JP2019035073A - Polycarbonate polyol and method for producing the same - Google Patents

Abstract

To produce high-quality polycarbonate diol with high productivity, which makes it possible to produce polyurethane having excellent flexibility, mechanical strength, solvent resistance and the like, using diethylene glycol as the raw material, by preventing the occurrence of dioxane, when producing polycarbonate diol by polycondensation of polyhydric alcohol containing diethylene glycol and carbonate compound.SOLUTION: Polyhydric alcohol containing diol (A) and carbonate compound are subjected to polycondensation to produce polycarbonate diol with hydroxyl value of 20-450 mgKOH/g. The diol (A) contains oxyalkylene glycol (A1) represented by the formula (1) of 60 wt.% or more, and the oxyalkylene glycol (A1) contains diethylene glycol. The amount of dioxane occurring in the polycondensation step is controlled to 1.0 wt.% or less relative to the amount of diethylene glycol to be added.SELECTED DRAWING: None

Description

  In the production of polycarbonate polyol by polycondensation of a polyhydric alcohol containing oxyalkylene glycol and a carbonate compound, the present invention suppresses the generation of dioxane and uses oxyalkylene glycol as a raw material, so that flexibility, mechanical strength, The present invention relates to a method for industrially advantageously producing a high-quality polycarbonate polyol capable of producing a polyurethane having excellent solvent resistance and the like. The present invention also relates to a high-quality polycarbonate polyol produced by suppressing the generation of dioxane, and a method for producing a polyurethane using the polycarbonate polyol.

  Conventionally, it is known to produce a polycarbonate diol-containing composition by polymerizing a dihydroxy compound and a carbonate compound by a transesterification reaction. Industrially produced polycarbonate diol-containing compositions include polycarbonate diol-containing compositions that use a dihydroxy compound such as 1,6-hexanediol as a raw material dihydroxy compound, and these polycarbonate diol-containing compositions are Generally, it is used as a raw material for polyurethane and polyurethane acrylate.

  Among the polycarbonate diols, the polycarbonate diol synthesized from 1,6-hexanediol is currently widely marketed. However, since this polycarbonate diol has high crystallinity, the cohesiveness of the soft segment is increased when polyurethane is used. In particular, there is a problem that flexibility, elongation, bending or elasticity recovery at low temperatures is poor, and its application is limited. Furthermore, it has been pointed out that the artificial leather produced from the obtained polyurethane as a raw material has a hard texture and has a “feel” that is poorer than that of natural leather.

  In order to solve these problems, polycarbonate diols having excellent flexibility and solvent resistance using oxyalkylene glycol as a raw material have been proposed. Patent Documents 1 and 2 describe polycarbonate diols using diethylene glycol. Has been. Patent Document 3 describes a polycarbonate diol obtained by copolymerizing 1,6-hexanediol and triethylene glycol.

  However, when a polycarbonate diol-containing composition is polymerized by a transesterification reaction using a dihydroxy compound containing diethylene glycol as a raw material, dioxane is adsorbed as a result of dehydration cyclization of diethylene glycol or decarboxylation cyclization of the terminal unit of the obtained polycarbonate diol. To be born. There was a problem that the productivity of the polycarbonate diol-containing composition deteriorated as the amount of by-products of dioxane increased. In addition, by-product dioxane causes coloring of the polycarbonate diol product, and polycarbonate diol obtained in a reaction system having a large amount of dioxane by-product has a problem of poor reactivity as a raw material of polyurethane. .

  In addition, dioxane is designated as a specified chemical substance in the Industrial Safety and Health Act, and there are restrictions on the amount released to the atmosphere. However, in the industrial production of polycarbonate diols that react under high vacuum conditions, it is difficult to capture low boiling point dioxane in terms of equipment, and dioxane by-products are used to improve the productivity of polycarbonate diols derived from oxyalkylene glycols. It was a problem.

  In addition, when dioxane remains in the raw material polycarbonate diol-containing composition when producing polyurethane or polyurethane acrylate, dioxane is also contained in the polyurethane solution used for paints, etc. There was also the problem of adverse health effects.

  In order to avoid problems related to dioxane by-products, conventionally, methods for reducing the amount of dioxane produced as a by-product when producing a polymer using a dihydroxy compound capable of by-producing dioxane as a raw material have been studied.

  For example, Patent Document 4 describes a method for reducing the amount of dioxane generated by devising monomer charging conditions and reaction temperature in a method for producing a polyester polyol using diethylene glycol as a raw material. However, Patent Document 4 relates to the production of polyester polyol, which requires higher reaction temperature, higher vacuum conditions and longer reaction time to remove the carbonate terminal derived from the raw material, which is a terminal structure that tends to remain, and dioxane. There is no description regarding an example in which it is applied to a polycarbonate polyol in which it is difficult to achieve both the suppression of the generation amount of the product and the acquisition of a high-quality product.

Japanese Patent No. 5448627 Japanese Patent No. 5111159 Japanese Patent No. 3684567 Special table 2012-529542 gazette

  The present invention has been made in view of the above-described conventional situation, and in the production of a polycarbonate polyol by polycondensation of a polyhydric alcohol containing diethylene glycol and a carbonate compound, generation of dioxane is suppressed as a raw material. Thus, an object of the present invention is to provide a method for producing a high-quality polycarbonate polyol capable of producing a polyurethane having excellent flexibility, mechanical strength, solvent resistance and the like with high productivity. Another object of the present invention is to provide a high-quality polycarbonate polyol produced by suppressing the generation of dioxane and a method for producing a polyurethane using the polycarbonate polyol.

As a result of repeated studies to solve the above-mentioned problems, the present inventors control the amount of dioxane generated relative to the amount of diethylene glycol added to a predetermined value or less in a polycondensation step using diethylene glycol as a polyhydric alcohol used as a raw material. It has been found that the above problems can be solved.
That is, the gist of the present invention is as follows.

[1] A method for producing a polycarbonate polyol comprising a step of polycondensing a polyhydric alcohol and a carbonate compound, wherein the polycarbonate polyol has a hydroxyl value of 20 mgKOH / g or more and 450 mgKOH / g or less, The diol (A) contains the oxyalkylene glycol (A1) represented by the following formula (1), and the content ratio of the oxyalkylene glycol (A1) in the diol (A) is 60 wt% or more, the oxyalkylene glycol (A1) contains diethylene glycol, and the terminal derived from the carbonate compound contained in the polycarbonate polyol is 1.0 mol% or less in the total terminal, in the polycondensation step Generation of dioxane The relative amount of the diethylene glycol, the production method of the polycarbonate polyol and controlling the 1.0 wt% or less.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)

[2] The method for producing a polycarbonate polyol according to [1], wherein the carbonate compound is diaryl carbonate.

[3] The method for producing a polycarbonate polyol according to [1] or [2], wherein in the polycondensation step, a metal salt of Group 2 of the long-period periodic table is used as a catalyst.

[4] The method for producing a polycarbonate polyol according to any one of [1] to [3], wherein a reaction temperature in the polycondensation step is 150 ° C. or higher and 180 ° C. or lower.

[5] The method includes a step of removing unreacted monomers of the polyhydric alcohol after the polycondensation step, and adding a phosphate deactivator before the step of removing the unreacted monomers. [1] A method for producing a polycarbonate polyol according to any one of [1] to [4].

[6] The polyhydric alcohol further includes a trivalent to hexavalent branched alcohol (B) having 3 to 12 carbon atoms, and the structural unit derived from the branched alcohol (B) in the polycarbonate polyol includes It is 0.005 mol% or more and 5.0 mol% or less with respect to the sum total of the structural unit derived from the said polyhydric alcohol in polycarbonate polyol, Any one of [1]-[5] characterized by the above-mentioned. A method for producing a polycarbonate polyol.

[7] The value of Hazen color number of the polycarbonate polyol (APHA value: compliant with JIS K0071-1 (1998)) is 50 or less, according to any one of [1] to [6] A method for producing polycarbonate polyol.

[8] A method for producing a polyurethane using the polycarbonate polyol produced by the method for producing a polycarbonate polyol according to any one of [1] to [7].

[9] A polycarbonate polyol which is a polycondensation reaction product of a polyhydric alcohol and a carbonate compound, having a hydroxyl value of 20 mgKOH / g or more and 450 mgKOH / g or less, and the terminal derived from the carbonate compound is 1 in all terminals. 0.0 mol% or less, and the value of Hazen color number (APHA value: conforming to JIS K0071-1 (1998)) is 50 or less, and the polyhydric alcohol is a diol (A) and a carbon number of 3 to 3. 12 trivalent to hexavalent branched alcohol (B), the diol (A) contains an oxyalkylene glycol (A1) represented by the following formula (1), and in the diol (A) The content of the oxyalkylene glycol (A1) is 60% by weight or more, and the oxyalkylene glycol (A1) is diethylene glycol. A polycarbonate polyol comprising recall.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)

[10] The structural unit derived from the branched alcohol (B) in the polycarbonate polyol is 0.005 mol% or more and 5.0 mol based on the total of the structural units derived from the polyhydric alcohol in the polycarbonate polyol. % Or less, the polycarbonate polyol according to [9].

