condensation reaction of polyol as a raw material is used as a raw material. There is no particular limitation as long as it is produced in such a proportion that it is greater than 10% and less than 30%, but preferably, in addition to the polyether polyol raw material, (b) polyisocyanate compound and (c) chain extension It is preferable to use an agent as a raw material. Furthermore, it is more preferable to react these raw materials in the presence of an aprotic solvent.

In order to produce the above polyurethane resin, all production methods generally used experimentally / industrially can be used. However, the present invention is characterized in that the urethane resin is produced in the presence of an aprotic 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 quantity of the said description.
An example of a production method in the presence of an aprotic solvent is shown below, but is not particularly limited as long as it is in the presence of an aprotic solvent.

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

<One-stage method>
The one-stage method is also called a one-shot method, and is a method in which a reaction is performed by charging (a), (b) and (c) together.
The amount of each compound used may be the amount described above.
In the present invention, the reaction can be carried out in the presence of an organic solvent rather than a solventless one-step method. Examples of the solvent used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, Aprotic polarities such as esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide Examples include solvents and mixtures of two or more thereof.

  In the present invention, among these organic solvents, when producing polyurethane, an aprotic polar solvent is preferable from the viewpoint of solubility, which is a feature of the present invention. Further, preferred specific examples of the aprotic polar solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, more preferably dimethylformamide and dimethylacetamide.

In the one-shot method (reacted in one step), the lower limit of the reaction equivalent ratio of NCO / active hydrogen group (polyether polyol and chain extender) is usually 0.50, preferably 0.8, and the upper limit is Usually in the range of 1.5, preferably 1.2.
If this ratio is too large, 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.

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, 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.

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

The present invention is characterized in that the two-stage method is carried out using an organic solvent rather than a solvent-free method. Examples of the solvent used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, Aprotic polarities such as esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide Examples include solvents and mixtures of two or more thereof.

  In the present invention, among these organic solvents, when producing polyurethane, an aprotic polar solvent is preferable from the viewpoint of solubility, which is a feature of the present invention. Further, preferred specific examples of the aprotic polar solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, more preferably dimethylformamide and dimethylacetamide.

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

The lower limit of the reaction equivalent ratio of NCO / active hydrogen group (polyether polyol) is usually 1, preferably 1.1, and the upper limit is usually 10, preferably 5, more preferably 3.
The amount of the chain extender is not particularly limited, but the lower limit is usually 0.8, preferably 1, and the upper limit is usually 2, preferably 1. with respect to the equivalent amount of NCO groups contained in the prepolymer. 2 range.

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.
Further, a monofunctional organic amine or alcohol may coexist during the reaction.
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, and if it is too high, side reactions and decomposition of the polyurethane resin occur. The reaction may be performed while degassing under reduced pressure.

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

<Physical properties of polyurethane>
Since the polyurethane obtained by the above production method is reacted in the presence of a solvent, it is generally obtained in a state dissolved in a solution. However, physical properties are not particularly limited in a solution state or a solid state. Unless otherwise, it is not limited to the state.
The weight average molecular weight of the polyurethane varies depending on the use, but is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, particularly preferably 100,000 to the polyurethane polymerization solution. 300,000. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.8 to 2.5, more preferably 1.9 to 2.3.
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 15 It is 10,000 to 350,000. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.8 to 2.5, more preferably 1.9 to 2.3.

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 thixotropic properties, which is convenient for processing into films, yarns, and the like. .
The polyurethane is usually 1 to 99% by weight, preferably 5 to 90% by weight, more preferably 10 to 70% by weight, particularly preferably 15 to 15% by weight based on the total weight of the solution dissolved in the aprotic solvent. 50% by weight. If the amount of polyurethane is too small, it is necessary to remove a large amount of solvent and the productivity tends to be low, and if it is too large, the viscosity of the solution is too high and the operability and workability tend to be poor. .
The polyurethane solution is not particularly specified, but is preferably stored in an atmosphere of an inert gas such as nitrogen or argon when stored over a long period of time.

<Polyurethane moldings / uses>
The polyurethane produced in the present invention and its urethane prepolymer solution have various characteristics.

And can be widely used in foams, elastomers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, and the like.