ADVANTAGE OF THE INVENTION According to this invention, the high quality polycarbonate polyol which uses the xylene alkylene glycol containing diethylene glycol as a raw material can be manufactured with sufficient productivity.
By polymerizing the polycarbonate polyol produced according to the present invention with isocyanate or the like, a polyurethane having high flexibility and mechanical strength and excellent solvent resistance can be provided. Moreover, the problem of volatilization of dioxane when using polyurethane is also prevented.

  The polyurethane produced by using the polycarbonate polyol of the present invention has good reactivity at the time of urethane polymerization, and has an excellent balance of flexibility, mechanical strength, and solvent resistance, elastic fiber, synthetic or artificial It is suitable for leather, paints, and high-performance elastomer applications, and is extremely useful industrially.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind. Further, in the present specification, “wt%” and “wt%”, “mass ppm” and “wt ppm”, and “mass part” and “weight part” are synonymous respectively. In addition, when “ppm” is simply described, it indicates “weight ppm”.

[1. Polycarbonate polyol and method for producing the same]
The method for producing a polycarbonate polyol of the present invention is a method for producing a polycarbonate polyol including a step of polycondensing a polyhydric alcohol and a carbonate compound, wherein the polycarbonate polyol has a hydroxyl value of 20 mgKOH / g or more and 450 mgKOH / g or less. The polyhydric alcohol contains a diol (A), the diol (A) contains an oxyalkylene glycol (A1) represented by the following formula (1), and the oxyalkylene glycol in the diol (A) The content ratio of (A1) is 60% by weight or more, the oxyalkylene glycol (A1) contains diethylene glycol, and the terminal derived from the carbonate compound contained in the polycarbonate polyol is 1.0 mol% or less in the total terminal. Yes, the polycondensation The generation amount of dioxane generated in step, with respect to the addition amount of the diethylene glycol, and controlling the 1.0 wt% or less.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)

  Hereinafter, the amount of dioxane generated relative to the amount of oxyalkylene glycol (A1) added in the polycondensation step according to the present invention is simply referred to as “dioxane generation amount”.

  The polycarbonate polyol of the present invention is a polycarbonate polyol that is a polycondensation reaction product of a polyhydric alcohol and a carbonate compound, having a hydroxyl value of 20 mgKOH / g or more and 450 mgKOH / g or less, and the terminal derived from the carbonate compound is , 1.0 mol% or less in all terminals, and Hazen color number value (APHA value: compliant with JIS K0071-1 (1998)) is 50 or less, and the polyhydric alcohol is a diol (A) And a trivalent to hexavalent branched alcohol (B) having 3 to 12 carbon atoms, the diol (A) includes an oxyalkylene glycol (A1) represented by the following formula (1), and The content ratio of the oxyalkylene glycol (A1) in the diol (A) is 60% by weight or more, and the oxyal Glycol (A1) is characterized in that it comprises a diethylene glycol.

  In the following, the terminal derived from the carbonate compound according to the present invention is referred to as “carbonate terminal”, and the ratio of the carbonate terminal in all terminals in the polycarbonate polyol is simply referred to as “carbonate terminal amount”.

According to the method for producing a polycarbonate polyol of the present invention, the above-described polycarbonate polyol of the present invention can be produced. Moreover, there is no restriction | limiting in particular in the method of manufacturing the said polycarbonate polyol of this invention, Preferably, it manufactures with the manufacturing method of the said polycarbonate polyol of this invention.
Hereinafter, the polycarbonate polyol produced by the method for producing a polycarbonate polyol of the present invention is also referred to as “polycarbonate polyol of the present invention”.

<1-1. Features of dioxane generation amount, carbonate terminal amount, APHA value>
In the method for producing a polycarbonate polyol of the present invention, the amount of dioxane generated in the polycondensation step of the polyhydric alcohol and the carbonate compound is controlled to 1.0% by weight or less with respect to the amount of charged diethylene glycol used for the production of the polycarbonate polyol. One of its features is to do.

When the amount of dioxane generated in the polycondensation step is larger than the above upper limit, the productivity decreases due to dioxane by-products, the physical properties of the obtained polycarbonate polyol deteriorate, and the coloration problem. Furthermore, polyurethane is produced using this polycarbonate polyol. This causes problems such as reduced reactivity and deterioration of the quality of the produced polyurethane, which is not preferable. The smaller the amount of dioxane generated, the more preferable from the viewpoint of the productivity of polycarbonate polyol and the quality of polycarbonate polyol and polyurethane, 1.0 wt% or less, preferably 0.7 wt% or less, more preferably 0.5 wt% or less. More preferably, the amount is controlled to be 0.3% by weight or less, particularly preferably 0.1% by weight or less.
The amount of dioxane generated can be analyzed by the method described in the Examples section below. Here, “0.1 wt% or less” means the detection limit of dioxane in the analysis of the polycarbonate polyol product. Equivalent to.

  One of the characteristics of the polycarbonate polyol of the present invention is that the carbonate terminal amount is 1.0 mol% or less and the APHA value is 50 or less.

  When the carbonate terminal amount exceeds the above upper limit, the reactivity when producing a polyurethane using this polycarbonate polyol is inferior, and it becomes difficult to produce a polyurethane having a high molecular weight and excellent mechanical strength, chemical resistance and the like. Further, a high APHA value of the polycarbonate polyol means that the polycarbonate polyol is colored, which is not preferable as the quality of the polycarbonate polyol itself. Moreover, since the polyurethane manufactured using this polycarbonate polyol will also be colored, it is not preferable.

Therefore, the carbonate terminal amount of the polycarbonate polyol of the present invention is preferably as small as possible, and is 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.1 mol% or less.
The carbonate terminal amount can be analyzed by the method described in the Examples section below. Here, “0.1 mol% or less” is the detection limit of the carbonate terminal amount in the analysis of the polycarbonate polyol product. It corresponds to.

  Also, the APHA value of the polycarbonate polyol is preferably low, and the APHA value of the polycarbonate polyol of the present invention is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less. When the APHA value exceeds 50, the color tone of the polyurethane obtained using the polycarbonate diol-containing composition as a raw material is deteriorated, and the commercial value is lowered or the thermal stability is deteriorated. In particular, a polycarbonate diol-containing composition using an aliphatic dihydroxy compound having an alcoholic hydroxyl group as a raw material exhibits various excellent performances such as flexibility, water resistance, and light resistance when processed into polyurethane. Heat history and coloration due to the catalyst tend to be more remarkable than when the compound is used as a raw material, and it is not easy to make the APHA value 50 or less. The APHA value of polycarbonate polyol is measured by the method described in the Examples section below.

<1-2. Achieving means of dioxane generation amount, carbonate end amount, APHA value>
Although there is no restriction | limiting in particular as a means for achieving the dioxane generation amount of 1.0 weight% or less in a polycondensation step, For example, the method of the following (1)-(5) is mentioned. The achievement means (1) to (5) below may be combined in some ways, and from the viewpoint of certainty of achievement, a plurality of achievement means (1) to (5) below are adopted in combination. It is preferable to adopt all of them.
Further, by adopting the following means (1) to (5) and controlling the dioxane generation amount to 1.0 wt% or less, the carbonate end amount is 1.0 mol% or less and the APHA value is 50 or less. It is also possible to produce a polycarbonate polyol.

(1) Diaryl carbonate, particularly preferably diphenyl carbonate, is used as the carbonate compound raw material. When a carbonate compound other than diaryl carbonate such as diphenyl carbonate is used, unreacted diethylene glycol is heated for a long time due to low reactivity with polyhydric alcohol, and the amount of dioxane generated tends to increase. That is, the amount of dioxane generated can be reduced by using a highly reactive diaryl carbonate such as diphenyl carbonate as the carbonate compound raw material. Moreover, since the catalyst concentration shown in the following (2) can be reduced due to the high reactivity, the amount of dioxane generated can be similarly reduced.

(2) In the polycondensation step, a metal salt of Group 2 of a long-period periodic table (in the present invention, simply referred to as “periodic table”) is used as a catalyst. When a catalyst other than the metal salt of Group 2 of the periodic table is used as the catalyst, the amount of dioxane generated tends to increase. For example, since the basicity is too high in the metal salt of Group 1 of the periodic table and the acidity is too high in the metal salt of Group 3 and Group 4, the reason is that the side reaction dioxane generation reaction is accelerated. It is done. On the other hand, when a metal salt of Group 2 of the periodic table is used, only a desired esterification reaction can be accelerated as a moderately basic catalyst, so that the amount of dioxane generated can be reduced.
When a metal salt of Group 2 of the periodic table is used, the concentration in terms of metal in the polycondensation reaction solution is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less, particularly preferably 15 ppm or less, The lower limit is preferably 1 ppm or more for more reliably reducing the amount of dioxane generated. Even if the concentration of the metal salt of Group 2 of the periodic table exceeds the upper limit or lower than the lower limit, the amount of dioxane generated tends to increase.

  The metal salt of Group 2 of the periodic table usually does not volatilize and remains in the polycarbonate diol. However, if too much catalyst remains, it becomes difficult to control the reaction during the polyurethane reaction, and the polyurethane reaction is more than expected. The amount of the residual component needs to be 50 ppm or less, preferably 30 ppm or less as a weight ratio in terms of metal with respect to polycarbonate diol. More preferably, it is 20 ppm or less, and particularly preferably 15 ppm or less. On the other hand, if the amount of the catalyst is small, the above-mentioned problems may be caused. Therefore, the amount in terms of metal relative to the polycarbonate diol is preferably 1 ppm or more.

(3) The reaction temperature in the polycondensation step is 150 ° C. or higher and 180 ° C. or lower. If the reaction temperature is less than 150 ° C., the polycondensation reaction cannot proceed smoothly, and a polycarbonate polyol having a sufficient molecular weight cannot be produced, or the residual amount of carbonate ends increases, but if it exceeds 180 ° C. There is a tendency that the amount of dioxane generated is increased or colored due to decomposition of diethylene glycol. The reaction temperature is particularly preferably 160 ° C. or higher and 170 ° C. or lower.

(4) The reaction time in the polycondensation step is 3 hours or more and 20 hours or less. If the reaction time is less than 3 hours, the polycondensation reaction cannot proceed sufficiently, and a polycarbonate polyol having a sufficient molecular weight cannot be produced, or the residual amount of carbonate ends increases, but if it exceeds 20 hours, There is a tendency for the amount of dioxane generated to increase or to be colored due to the decomposition of diethylene glycol or the decarboxylation cyclization of the terminal unit of the polycarbonate diol. The reaction time is particularly preferably 5 hours or more and 10 hours or less.

(5) Adjust the degree of decompression. Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, it is usually preferable to carry out the reaction while distilling off the light boiling component produced by gradually reducing the pressure from the middle of the reaction.
In particular, it is preferable to increase the degree of vacuum at the end of the reaction because the by-produced monoalcohol, phenol, and other light boiling components can be distilled off. That is, the minimum pressure is preferably less than 1.5 kPa, particularly preferably 1.0 kPa or less, and particularly preferably 0.8 to 0.1 kPa. When this pressure exceeds the above upper limit, the reactivity is lowered and the reaction time is prolonged, the amount of dioxane generated may be increased, or the APHA of the obtained polycarbonate diol may be increased. However, if this pressure is too low, the rate of distilling off the by-product phenol is high, so that the polymerization rate becomes high and it is difficult to control the molecular weight.

<1-3. Structural features derived from raw polyhydric alcohols>
<1-3-1. Oxyalkylene glycol (A1) and its content>
The polycarbonate polyol of the present invention contains 60% by weight or more of the oxyalkylene glycol (A1) represented by the following formula (1) in the raw material diol (A), and diethylene glycol as an essential component in the oxyalkylene glycol (A1). By including oxyalkylene glycol (A1) at such a ratio, it becomes excellent in flexibility and solvent resistance (hereinafter referred to as solvent resistance including chemical resistance). From the viewpoint of flexibility and solvent resistance, the content of the oxyalkylene glycol (A1) in the diol (A) is preferably 70% by weight or more, particularly preferably 80% by weight or more, and 90% by weight or more. Is particularly preferred.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)

  The polycarbonate polyol of the present invention obtained using oxyalkylene glycol (A1) at such a ratio has a ratio of structural units derived from oxyalkylene glycol (A1) to the total of structural units derived from diol (A). The amount is usually 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

As the oxyalkylene glycol (A1), diethylene glycol is essential, and any oxyalkylene glycol (A1) may be used as long as it is represented by the above formula (1), and is not particularly limited, but in terms of flexibility and solvent resistance, the formula (1) The number of carbon atoms of ^RA is preferably 2 or 3, and more preferably 2. As good a carbon chain optionally contain branched 2-5 carbon atoms R ^A, and specific examples thereof include linear or branched alkylene group having 2 to 5 carbon atoms.

  Specific examples of the oxyalkylene glycol (A1) other than diethylene glycol include triethylene glycol, tetraethylene glycol, and dipropylene glycol. These oxyalkylene glycols (A1) may be used alone or in combination of two or more.

As the oxyalkylene glycol (A1), it is particularly preferable to use diethylene glycol or diethylene glycol and triethylene glycol, and the total content of diethylene glycol and triethylene glycol in the raw material diol (A) is 60% by weight or more, preferably 70 It is preferable from a viewpoint of a softness | flexibility and chemical-resistance that it is more than weight%, especially 80 weight% or more, especially 90 weight% or more. Further, the upper limit of the content is usually preferably 99.5% by weight or less, more preferably 99% by weight or less, and still more preferably 98% by weight or less.
The oxyalkylene glycol (A1) used in the present invention contains diethylene glycol, and the content ratio of diethylene glycol in the raw material diol (A) is 50% by weight or more, preferably 60% by weight or more, particularly 70% by weight or more. Is preferable from the viewpoints of flexibility and chemical resistance.

  In particular, the combined use of diethylene glycol and triethylene glycol as the oxyalkylene glycol (A1) prevents aggregation due to hydrogen bonds by disturbing the regularity of the structural units in the polycarbonate polyol chain, thereby increasing flexibility. In this case, the ratio of diethylene glycol and triethylene glycol used is diethylene glycol: triethylene glycol = 10: 90 to 90:10, particularly 20:80 to 80:20. Is more preferable, 30:70 to 70:30 is more preferable, and 40:60 to 60:40 is particularly preferable.

  In addition, when the raw material diol (A) of the polycarbonate polyol of the present invention contains a diol other than the oxyalkylene glycol (A1) represented by the formula (A1), other diols include ethylene glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane C2-C20 linear diol such as diol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2 , 2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl 1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,2,4,4-tetramethyl-1,5-pentanediol Branched diols having 4 to 20 carbon atoms such as 2-ethyl-1,6-hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethyl C6-C20 cyclic diols such as methanediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 4,4'-isopropylidenedicyclohexanol, norbornane-2,3-dimethanol, and other isosorbides 3,4-dihydroxytetrahydrofuran, 3,9-bis (1,1-dimethyl-2-hydroxy Til) -2,4,8,10-tetraoxaspiro [5.5] undecane (cas number: 1455-42-1), 2- (5-ethyl-5-hydroxymethyl-1,3-dioxane-2) -Il) -2-methylpropan-1-ol (cas number: 59802-10-7) and the like, and cyclic diols having a hetero atom in the ring.

  These other diols may be used alone or in combination of two or more, but as described above, the effect of improving flexibility and solvent resistance by using oxyalkylene glycol (A1). In order to obtain it, the content in the diol (A) is 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

<1-3-2. Branched alcohol (B) and its content>
In the polycarbonate polyol of the present invention, the branched alcohol (B) may be used as a raw material polyhydric alcohol together with the diol (A) containing the oxyalkylene glycol (A1) at the above ratio. In this case, the structural unit derived from the branched alcohol (B) in the polycarbonate polyol is 0.005 mol% or more and 5.0 mol% or less with respect to the total of the structural units derived from the polyhydric alcohol in the polycarbonate polyol. Therefore, the crosslinked structure introduced by the branched alcohol (B) without impairing the flexibility and solvent resistance due to the oxyalkylene glycol (A1) can be excellent in mechanical strength, which is preferable.

  From the viewpoint of compatibility between flexibility and solvent resistance and mechanical strength, the proportion of the structural unit derived from the branched alcohol (B) in the structural unit derived from the polyhydric alcohol in the polycarbonate polyol of the present invention is 0.005. It is preferably ˜5.0 mol%, more preferably 0.05 to 3.0 mol%, and further preferably 0.5 to 2.0 mol%.

In order to set the structural unit derived from the branched alcohol (B) in the structural unit derived from the polyhydric alcohol in the polycarbonate polyol within the above range, the mole of the branched alcohol (B) in the polyhydric alcohol used as a raw material for the polycarbonate polyol. What is necessary is just to make content rate into the said range.
That is, in general, the ratio of each polyhydric alcohol in the raw material polyhydric alcohol is the ratio of the structural unit derived from each polyhydric alcohol to the total of the structural units derived from the polyhydric alcohol in the obtained polycarbonate polyol. It will be almost equal.

  The trivalent to hexavalent branched alcohol (B) having 3 to 12 carbon atoms contained in the raw material polyhydric alcohol of the polycarbonate polyol of the present invention includes glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, and trimethylolbutane. 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, penta Erythritol, diglycerol, triglycerol, polyglycerol, bis (trimethylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, sugars such as glucose, sugar derivatives such as sorbitol Used to go, and the like. The polycarbonate polyol of the present invention may contain only one type of structural unit derived from these branched alcohols (B), or may contain two or more types. That is, the branched alcohol (B) used as the raw material polyhydric alcohol of the polycarbonate polyol of the present invention may be one type or two or more types.

  Among these, from the viewpoint of the introduction efficiency of the crosslinked structure, a branched alcohol containing at least a part, preferably all of the hydroxyl group as a methylol group is preferred, and a smaller number of carbon atoms is preferred. That is, the methylol group has a structure having a hydroxyl group via a methylene group, and thus has high reactivity. Further, when the same number of moles of branched alcohol is added, the crosslinking density can be increased when the number of carbon atoms is smaller. However, when the number of carbon atoms of the branched alcohol (B) is too small, the reactivity of each hydroxyl group is deteriorated due to steric hindrance, and the crosslinking is difficult to proceed. In addition, cross-linking points may be too dense and promote gelation. Therefore, the branched alcohol (B) is preferably a branched alcohol having a trivalent to hexavalent methylol group having 3 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. Specifically, trivalent alcohols such as glycerol, trimethylolpropane, trimethylolethane, and trimethylolmethane, tetrahydric alcohols such as pentaerythritol and ditrimethylolpropane, and hexavalent alcohols such as dipentaerythritol are preferable, and particularly appropriate. A trihydric alcohol capable of forming a structural unit having a crosslinking density and preventing gelation is preferred, and trimethylolpropane, which contains three highly reactive methylol groups, is easily available industrially and is inexpensive, is most preferred.