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

  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. Also, 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, automobile parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, tire chain substitutes, and the like. Further examples include films such as keyboard films and 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 applied 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, blocked isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, UV-curable paints, etc. For example, plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring materials, overprint varnishes such as paper, wood grain printing films, wood varnishes, coil coats for high processing, optical fiber protective coatings , Solder resist, top coat for metal printing, base coat for vapor deposition, white coat for food cans, etc.

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.
The polyurethane and its urethane prepolymer solution produced in the present invention are magnetic recording media, 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, such as a concrete wall, induction joint, sash area, wall-type PC joint, ALC joint, board joint, and composite glass sealant. Can be used for heat insulating sash sealant, automotive sealant, etc.

The polyurethane and its urethane prepolymer solution produced in the present invention can be used as a medical material. As a blood compatible material, a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc., and as a disposable material, a catheter, Can be used for tubes, bags, surgical gloves, artificial kidney potting materials, etc.
The polyurethane, polyurethane urea and its 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 an optical fiber coating composition.

In particular, it is preferable to use the elastic performance and moisture permeability characteristics of the polyurethane produced in 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 specified, and a known method can be used. For example, as a film production 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 a support or a release material. Examples thereof include a dry film forming method in which the solvent is dried by applying and heating or reducing 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 where drying is insufficient or rapid solvent removal does not occur. Preferably it is the range of room temperature-300 degreeC, More preferably, it is the range of 60 degreeC-200 degreeC.

<Physical properties of film>
The thickness of the film of the present invention is usually 10 to 1000 μm, preferably 10 to 500 μm, and more preferably 10 to 100 μm. If the film is too thick, there is a tendency that sufficient moisture permeability cannot be obtained. If the film is too thin, pinholes are easily formed, and the film is easily blocked and difficult to handle.
Tend to be. 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% elongation or more, preferably 200% or more, more preferably 300% or more, still more preferably 500% or more, and even more preferably 800% or more.
The breaking strength is usually 5 MPa, preferably 10 MPa or more, more preferably 20 MPa or more, still more preferably 30 MPa or more, and even more preferably 60 MPa or more.

The elastic retention (Hrn / Hn) at 150% at 23 ° C. is usually 10% or more at the first time, preferably 20% or more, more preferably 30% or more, and further preferably 40% or more. In the fifth time, it is usually 30% or more, preferably 50% or more, more preferably 70% or more, and still more preferably 85% or more.
Moreover, the elastic retention (H2 / H1) at 150% at 23 ° C. is usually 20% or more, preferably 40% or more, more preferably 50% or more, and further preferably 60% or more.

The second residual strain in the repeated 300% stretching-shrinkage test at 23 ° C. is usually 40% or less, preferably 30% or less, more preferably 20% or less, and even more preferably 15% or less. The residual strain at the fifth time is usually 50% or less, preferably 35% or less, more preferably 25% or less, and most preferably 20% or less.
The residual strain at −10 ° C. is usually 300% or less, preferably 120% or less, more preferably 100% or less, and still more preferably 60% or less.

The elastic retention (Hr1 / H2) at −10 ° C. is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.
The deterioration rate of the residual strain calculated from the second residual strain at 23 ° C. and the second residual strain at −10 ° C. is preferably 300% or less, more preferably 200% or less, and even more preferably 150% or less.
The moisture permeability is usually 500 g / m 2 · 24 h, preferably 1000 g / m 2 · 24 h, more preferably 2000 g / m 2 · 24 h, and still more preferably 3000 g / m 2 · 24 h when converted to a film thickness of 50 μm.
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).