<1-3-3. Suitable raw material polyhydric alcohol>
The polycarbonate polyol of the present invention is preferably one using diethylene glycol or a diol (A) containing diethylene glycol and triethylene glycol and a branched alcohol (B) containing trimethylolpropane as the raw material polyhydric alcohol. , Using triethylene glycol and trimethylolpropane, those using 30 to 70 mol% diethylene glycol, 30 to 70 mol% triethylene glycol, and 0.005 to 5 mol% trimethylolpropane with respect to a total of 100 mol%, It is preferable from the viewpoints of flexibility, solvent resistance and mechanical strength.

  In addition, the raw material polyhydric alcohol of the polycarbonate polyol of the present invention includes polyhydric alcohols other than the diol (A) and the branched alcohol (B) described above, for example, a trihydric or higher linear alcohol or a trihydric or higher cyclic alcohol. However, in order to effectively obtain the above-described effects by using the diol (A) and the branched alcohol (B), a polyvalent other than the diol (A) and the branched alcohol (B) in the raw material polyhydric alcohol may be used. The alcohol content is 30% by weight or less, particularly 20% by weight or less, more preferably 10% by weight or less, and most preferably, these alcohols are not contained in the starting polyhydric alcohol.

<1-4. Carbonate compound>
Although it does not limit as a carbonate compound used for manufacture of the polycarbonate polyol of this invention unless the effect of this invention is impaired, a dialkyl carbonate, a diaryl carbonate, or an alkylene carbonate is mentioned.
Among these, when diaryl carbonate is used, there is an advantage that the reaction proceeds promptly or reacts with a structural unit in the low-reactivity polyhydric alcohol and polycarbonate polyol, and as a result, the proportion of the carbonate terminal structure can be reduced. .
As described above, from the viewpoint of reducing the amount of dioxane generated, it is preferable to use a diaryl carbonate such as diphenyl carbonate as the carbonate compound.

  Specific examples of the dialkyl carbonate, diaryl carbonate, and alkylene carbonate that can be used in the production of the polycarbonate polyol according to the present invention are as follows.

  Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, ethyl isobutyl carbonate, and preferably dimethyl carbonate and diethyl carbonate.

  Examples of diaryl carbonates include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, and preferably diphenyl carbonate.

  Examples of alkylene carbonates include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2- Examples include pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate. Preferably, it is ethylene carbonate.

  These may be used alone or in combination of two or more.

  Among these, diaryl carbonate is preferable because it is rich in reactivity and efficient in industrial production, and diphenyl carbonate that is easily available at low cost as industrial raw material is more preferable. As described above, diphenyl carbonate is preferable from the viewpoint of reducing the amount of dioxane generated, the amount of carbonate ends, and the APHA value.

  In the production of the polycarbonate polyol of the present invention, the amount of the carbonate compound used is not particularly limited, but the lower limit is preferably 0.35, more preferably 0.50, usually in a molar ratio with respect to a total of 1 mol of the starting polyhydric alcohol. More preferably, it is 0.60, and the upper limit is preferably 1.00, more preferably 0.98, and still more preferably 0.97. If the amount of the carbonate compound used exceeds the upper limit, the proportion of the polycarbonate polyol end group that is not a hydroxyl group may increase or the molecular weight may not be within the predetermined range. If the amount is less than the lower limit, polymerization proceeds to the predetermined molecular weight. In some cases, the raw material polyhydric alcohol may remain.

<1-5. Transesterification Catalyst>
The polycarbonate polyol of the present invention can be produced by polycondensing the aforementioned polyhydric alcohol and a carbonate compound by a transesterification reaction.

  In the production of the polycarbonate polyol of the present invention, a transesterification catalyst (hereinafter sometimes referred to as a catalyst) is usually used to promote polycondensation. As the transesterification catalyst, any compound that is generally considered to have transesterification ability can be used without limitation.

  Examples of transesterification catalysts include lithium, sodium, potassium, rubidium, cesium and other periodic table group 1 metal compounds; magnesium, calcium, strontium, barium and other periodic table group 2 metal compounds; titanium, zirconium Periodic Table Group 4 metal compounds such as Hafnium; Periodic Table Group 5 metal compounds such as hafnium; Periodic Table Group 9 metal compounds such as cobalt; Periodic Table Group 12 metal compounds such as zinc; Periodic table group 13 metal compounds; germanium, tin, lead, etc. periodic table group 14 metal compounds; antimony, bismuth, etc. periodic table group 15 metal compounds; lanthanides such as lanthanum, cerium, europium, ytterbium Examples thereof include metal compounds. Among these, from the viewpoint of increasing the transesterification reaction rate, compounds of Group 1 metal of the periodic table, compounds of Group 2 metal of the periodic table, compounds of Group 4 metal of the periodic table, compounds of Group 5 metal of the periodic table, Periodic table Group 9 metal compound, Periodic table Group 12 metal compound, Periodic table Group 13 metal compound, Periodic table Group 14 metal compound are preferred, Periodic table Group 1 metal compound, Periodic table A compound of Group 2 metal is more preferable, and a compound of Group 2 metal of the periodic table is more preferable. Among the compounds of Group 1 metals of the periodic table, lithium, potassium, and sodium compounds are preferable, lithium and sodium compounds are more preferable, and sodium compounds are more preferable. Among the compounds of Group 2 metals of the periodic table, magnesium, calcium and barium compounds are preferred, calcium and magnesium compounds are more preferred, and magnesium compounds are more preferred. These metal compounds are mainly used as hydroxides and salts. Examples of salts when used as salts include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonate and toluenesulfonate And sulfonates such as trifluoromethanesulfonate; phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; and acetylacetonate salts. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

Of these, preferred are acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, alkoxides of at least one metal selected from Group 2 metals of the periodic table, and more Preferred are acetates, carbonates and hydroxides of Group 2 metals of the periodic table, more preferred are acetates, carbonates and hydroxides of magnesium and calcium, and particularly preferred are acetates of magnesium and calcium. Most preferably, it is magnesium acetate.
From the viewpoint of reacting the low-reactivity oxyalkylene glycol (A1), the branched alcohol (B), the terminal group of the oxyaryl structure derived from the carbonate compound, etc. There are low electronegativity and strong coordinating property to the carbonate compound, so it exhibits high transesterification catalysis, Group 1 metal compounds of the periodic table, Group 2 metal compounds of the periodic table, Group 4 of the periodic table Metal acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, and alkoxides are preferred. On the other hand, with strong acidity or strong basicity, decomposition of the oxyalkylene glycol (A1) contained in the raw material and the polycarbonate polyol structural unit occurs, the molecular weight does not increase, and harmful low molecular weight compounds (1,4-dioxane) are secondary. Because of the problem of production, periodic table group 2 metal compounds having moderate basicity are preferred. In particular, to reduce the branched alcohol (B) having low reactivity, the terminal group of the oxyaryl structure derived from the carbonate compound, etc., magnesium, calcium acetate and carbonate, which are highly stable even when reacted for a long time, hydroxylation The most preferred is magnesium acetate.
Further, as described above, from the viewpoint of reducing the amount of dioxane generated in the polycondensation step, the carbonate terminal amount of the resulting polycarbonate polyol, and the reduction of the APHA value, a metal salt of Group 2 of the periodic table is preferable, and magnesium, calcium acetate, Carbonates are preferred, most preferably magnesium acetate.

  When the above catalyst is used, if an excessive amount of catalyst remains in the obtained polycarbonate polyol, the reaction is inhibited or excessively accelerated when a polyurethane is produced using the polycarbonate polyol. There is a case.

Therefore, when a transesterification catalyst is used, the amount used is preferably an amount that does not affect the performance even if it remains in the obtained polycarbonate polyol, and is a metal-based weight ratio to the weight of the total polyhydric alcohol. The upper limit is preferably 500 ppm, more preferably 100 ppm, still more preferably 50 ppm, and particularly preferably 10 ppm. On the other hand, the lower limit is an amount that provides sufficient polymerization activity, and is preferably 0.01 ppm, more preferably 0.1 ppm, and even more preferably 1 ppm.
Further, when using a group 2 metal compound of the periodic table as a catalyst, the total amount of all the metal atoms is preferably 5 μmol or more, more preferably 7 μmol or more, more preferably 10 μmol per 1 mol of all polyhydric alcohols used as raw materials. As mentioned above, Preferably it is 500 micromol or less, More preferably, it is 300 micromol or less, More preferably, it is 100 micromol or less, Most preferably, it is 50 micromol or less.