<Method for producing polyurethane urea resin and elastic fiber>
Among the polyurethanes of the present invention, polyurethane urea can be used for various applications, and particularly when used as an elastic fiber, it exhibits excellent performance. The preferable production conditions are exemplified.
First, a polyether polyol containing 50 mol% or more of 1,3-propanediol units obtained by a dehydration condensation reaction of MDI and polyol is reacted at NCO / OH = 1.1 to 3.0 to obtain a prepolymer of terminal NCO groups Manufacturing. In the reaction, if necessary, a monool such as BuOH or hexanol may be added and reacted in an amount of about 500 to 5000 ppm with respect to the polyether polyol. In this case, it is preferable that the reaction is carried out in a bulk state without using a solvent because side reactions hardly occur. The obtained prepolymer is dissolved in an aprotic polar solvent such as dimethylacetamide (DMAc) or dimethylformamide (DMF), and is preferably cooled to 0 to 30 ° C, more preferably to 0 to 10 ° C. At this time, if the prepolymer solution temperature is too high, the reaction is too fast during the chain extension reaction in the next step, resulting in a heterogeneous reaction, which may cause an abnormal reaction such as gelation. On the other hand, if it is too low, it may take time to dissolve the prepolymer, or the prepolymer may not be sufficiently dissolved and may precipitate and be unable to react well. The concentration of the prepolymer solution is not particularly limited, but is 10 to 90% by weight, preferably 20 to 70% by weight, more preferably 35 to 50% by weight. Then, the cooled prepolymer solution and an aliphatic diamine having a methylene chain length of 6 or less such as propanediamine, ethylenediamine, 2-methyl-1,5-pentanediamine, and hexanediamine, or an aromatic diamine such as xylylenediamine are DMAc, Alternatively, the chain is extended by reacting with an amine solution dissolved in DMF. If an aliphatic diamine having an excessively long methylene chain is used alone, the physical properties may be lowered when a polyurethane elastic fiber is formed. It is preferable to use 50 mol% or more of ethylenediamine as a main component as a diamine chain extender. More preferably 70 mol% or more, still more preferably 80%, and still more preferably 90% or more.

When using a highly reactive aliphatic amine, the reaction is preferably carried out without adding a catalyst.
The total amount of the diamine chain extender used when the present invention is applied to polyurethane urea elastic fibers is 1 to 30% by weight, preferably 2 to 20% by weight, more preferably 3%, based on the polyurethane urea polymer. An amount that produces a hard segment amount of -15%, even more preferably 3-10%, and even more preferably 3-9%. If the amount of the hard segment is too large, the polyurethane urea elastic yarn or film becomes difficult to dissolve in a solvent for spinning or forming a film, or elongation as a fiber or film is insufficient. If the amount of the hard segment is too small, the fiber or film may be too soft, the strength may be too weak, the elastic recovery force or the stress maintenance rate may be low, and the residual strain may increase.

  After completion of the chain extension reaction, the reaction is stopped by adding a DMAc or DMF solution of an aliphatic monoamine such as diethylamine, dibutylamine, monoethanolamine or diethanolamine. At this time, monoamine may be mixed with diamine in advance, and chain extension reaction and chain termination reaction may proceed simultaneously. In the chain extension reaction, the prepolymer solution may be added to the diamine solution, the diamine solution may be added to the prepolymer solution, or the reaction may be continuously performed using a two-component quantitative discharge mixing device. . The obtained polyurethane urea resin solution is mixed with additives such as antioxidants, ultraviolet absorbers, yellowing inhibitors, etc., and after removing foreign matter with a filter as necessary, dry spinning, wet spinning, etc. Polyurethane urea elastic fiber is produced by the spinning method.

  Although the weight average molecular weight of polyurethane urea varies depending on the purpose of use, it is usually 10,000 to 1,000,000, preferably 50,000 to 500,000, more preferably 100,000 to 400,000, particularly preferably as a polyurethane urea polymerization solution. 100,000 to 300,000. The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.8 to 2.5, more preferably 1.9 to 2.3.

As an elastic fiber, the weight average molecular weight of polyurethane urea 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 350,000. . The molecular weight distribution is Mw / Mn = 1.5 to 3.5, preferably 1.8 to 2.5, more preferably 1.9 to 2.3.
The polyurethaneurea solution obtained in the present invention is convenient for producing elastic yarns because it is less prone to gelation, has good storage stability such as a small change in viscosity over time, and has low thixotropic properties.

  The polyurethane urea elastic fiber obtained in this way has a high elongation at break, a small stress fluctuation with respect to the deformation strain at the time of expansion, a small hysteresis loss of the stress at the time of expansion and contraction, and after the expansion under the low temperature condition Due to low residual strain, underwear, leg knit, stockings, diaper cover, paper diaper cather, foundation, tie, wig base fabric, sock mouth rubber, sports clothing, swimwear, various belts, narrow tape, sports, outer use It can also be used in fields that require high elasticity, low temperature characteristics, etc.

Moreover, a well-known technique can be utilized regarding the method of manufacturing a fiber from the polyurethane which uses a short chain polyol as a chain extender.
<Physical properties of polyurethane elastic fiber>
Polyurethane elastic fibers have better performance than other elastic fibers in terms of strength, elongation at break, stretch recovery, UV resistance, heat deterioration resistance, hydrolysis resistance, low temperature characteristics, and the like. In particular, when a polyether polyol obtained by a dehydration condensation reaction of a polyol containing 50 mol% or more of 1,3-propanediol of the present invention is used, the characteristics may be conspicuous.

The breaking strength is usually 0.1 g / d or more, preferably 0.9 g / d or more. The elongation at break is usually 300% or more, preferably 500% or more, more preferably 600% or more, and even more preferably

Preferably it is 650% or more.
As the extension recovery rate, the recovery rate after holding for 24 hours at an extension rate of 100% is usually 80% or more, preferably 85% or more, more preferably 90% or more, and further preferably 92% or more.

As ultraviolet resistance, the strength retention after irradiation with Fade-O-meter for 45 hours is usually 50% or more, preferably 70% or more, more preferably 80% or more, more preferably 90% or more.
As heat resistance, the strength retention after a 24 hour holding test at 120 ° C. is usually 50% or more, preferably 70% or more, more preferably 80% or more, and even more preferably 90%, compared to before the test That's it.

<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 the elastic fiber is characterized by being less stuffy and comfortable to wear when used in clothing.
In addition, the characteristic that the rate of variation of stress is small or the modulus is small is that, for example, it is possible to pass the sleeve with a small force when wearing it as clothing, and it is very easy to remove and attach even for small children and the elderly. It has. In addition, since it has good fit and movement following ability, it can be used for sports clothing and clothing with higher fashion.

In addition, since the elastic retention rate in the repeated extension test is high, there is also a feature that the elastic performance is hardly impaired even in repeated use.
Since the residual strain is small, it is difficult to sag as an elastic fiber, and the elasticity can be maintained for a long time.
In addition, the residual strain at -10 ° C is small and the stress retention is excellent because it is a characteristic of elastic fibers even when exposed to low temperatures such as using products using this material in cold regions. There is an advantage that can be held. Moreover, the point that the difference in residual strain at 23 ° C. and −10 ° C. is small is advantageous in that the characteristics as an elastic fiber can be maintained regardless of the difference in temperature.

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.
<Number average molecular weight of polytrimethylene ether glycol>
In the examples, the number average molecular weight of polytrimethylene ether glycol was determined from the hydroxyl value (KOH (mg) / g).

<Analysis of terminal allyl group>
The ratio of the allyl terminal of polytrimethylene ether glycol was calculated by 1H-NMR (AVANCE400 manufactured by BRUKE®). Polyurethane physical properties were measured according to JIS-K6301.

<Molecular weight distribution of polyether polyol>
For the measurement of the molecular weight distribution of the polyether polyol, a THF solution of the polyether polyol was prepared, and a GPC apparatus (manufactured by Tosoh Corporation, product name: HLC-8220 (column: TSKgelSuperHZM-N (three)) was used. A calibration curve was prepared using a tetrahydrofuran calibration kit (Polymer Laboratories).

<Polyurethane and polyurethane urea weight number average molecular weight>
The molecular weight of the obtained polyurethane and polyurethane urea was measured by preparing a DMAC solution of polyurethane and using a GPC apparatus (manufactured by Tosoh Corporation, product name: HLC-8120 (column: Tskel H3000 / H4000 / H6000)) Standard polystyrene conversion weight average molecular weight was defined as molecular weight.

<Hard segment amount>
Hard segment amount J. et al. Based on Flory, Journal of American Chemical Society, Vol. 58, pp. 1877-1885 (1936), the calculation was made as follows.
% HS = 100 (R-1) (Mdi + Mda) / [Mp + RMdi + (R-1) Mda + GcMc]
(Weight of amine + isocyanate bond) / (total weight of polyol + isocyanate + amine + terminal allyl group)
M = number average molecular weight
Gc = Equivalent of terminal allyl group (terminal allyl group per mole of polyether polyol)
Le)
R = number of moles of isocyanate / (number of moles of hydroxyl group of polyether polyol + terminal)
Number of moles of allyl group)
p = polyether polyol
di = diisocyanate
da = diamine (molar average molecular weight)
c = terminal allyl group