  In addition, as described above, from the viewpoint of reducing the amount of dioxane generated in the polycondensation step, the carbonate terminal amount of the resulting polycarbonate polyol, and the reduction of the APHA value, when using a metal salt of Group 2 of the periodic table as a catalyst, The concentration in terms of metal in the polycondensation reaction solution is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less, particularly preferably 15 ppm or less, and the lower limit is preferably 1 ppm or more.

<1-6. Production method of polycarbonate polyol>
The polycarbonate polyol of the present invention uses the above-mentioned polyhydric alcohol and the above-mentioned carbonate compound in the above-mentioned proportions, and in the presence of the transesterification catalyst used as necessary, the above-mentioned (1) to (5) It can be produced by transesterification and polycondensation using the achievement means. The manufacturing method will be described below.

There are no particular restrictions on the method of charging the reaction raw materials, and a method in which the total amount of polyhydric alcohol, carbonate compound and transesterification catalyst is charged simultaneously, and when the carbonate compound is solid, the carbonate compound is first charged and heated and melted. After that, a method of adding a polyhydric alcohol and a transesterification catalyst, a method of charging a polyhydric alcohol first and melting it, and adding a carbonate compound and a transesterification catalyst thereto, The method can be freely selected, such as a method in which a diester carbonate derivative of a polyhydric alcohol is synthesized by reacting a portion with a carbonate compound or a chlorocarbonate to react with the remaining polyhydric alcohol.
In the method for producing the polycarbonate polyol of the present invention, it is possible to employ a method in which a part of the polyhydric alcohol to be used is added at the end of the reaction in order to reduce the amount of terminal carbonate. In that case, the upper limit of the amount of polyhydric alcohol added last is usually 20% of the amount of polyhydric alcohol to be charged, preferably 15%, more preferably 10%, and the lower limit is usually It is 0.1%, preferably 0.5%, and more preferably 1.0%.

  The preferred reaction temperature for the polycondensation reaction is as described above. If the reaction temperature is too high, the resulting polycarbonate polyol may be colored, or the ether structure may be added as a result of decarboxylation of carbonate groups or dehydration condensation between polyhydric alcohols. May cause quality problems, such as Further, since the polycarbonate polyol of the present invention contains a structural unit derived from odiethylene glycol, there are problems such as cleavage of the oxyalkylene chain or generation of harmful dioxane by dehydration condensation when the upper limit is exceeded.

Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, usually, it is preferable to carry out the reaction in the latter half of the reaction while distilling off the light boiling component under reduced pressure conditions. Or it is also possible to make it react, distilling off the light boiling component produced | generated by reducing pressure gradually from the middle of reaction.
In particular, it is preferable to increase the degree of vacuum at the end of the reaction, because by-produced alcohols and phenols can be distilled off.
In this case, the reaction pressure at the end of the polycondensation reaction is preferably set so as to be the above-described degree of reduced pressure.
At this time, in order to effectively distill the light boiling component, the reaction can be performed while passing a small amount of an inert gas such as nitrogen, argon or helium into the reaction system.

  In order to prevent the raw material from being distilled off at the initial stage of the reaction, it is possible to attach a reflux tube to the reactor and perform the reaction while refluxing the carbonate compound and the polyhydric alcohol. In this case, it is preferable because the charged raw materials are not lost and the amount ratio of the reagents can be accurately adjusted.

  The reaction time is also as described above, and is preferably 3 hours or more and 20 hours or less, particularly preferably 5 hours or more and 10 hours or less.

  As described above, when a transesterification catalyst is used in the polycondensation reaction, the transesterification catalyst remains in the obtained polycarbonate polyol, and the reaction control is performed when the polyurethane conversion reaction is performed with the transesterification catalyst remaining. May not be possible. In order to suppress the influence of this residual catalyst, a phosphate deactivator may be added after the polycondensation step and before the step of removing unreacted monomers. Furthermore, the transesterification catalyst can be efficiently deactivated by heat treatment as described later after the addition of the phosphoric acid-based deactivator.

Examples of the phosphoric acid deactivator used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate and triphosphate. Examples thereof include organic phosphates such as phenyl and triphenyl phosphite.
These may be used alone or in combination of two or more.

  The amount of the phosphoric acid deactivator used is not particularly limited, but is preferably approximately equimolar with the transesterification catalyst used, and specifically, with respect to 1 mol of the transesterification catalyst used. The upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.6 mol, more preferably 0.8 mol, and still more preferably 1.0 mol. When a smaller amount of the phosphoric acid deactivator is used, the transesterification catalyst is not sufficiently deactivated, and when the obtained polycarbonate polyol is used as a raw material for polyurethane production, for example, the isocyanate group of the polycarbonate polyol is used. In some cases, the reactivity with respect to can not be sufficiently reduced. Moreover, when the phosphoric acid type quencher exceeding this range is used, the obtained polycarbonate polyol may be colored.

Inactivation of the transesterification catalyst by adding a phosphoric acid-based deactivator can be performed even at room temperature, but it is more efficient when heated. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 180 ° C, more preferably 150 ° C, still more preferably 120 ° C, particularly preferably 100 ° C, and the lower limit is preferably 50 ° C, more preferably. Is 60 ° C., more preferably 70 ° C. When the temperature is lower than this, it takes time to deactivate the transesterification catalyst, which is not efficient, and the degree of deactivation may be insufficient. On the other hand, at a temperature exceeding the upper limit, the obtained polycarbonate polyol may be colored.
The time for reacting with the phosphate deactivator is not particularly limited, but is usually 0.1 to 5 hours.

  After the polycondensation reaction, the terminal structure in the polycarbonate polyol is an impurity having an alkyloxy group, an impurity having an aryloxy group, phenols, unreacted monomers such as polyhydric alcohol and carbonate compounds as raw materials, and an added catalyst. It is preferable to carry out purification for the purpose of removing. In the purification at that time, a method of distilling off a light boiling compound by distillation can be employed. The specific method of distillation is not particularly limited, such as vacuum distillation, steam distillation, thin film distillation, etc., but thin film distillation is particularly effective. Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent solution or the like. In that case, the compound dissolved in water can be selected arbitrarily.

Although there is no restriction | limiting in particular as thin film distillation conditions, As for the temperature at the time of thin film distillation, it is preferable that an upper limit is 250 degreeC, and it is preferable that it is 200 degreeC. Moreover, it is preferable that a minimum is 120 degreeC, and it is more preferable that it is 150 degreeC.
By setting the lower limit of the temperature at the time of thin-film distillation to the above value, the effect of removing light boiling components becomes sufficient. Moreover, there exists a tendency which prevents the polycarbonate polyol obtained after thin film distillation from coloring by making an upper limit into 250 degreeC.

The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure during thin film distillation to the upper limit value or less, the effect of removing light boiling components tends to be sufficiently obtained.
Moreover, the upper limit of the temperature of the polycarbonate polyol just before thin film distillation is preferably 250 ° C, more preferably 150 ° C. Moreover, it is preferable that a minimum is 80 degreeC, and it is more preferable that it is 120 degreeC.

  By setting the temperature for keeping the polycarbonate polyol immediately before the thin film distillation to the above lower limit or more, the fluidity of the polycarbonate polyol immediately before the thin film distillation tends to be prevented from being lowered. On the other hand, by setting it to the upper limit or less, there is a tendency to prevent the polycarbonate polyol obtained after thin film distillation from being colored.

<1-7. Properties of polycarbonate polyol>
<1-7-1. Hydroxyl value>
The lower limit of the hydroxyl value of the polycarbonate polyol of the present invention is 20 mgKOH / g, preferably 25 mgKOH / g, more preferably 30 mgKOH / g, still more preferably 35 mgKOH / g. The upper limit of the hydroxyl value of the polycarbonate polyol is 450 mgKOH / g, preferably 230 mgKOH / g, more preferably 150 mgKOH / g, more preferably 120 mgKOH / g, still more preferably 75 mgKOH / g, particularly preferably 60 mgKOH / g, most preferably Preferably it is 45 mgKOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high and handling during polyurethane formation may be difficult. If the upper limit is exceeded, physical properties such as flexibility and low-temperature characteristics may be insufficient when polyurethane is used.

<1-7-2. Molecular weight distribution>
The weight average molecular weight / number average molecular weight (Mw / Mn), which is the molecular weight distribution of the polycarbonate polyol of the present invention, is not particularly limited, but the lower limit is preferably 1.5, and more preferably 1.8. The upper limit of the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 3.5, more preferably 3.0. When the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this polycarbonate polyol tend to become hard at low temperatures or decrease in elongation, and an attempt is made to produce a polycarbonate polyol having a molecular weight distribution less than the above range. Then, an advanced purification operation such as removing the oligomer may be necessary.
The weight average molecular weight of the polycarbonate polyol of the present invention is a polystyrene equivalent weight average molecular weight, the number average molecular weight of the polycarbonate polyol of the present invention is a polystyrene equivalent number average molecular weight, and these are usually gel permeation chromatography (GPC). (It may be abbreviated in some cases).

<1-7-3. Molecular chain end>
The molecular chain terminal of the polycarbonate polyol of the present invention is mainly a hydroxyl group. However, in the case of a polycarbonate polyol obtained by the reaction of a polyhydric alcohol and a carbonate compound, there is a possibility that some molecular chain terminals are not hydroxyl groups as impurities. As specific examples thereof, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many have a carbonate terminal structure.