<Elasticity retention>
At a temperature of 23 ° C. (relative humidity 55%), a film having a width of 10 mm and a thickness of about 50 μm is set at a length of 50 mm, stretched to 300% at a speed of 500 mm / min, and continuously up to the original length of 500 mm / min. Shrink at speed. This was repeated 5 times. The height at the 150% modulus of the SS curve at the n-th extension was Hn, and the height at 150% modulus of the SS curve at the return was Hrn. The elastic retention rate was expressed as Hr _n / H _n as a numerical value representing the return stress with respect to the stress at the n-th extension, and the retention rate of the n + 1-th stress with respect to the stress at the n-th extension was expressed as Hn + 1 / Hn. A larger value is preferable because the elastic retention rate is higher.

<Residual strain>
At a temperature of 23 ° C. (relative humidity 55%), a film having a width of 10 mm and a thickness of about 50 μm is set at a length of 50 mm, stretched to 300% at a speed of 500 mm / min, and continuously up to the original length of 500 mm / min. Shrink at speed. This was repeated 5 times. The point at which the stress during the n-th extension rises was defined as the n-th residual strain.

<Residual strain and elastic retention at −10 ° C.>
At a temperature of −10 ° C. (relative humidity is not measured), a film having a width of 10 mm and a thickness of about 50 μm is set at a length of 50 mm, stretched to 300% at a speed of 500 mm / min, and then continued to the original length of 500 mm / min. Shrink at a speed of This was repeated twice. The height at the 150% modulus of the SS curve at the first extension is H1, the height at the 150% modulus of the SS curve at the return is Hr1, the height at the 150% modulus of the SS curve at the first and second extension. The height was H2. Hr1 / H2 at this time was defined as an elastic retention at −10 ° C. The point at which the stress at the time of the second extension rises was defined as residual strain at −10 ° C.
<Deterioration rate of residual strain>
From the residual strain at 23 ° C. and −10 ° C., the deterioration rate of the residual strain was calculated by the following equation.
Deterioration rate of residual strain (%) = {(residual strain at −10 ° C.) − (Residual strain at 23 ° C.)} / (2
Residual strain at 3 ° C) x 100

<Physical properties of film>
The polyurethane resin test piece is a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm, and is measured using a tensile tester (manufactured by Orientec Co., Ltd., product name: Tensilon UTM-III-100) according to JIS K6301. did. At a distance between chucks of 50 mm and a tensile speed of 500 mm / min, measurement was carried out at a temperature of 23 ° C. (relative humidity 55%), tensile breaking strength, tensile breaking elongation, and stress fluctuation rate to 100 to 600%. The stress retention of 100 to 600% indicates the magnification of the stress at 600% in the 23 ° C. tensile test with respect to the stress at 100%.

Reference example 1
Production of polytrimethylene ether glycol
<Dehydration condensation reaction of 1,3-propanediol>
While supplying nitrogen at 1 NL / min to a 1000 mL four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a mercury thermometer, and a stirrer, 500 g of 1,3-propanediol was charged. To this was added 0.348 g of sodium carbonate, and 6.78 g of 95% by weight concentrated sulfuric acid was gradually added while stirring. This flask was immersed in an oil bath and heated, and the liquid temperature in the flask was allowed to reach 163 ° C. in about 1.5 hours. The time when the liquid temperature in the flask reached 163 ° C. was set as the reaction start point, and the reaction was continued for 18 hours while maintaining the liquid temperature at 163 ° C. Generated by reaction
The water was distilled off with nitrogen.

The reaction solution allowed to cool to room temperature was transferred to a 2 L four-necked flask containing 500 g of demineralized water and refluxed for 8 hours to hydrolyze the sulfate ester. After adding 5.84 g of calcium hydroxide and neutralizing by stirring at 70 ° C. for 2 hours, nitrogen was bubbled while heating in an oil bath to distill off most of the water. Boiling dehydration was performed. After solids were filtered off by pressure filtration, toluene was distilled off with an evaporator. Furthermore, the polyether was dried under reduced pressure of 5 mmHg at 120 ° C. for 2 hours to obtain polytrimethylene ether glycol (A). The number average molecular weight determined by NMR was 1995, and the ratio of terminal allyl groups was 1.40%.