For example, when diphenyl carbonate is used as the carbonate compound, a phenoxy group (PhO-) is used as the aryloxy group at the carbonate terminal, and when dimethyl carbonate is used, a methoxy group (MeO-) or diethyl carbonate is used as the alkyloxy group. Is an ethoxy group (EtO-), and when ethylene carbonate is used, a hydroxyethoxy group (HOCH ₂ CH ₂ O-) may remain as a molecular chain end (where Ph represents a phenyl group, Me represents methyl Group, Et represents an ethyl group).
As described above, the carbonate terminal amount of the polycarbonate polyol of the present invention is preferably 1.0 mol% or less, more preferably 0.8 mol% or less, still more preferably 0.5 mol% or less, particularly preferably 0.1 mol% or less. is there. The terminal structure and terminal amount can be usually determined by ¹ H-NMR measurement.

<1-7-4. Residual monomers, etc.>
For example, when diaryl carbonate such as diphenyl carbonate is used as a raw material, phenols are by-produced during the production of polycarbonate polyol. Since phenols are monofunctional compounds, they may be an inhibitory factor in the production of polyurethane, and the urethane bonds formed by phenols are weak in their bonding strength, so they are heated by subsequent processes. It may dissociate, causing isocyanates and phenols to be regenerated and causing problems. Moreover, since phenols are also stimulating substances, it is preferable that the residual amount of phenols in the polycarbonate polyol is smaller. Specifically, the weight ratio to the polycarbonate polyol is preferably 1000 ppm by weight or less, more preferably 500 ppm by weight or less, still more preferably 300 ppm by weight or less, and particularly preferably 100 ppm by weight or less. In order to reduce phenols in the polycarbonate polyol, it is effective to set the pressure of the polymerization reaction of the polycarbonate polyol to a high vacuum of 1 kPa or less as an absolute pressure, or to perform thin film distillation after the polymerization of the polycarbonate polyol.

  Moreover, the carbonate compound used as a raw material at the time of manufacture may remain in polycarbonate polyol. The residual amount of the carbonate compound in the polycarbonate polyol is not limited, but a smaller amount is preferable, and the upper limit of the weight ratio with respect to the polycarbonate polyol is preferably 5% by weight, more preferably 3% by weight, still more preferably 1% by weight. is there. If the carbonate compound content of the polycarbonate polyol is too large, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit is not particularly limited, but is preferably 0.1% by weight, more preferably 0.01% by weight, and still more preferably 0% by weight.

  Moreover, the polyhydric alcohol used at the time of manufacture may remain in the polycarbonate polyol. The residual amount of the polyhydric alcohol in the polycarbonate polyol is not limited, but is preferably less, preferably 1% by weight or less, more preferably 0.1% by weight or less, and more preferably 0.1% by weight or less. Preferably it is 0.05 weight% or less. When the residual amount of the polyhydric alcohol in the polycarbonate polyol is large, the molecular length of the soft segment site when polyurethane is used may be insufficient, and desired physical properties may not be obtained.

  Further, the polycarbonate polyol may contain cyclic carbonate (cyclic oligomer) by-produced during production. For example, when 1,3-propanediol is used, 1,3-dioxan-2-one or a compound obtained by forming two or more of these molecules into a cyclic carbonate may be produced and contained in the polycarbonate polyol. is there. Since these compounds may cause side reactions in the polyurethane-forming reaction and cause turbidity, the pressure of the polymerization reaction of the polycarbonate polyol is set to a high vacuum of 1 kPa or less as an absolute pressure, or the synthesis of the polycarbonate polyol. It is preferable to remove as much as possible by performing thin film distillation or the like later. The content of these cyclic carbonates contained in the polycarbonate polyol is not limited, but is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less as a weight ratio to the polycarbonate polyol. .

[2. Method for producing polyurethane]
A polyurethane can be produced using the polycarbonate polyol of the present invention.
Hereinafter, the polyurethane produced using the polycarbonate polyol of the present invention is referred to as “the polyurethane of the present invention”.
In the method for producing the polyurethane of the present invention using the polycarbonate polyol of the present invention, known polyurethane reaction conditions for producing a polyurethane are usually used.

For example, the polyurethane of the present invention can be produced by reacting the polycarbonate polyol of the present invention with a polyisocyanate and a chain extender in the range of room temperature to 200 ° C.
Also, the polyurethane polyol of the present invention is produced by first reacting the polycarbonate polyol of the present invention with excess polyisocyanate to produce a prepolymer having an isocyanate group at the terminal, and further increasing the degree of polymerization using a chain extender. Can do.

<2-1. Polyisocyanate>
Examples of the polyisocyanate used for producing polyurethane using the polycarbonate polyol of the present invention include various known polyisocyanate compounds such as aliphatic, alicyclic or aromatic.

  For example, the carboxyl groups of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid were converted to isocyanate groups. Aliphatic diisocyanates such as dimerisocyanate; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1 , 4-bis (isocyanatomethyl) cyclohexane and 1,3-bis (isocyanatomethyl) cyclohex Alicyclic diisocyanates such as ethylene; xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4 '-Biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate Which aromatic diisocyanate. These may be used alone or in combination of two or more.

  Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone are preferable in that the balance of physical properties of the obtained polyurethane is preferable and that a large amount can be obtained industrially at low cost. Diisocyanate is preferred.

<2-2. Chain extender>
The chain extender used in producing the polyurethane of the present invention is a low molecular weight compound having at least two active hydrogens that react with an isocyanate group in the production of a prepolymer having an isocyanate group, which will be described later. And polyamines.

  Specific examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. Linear diols such as 1,10-decanediol and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2 -Ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl Diols having a branched chain such as lu-2-ethyl-1,3-propanediol and dimer diol; Diols having an ether group such as diethylene glycol and propylene glycol; 1,4-cyclohexanediol and 1,4-cyclohexanedi Diols having an alicyclic structure such as methanol and 1,4-dihydroxyethylcyclohexane, diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, and 4,4′-methylenebis (hydroxyethylbenzene); Polyols such as glycerin, trimethylolpropane and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, Liethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2 -Polyamines such as hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis (o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, N, N'-diaminopiperazine; and water Etc.

  These chain extenders may be used alone or in combination of two or more. Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, 4, 4'-diaminodicyclohexylmethane is preferred.

  Moreover, the chain extender in the case of producing the prepolymer having a hydroxyl group described later is a low molecular weight compound having at least two isocyanate groups, specifically <2-1. And polyisocyanates>.

<2-3. Chain terminator>
In producing the polyurethane of the present invention, a chain terminator having one active hydrogen group can be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane.

These chain terminators include aliphatic monools such as methanol, ethanol, propanol, butanol and hexanol having one hydroxyl group, diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having one amino group. And aliphatic monoamines such as morpholine.
These may be used alone or in combination of two or more.

<2-4. Catalyst>
In the polyurethane formation reaction in producing the polyurethane of the present invention, an amine catalyst such as triethylamine, N-ethylmorpholine, triethylenediamine, or an acid catalyst such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, trimethyltin laurate Further, known urethane polymerization catalysts represented by tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate and dioctyltin dineodecanate, and organic metal salts such as titanium compounds can also be used. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

<2-5. Polyols other than the polycarbonate polyol of the present invention>
In the polyurethane formation reaction when producing the polyurethane of the present invention, the polycarbonate polyol of the present invention may be used in combination with other polyols as necessary. Here, the polyol other than the polycarbonate polyol of the present invention is not particularly limited as long as it is used in normal polyurethane production. For example, polyether polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol other than the present invention include Can be mentioned. For example, when used in combination with a polyether polyol, a polyurethane having further improved flexibility, which is a feature of the polycarbonate polyol of the present invention, can be obtained. Here, the weight ratio of the polycarbonate polyol of the present invention to the combined weight of the polycarbonate polyol of the present invention and the other polyol is preferably 70% or more, and more preferably 90% or more. When the weight ratio of the polycarbonate polyol of the present invention is small, there is a possibility that the balance between flexibility and solvent resistance, which are the characteristics of the polycarbonate polyol of the present invention, is lost.

  In the present invention, the above-described polycarbonate polyol of the present invention can be modified for use in the production of polyurethane. As a modification method of the polycarbonate polyol, a method of introducing an ether group by adding an epoxy compound such as ethylene oxide, propylene oxide, or butylene oxide to the polycarbonate polyol, or a polycarbonate lactone with a cyclic lactone such as ε-caprolactone, adipic acid, or succinic acid is used. There is a method of introducing an ester group by reacting with dicarboxylic acid compounds such as sebacic acid and terephthalic acid and ester compounds thereof. Ether modification is preferred for reasons such as handling because the viscosity of the polycarbonate polyol is reduced by modification with ethylene oxide, propylene oxide or the like. In particular, the polycarbonate polyol of the present invention is modified with ethylene oxide or propylene oxide, so that the crystallinity of the polycarbonate polyol is lowered and the flexibility at low temperature is improved. Since the water absorption and moisture permeability of the formed polyurethane are increased, the performance as an artificial leather / synthetic leather may be improved. However, when the addition amount of ethylene oxide or propylene oxide increases, the physical properties such as mechanical strength, heat resistance and solvent resistance of the polyurethane produced using the modified polycarbonate polyol are lowered. -50 wt% is suitable, preferably 5-40 wt%, more preferably 5-30 wt%. In addition, the method of introducing an ester group is preferable for reasons such as handling because the viscosity of the polycarbonate polyol is reduced by modification with ε-caprolactone. The amount of ε-caprolactone added to the polycarbonate polyol is preferably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. When the added amount of ε-caprolactone exceeds 50% by weight, the hydrolysis resistance, chemical resistance and the like of the polyurethane produced using the modified polycarbonate polyol are lowered.

<2-6. Solvent>
A solvent may be used for the polyurethane formation reaction in producing the polyurethane of the present invention.
Preferred solvents include amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ketone solvents such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; tetrahydrofuran, dioxane and the like. Examples include ether solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents may be used alone or as a mixed solvent of two or more.

Among these, preferred organic solvents are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
Moreover, the polyurethane of an aqueous dispersion can also be manufactured from the polyurethane composition by which the polycarbonate polyol of this invention, polydiisocyanate, and the said chain extender were mix | blended.

<2-7. Polyurethane production method>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagent, a production method generally used experimentally or industrially can be used.
Examples thereof include the polycarbonate polyol of the present invention, polyols other than the polycarbonate polyol of the present invention used as necessary (hereinafter sometimes referred to as “other polyols”), polyisocyanate and chain extender. A method of mixing and reacting (hereinafter sometimes referred to as “one-step method”), or after first preparing a prepolymer having isocyanate groups at both ends by reacting the polycarbonate polyol of the present invention, other polyols and polyisocyanate. And a method of reacting the prepolymer with a chain extender (hereinafter sometimes referred to as “two-stage method”).

  In the two-stage method, the polycarbonate polyol of the present invention and other polyol are reacted in advance with one or more equivalents of a polyisocyanate to prepare a part of both-end isocyanate intermediate corresponding to the soft segment of polyurethane. It is. In this way, once the prepolymer is prepared and reacted with the chain extender, it may be easy to adjust the molecular weight of the soft segment part, and when it is necessary to ensure phase separation of the soft segment and the hard segment. Is useful.

<2-8. 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 the polycarbonate polyol of the present invention, other polyols, polyisocyanate and a chain extender all at once.

The amount of polyisocyanate used in the one-step method is not particularly limited, but the total number of hydroxyl groups of the polycarbonate polyol of the present invention and other polyols, and the total number of hydroxyl groups and amino groups of the chain extender is 1 equivalent. The lower limit is preferably 0.5 equivalents, more preferably 0.6 equivalents, still more preferably 0.7 equivalents, particularly preferably 0.8 equivalents, and the upper limit is preferably 2.0 equivalents, more preferably 1.5 equivalents, more preferably 1.2 equivalents, particularly preferably 1.0 equivalents.
In addition, the equivalent ratio of the total value of the total isocyanate groups derived from the raw materials used and the total number of hydroxyl groups and total amino groups may be described as the NCO / OH ratio.

  If the amount of polyisocyanate used is too large, unreacted isocyanate groups will cause side reactions, and the resulting polyurethane will have too high a viscosity, making it difficult to handle and tending to reduce flexibility. If it is too high, the molecular weight of the polyurethane will not be sufficiently large, and there will tend to be insufficient polyurethane strength and solvent resistance.

  The amount of the chain extender is not particularly limited, but when the number obtained by subtracting the total number of hydroxyl groups of the polycarbonate polyol of the present invention and other polyols from the number of isocyanate groups of the polyisocyanate is 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, still more preferably Is 1.5 equivalents, particularly preferably 1.1 equivalents. If the amount of chain extender used is too large, the resulting polyurethane tends to be difficult to dissolve in the solvent and difficult to process. If too small, the resulting polyurethane is too soft and has sufficient strength, hardness, elastic recovery performance and elasticity. There is a case where the holding performance cannot be obtained or the heat resistance is deteriorated.

<2-9. Two-stage method>
The two-stage method is also called a prepolymer method, and mainly includes the following methods.
(A) The polycarbonate polyol of the present invention and other polyols and an excess of polyisocyanate are preliminarily added to the polyisocyanate / (polycarbonate polyol of the present invention and other polyols) in an amount exceeding 1 to 10.0 or less. To produce a prepolymer having a molecular chain terminal that is an isocyanate group, and then adding a chain extender thereto to produce a polyurethane.
(B) A polyisocyanate, an excess of the polycarbonate polyol of the present invention and other polyol, and a reaction equivalent ratio of polyisocyanate / (polycarbonate polyol of the present invention and other polyol) of from 0.1 to less than 1.0 To produce a prepolymer having a hydroxyl group at the molecular chain end, and then reacting a polyisocyanate having an isocyanate group at the end as a chain extender to produce a polyurethane.

The two-stage method can be carried out without a solvent or in the presence of a solvent.
The polyurethane production by the two-stage method can be carried out by any of the methods (1) to (3) described below.
(1) Without using a solvent, first, a polyisocyanate, a polycarbonate polyol of the present invention and another polyol are reacted directly to synthesize a prepolymer, which is used as it is for a chain extension reaction.
(2) A prepolymer is synthesized by the method of (1), then dissolved in a solvent, and used for the subsequent chain extension reaction.
(3) Using a solvent from the beginning, the polyisocyanate, the polycarbonate polyol of the present invention and another polyol are reacted, and then a chain extension reaction is performed.

  In the case of the method (1), in the chain extension reaction, the polyurethane coexists with the solvent by dissolving the chain extender in the solvent or simultaneously dissolving the prepolymer and the chain extender in the solvent. It is important to get in.

  The amount of polyisocyanate used in the method of the two-stage method (a) is not particularly limited, but the lower limit of the number of isocyanate groups when the number of total hydroxyl groups of the polycarbonate polyol of the present invention and other polyols is 1 equivalent. Is preferably more than 1.0 equivalent, more preferably 1.2 equivalent, still more preferably 1.5 equivalent, and the upper limit is preferably 10.0 equivalent, more preferably 5.0 equivalent, still more preferably 3 A range of 0.0 equivalents.

  If the amount of isocyanate used is too large, there will be a tendency for excess isocyanate groups to cause side reactions and it will be difficult to reach the desired properties of polyurethane, and if it is too small, the molecular weight of the resulting polyurethane will not increase sufficiently and the strength and heat stability will be increased. May be low.

  The amount of chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and even more preferably 0 with respect to several equivalents of isocyanate groups contained in the prepolymer. 0.8 equivalent, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and still more preferably 2.0 equivalents.

  When performing the chain extension reaction, monofunctional organic amines or alcohols may coexist for the purpose of adjusting the molecular weight.

  The amount of polyisocyanate used in preparing the prepolymer having a hydroxyl group at the end in the two-step method (b) is not particularly limited, but the number of total hydroxyl groups of polycarbonate polyol and other polyols is 1 equivalent. As the number of isocyanate groups, the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0. .98 equivalents, more preferably 0.97 equivalents.

  If the amount of isocyanate used is too small, the process until obtaining the desired molecular weight in the subsequent chain extension reaction tends to be long and production efficiency tends to decrease.If the amount is too large, the viscosity becomes too high and the flexibility of the polyurethane obtained is too high. In some cases, the productivity may be lowered or the productivity may be poor.

  The amount of the chain extender is not particularly limited, but when the number of total hydroxyl groups of the polycarbonate polyol and other polyols used in the prepolymer is 1 equivalent, the total equivalent of the equivalent of the isocyanate group used in the prepolymer is added. The lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99 equivalents, still more preferably The range is 0.98 equivalent.

  When performing the chain extension reaction, monofunctional organic amines or alcohols may coexist for the purpose of adjusting the molecular weight.

  The chain extension reaction is usually carried out at 0 ° C. to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, etc., and is not particularly limited. If the temperature is too low, the progress of the reaction may be delayed, or the production time may be prolonged due to low solubility of the raw materials and the polymer, and if it is too high, side reactions and decomposition of the resulting polyurethane may occur. . The chain extension reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added to chain extension reaction as needed.
Examples of the catalyst include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one kind may be used alone, or two or more kinds may be used. You may use together. Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N, N′-di-2-naphthyl-1,4-phenylenediamine, tris (dinonylphenyl) phosphite, and the like. These compounds may be used, and one kind may be used alone, or two or more kinds may be used in combination. In the case where the chain extender is highly reactive such as a short chain aliphatic amine, the reaction may be carried out without adding a catalyst.

<2-10. Water-based polyurethane emulsion>
It is also possible to produce an aqueous polyurethane emulsion using the polycarbonate polyol of the present invention.

  In that case, when a prepolymer is produced by reacting a polyol containing the polycarbonate polyol of the present invention with an excess of polyisocyanate, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is used. A prepolymer is formed by mixing, and a water-based polyurethane emulsion is obtained through a neutralization chlorination step of hydrophilic functional groups, an emulsification step by addition of water, and a chain extension reaction step.

  The hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used here is, for example, a carboxyl group or a sulfonic acid group, and can be neutralized with an alkaline group. It is a basic group. The isocyanate-reactive group is a group that generally reacts with isocyanate to form a urethane bond or a urea bond, such as a hydroxyl group, a primary amino group, or a secondary amino group, and these are mixed in the same molecule. It does not matter.