Example 1
To the 3 L separable flask was added 1958.5 g of polytrimethylene ether glycol (number average molecular weight 2180, terminal allyl group ratio 1.12% calculated from hydroxyl value) to which 5 ppm of phosphoric acid previously heated to 40 ° C. was added. Then, 541.5 g of diphenylmethane diisocyanate (MDI) heated to 40 ° C. was added (NCO / OH ratio = 2.39). Set in an oil bath at 45 ° C., and stir with a vertical stirring blade (150 rpm) under a nitrogen stream, raise the temperature of the oil bath to 70 ° C. over 1 hour, then at 70 ° C. for 3 hours, The temperature was raised to 80 ° C. and held for 2 hours. After confirming that the NCO reaction rate exceeded 98% by titration, the prepolymer was transferred to a 3 L tin can and kept in a constant temperature bath at 40 ° C. overnight.

  1792.5 g of prepolymer and 2689 g of dehydrated dimethylacetamide (DMAC, Kanto Chemical) were added to the prepolymer tank, stirred and dissolved at room temperature, then cooled to 10 ° C. and held. A 2% DMAC solution of ethylenediamine (EDA) / propylenediamine (PDA) / diethylamine (DEA) = 74.3 / 18.6 / 7.1 (molar ratio) is prepared in an amine tank and cooled to 10 ° C. and held. did. Metering pump with metering pump drive motor rotation speed controlled by an inverter using a casting machine (two-component metering discharge mixing device). Amine / NCO ratio of 0.98 to 1.02 Experiments were performed so that the flow rate ratio was adjusted in increments of 0.02 up to 1.06 and the total flow rate was 120 g / min, and samples were collected when the reaction temperature was stabilized. (When amine / NCO = 1.00, flow rate of prepolymer solution 75.88 g / min, amine solution 49.18 g / min). In the power mixing unit, the mixer cooled the jacket at 10 ° C., mixed by high-speed stirring, and reacted to obtain a polyurethane urea DMAC solution. This solution was aged overnight in a constant temperature bath at 40 ° C., and then molecular weight and molecular weight distribution were measured by GPC. Polyurethane urea having a weight average molecular weight of about 180 to 200,000 is selected from those near amine / NCO = 1.02, this solution is cast on a glass plate, dried at 60 ° C., and a film having a thickness of about 50 μm. Got. Further, an elastic fiber was obtained by a wet spinning method.

Example 2, Comparative Examples 1, 2, 3
Polyurethane urea was synthesized and formed into a film in the same manner as in Example 1 except that the concentration of the mixed amine in DMAC was changed to 3%.
As can be seen from Table 1, the molecular weight of the polytrimethylene ether glycol containing a terminal allyl group can be adjusted by reducing the amount of monoamine serving as a chain terminator.

The ratio of #terminal allyl group is represented by the number of moles of terminal allyl group / number of moles of terminal hydroxyl group * 100.
# 1 Functional component mol% = (polyol terminal allyl group + monoamine) ÷ (polyol hydroxyl group + polyol terminal allyl group + diamine + monoamine)

  Thus, by appropriately selecting the hard segment amount of the polyurethane polymer, it is possible to exhibit excellent elastic performance and durability at low temperatures.

Claims (8)

  A polyurethane comprising at least a polyether polyol unit containing 50 mol% or more of 1,3-propanediol units, wherein the amount of hard segments is higher than 10% and lower than 30% with respect to the total weight of the polyurethane polymer. Polyurethane characterized by containing in proportion.   The polyurethane according to claim 1, wherein the polyether polyol is obtained by a dehydration condensation reaction.   The polyurethane according to claim 1 or 2, wherein the polyether polyol has a molecular weight distribution (Mw / Mn) of 1.5 or more. The polyurethane according to claim 1, wherein the polyurethane is produced in the presence of an aprotic solvent. The number average molecular weight of polyether polyol is 1500-4500, The polyurethane of Claims 1-4 characterized by the above-mentioned.   A film formed by molding the polyurethane according to claim 1.   The fiber formed by shape | molding the polyurethane of any one of Claims 1-5.   The fiber according to claim 7, which is an elastic fiber.