  Specific examples of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2′-dimethylolpropionic acid, 2,2-methylolbutyric acid, 2,2 ′. -Dimethylol valeric acid etc. are mentioned. Further, diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid and the like can also be mentioned. These may be used alone or in combination of two or more. When these are actually used, they are used after neutralizing with an amine such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine or triethanolamine, or an alkaline compound such as sodium hydroxide, potassium hydroxide or ammonia. be able to.

  When an aqueous polyurethane emulsion is produced, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is used in order to increase the dispersion performance in water. Preferably it is 1 weight% with respect to the total weight of a polycarbonate polyol and another polyol, More preferably, it is 5 weight%, More preferably, it is 10 weight%. On the other hand, if too much is added, the properties of the polycarbonate polyol of the present invention may not be maintained, so the upper limit is preferably 50% by weight, more preferably 40% by weight, still more preferably 30% by weight. It is.

  In the case of producing an aqueous polyurethane emulsion, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone or N-methyl-2-pyrrolidone in the prepolymer process, or may be carried out without a solvent. Moreover, when using a solvent, after manufacturing an aqueous | water-based emulsion, it is preferable to distill a solvent off by distillation.

  When the water-based polyurethane emulsion is produced in the absence of a solvent using the polycarbonate polyol of the present invention as the raw material, the upper limit of the number average molecular weight determined from the hydroxyl value of the polycarbonate polyol is preferably 5000, more preferably 4500, and still more preferably 4000. . The lower limit of the number average molecular weight is preferably 300, more preferably 500, and still more preferably 800. When the number average molecular weight obtained from the hydroxyl value exceeds 5000 or becomes smaller than 300, emulsification may be difficult.

  Anionic surfactants typified by higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oil, sulfosuccinates, etc., in the synthesis or storage of aqueous polyurethane emulsions , Cationic surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, or known ethylene oxide and long-chain fatty alcohols or phenols Emulsion stability may be maintained by using a nonionic surfactant or the like typified by a reaction product.

  In addition, when preparing a water-based polyurethane emulsion, water is mechanically mixed under high shear in the presence of an emulsifier in the presence of an emulsifier in a prepolymer organic solvent solution, if necessary, to produce an emulsion. You can also

  The water-based polyurethane emulsion thus produced can be used for various applications. In particular, recently, there has been a demand for chemical raw materials with a small environmental load, and it is possible to replace conventional products for the purpose of using no organic solvent.

  As a specific use of the water-based polyurethane emulsion, for example, use in coating agents, water-based paints, adhesives, synthetic leather, and artificial leather is preferable. In particular, the water-based polyurethane emulsion produced using the polycarbonate polyol of the present invention has a structural unit derived from oxyalkylene glycol (A1) in the polycarbonate polyol, so that it is flexible and effective as a coating agent or the like. It is possible to use.

<2-11. Additives>
The polyurethane of the present invention produced using the polycarbonate polyol of the present invention includes a heat stabilizer, a light stabilizer, a colorant, a filler, a stabilizer, an ultraviolet absorber, an antioxidant, an anti-tacking agent, a flame retardant, and aging. Various additives such as an inhibitor and an inorganic filler can be added and mixed as long as the properties of the polyurethane of the present invention are not impaired.

  Compounds that can be used as heat stabilizers include phosphoric acid, phosphorous acid aliphatic, aromatic or alkyl group-substituted aromatic esters and hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkyl Phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, thiodipropionic acid esters, etc. Compounds containing sulfur; tin compounds such as tin malate and dibutyltin monoxide can be used.

Specific examples of the hindered phenol compound include “Irganox 1010” (trade name: manufactured by BASF Japan Ltd.), “Irganox 1520” (trade name: manufactured by BASF Japan Ltd.), “Irganox 245” (trade name: manufactured by BASF Japan Ltd.). ) And the like.
Examples of phosphorus compounds include “PEP-36”, “PEP-24G”, “HP-10” (all trade names: manufactured by ADEKA Corporation), “Irgafos 168” (trade name: manufactured by BASF Japan Corporation), and the like. Is mentioned.
Specific examples of the sulfur-containing compound include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).

  Examples of the light stabilizer include benzotriazole-based compounds, benzophenone-based compounds, and the like. Specifically, “TINUVIN 622LD”, “TINUVIN 765” (manufactured by Ciba Specialty Chemicals Co., Ltd.), “SANOL LS-2626”. "SANOL LS-765" (manufactured by Sankyo Co., Ltd.) or the like can be used.

  Examples of the ultraviolet absorber include “TINUVIN 328” and “TINUVIN 234” (manufactured by Ciba Specialty Chemicals Co., Ltd.).

  Examples of the colorant include direct dyes, acid dyes, basic dyes, metal complex dyes and the like; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; and coupling azo series, condensed azo series, And organic pigments such as anthraquinone, thioindigo, dioxazone, and phthalocyanine.

  Examples of the inorganic filler include short glass fiber, carbon fiber, alumina, talc, graphite, melamine, and clay.

  Examples of the flame retardant include phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like, and reactive flame retardants.

  These additives may be used alone or in combination of two or more in any combination and ratio.

  The lower limit of the additive amount of these additives is preferably 0.01% by weight, more preferably 0.05% by weight, still more preferably 0.1% by weight, and the upper limit is preferably 10% by weight with respect to the polyurethane. % By weight, more preferably 5% by weight, still more preferably 1% by weight. If the amount of the additive added is too small, the effect of the addition cannot be sufficiently obtained, and if it is too large, it may precipitate in the polyurethane or generate turbidity.

<2-12. Polyurethane Film / Polyurethane Plate>
When a film is produced using the polyurethane of the present invention, the lower limit of the thickness of the film is preferably 10 μm, more preferably 20 μm, still more preferably 30 μm, and the upper limit is preferably 1000 μm, more preferably 500 μm, still more preferably. Is 100 μm.
If the film is too thick, sufficient moisture permeability tends not to be obtained, and if it is too thin, pinholes are formed or the film tends to be blocked and difficult to handle.

<2-13. Molecular weight>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited, but is 50,000 to 500,000 as a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC). It is preferable that it is 100,000 to 300,000. If Mw is smaller than the lower limit, sufficient strength and hardness may not be obtained. If Mw is larger than the upper limit, handling properties such as workability tend to be impaired. In particular, by using the polycarbonate polyol of the present invention, a polyurethane having an Mw of 100,000 or more can be easily produced due to its excellent reactivity, and sufficient mechanical strength can be obtained.

<2-14. Solvent resistance>
<2-14-1. Olein resistance>
The polyurethane of the present invention has a rate of change in the weight of the polyurethane test piece after being immersed in oleic acid with respect to the weight of the polyurethane test piece before being immersed in oleic acid, for example, in the evaluation by the method described in the Examples section below. (%) Is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, particularly preferably 4% or less, and most preferably 3% or less.
If the weight change rate exceeds the upper limit, sufficient oleic acid resistance may not be obtained.

<2-14-2. Ethanol resistance>
The polyurethane of the present invention is, for example, evaluated by the method described in the Examples section below, and the change rate (%) of the weight of the polyurethane test piece after being immersed in ethanol relative to the weight of the polyurethane test piece before being immersed in ethanol. ) Is preferably 20% or less, more preferably 18% or less, still more preferably 15% or less, particularly preferably 10% or less, and most preferably 8% or less.
If the weight change rate exceeds the upper limit, sufficient ethanol resistance may not be obtained.

<2-14-3. Ethyl acetate resistance>
The polyurethane of the present invention has a rate of change in the weight of the polyurethane test piece after being immersed in a chemical with respect to the weight of the polyurethane test piece before being immersed in ethyl acetate (e.g., in the evaluation by the method described in the Examples section below). %) Is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less.
If the weight change rate exceeds the upper limit, desired chemical resistance may not be obtained.

<2-15. Tensile breaking elongation>
The polyurethane of the present invention was measured on a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of about 50 to 100 μm at a temperature of 23 ° C. and a relative humidity of 50% at a chuck distance of 50 mm and a tensile speed of 500 mm / min. The tensile elongation at break and the breaking strength are preferably in the following ranges.
That is, the lower limit of the elongation at break is preferably 150%, more preferably 200%, still more preferably 300%, and the upper limit is preferably 3000%, more preferably 2000%, still more preferably 1500%. If the elongation at break is less than the above lower limit, handling properties such as workability tend to be impaired, and if it exceeds the upper limit, sufficient solvent resistance may not be obtained.
Further, the lower limit of the breaking strength is preferably 1.0 MPa, more preferably 2.0 MPa, still more preferably 3.0 MPa, and the upper limit is preferably 100 MPa, more preferably 8.0 MPa, still more preferably 6.0 MPa. . If the breaking strength is less than the above lower limit, handling properties such as workability tend to be impaired, and if it exceeds the upper limit, flexibility may be impaired.

<2-16. 100% and 300% modulus>
The polyurethane of the present invention is a one-stage process under the condition that the total of 4,4′-diphenylmethane diisocyanate and 1,4-butanediol is 17 to 20% by weight based on the total polyurethane amount with respect to the polycarbonate polyol of the present invention. When polyurethane was obtained by reaction, a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of about 50 to 100 μm was measured at a temperature of 23 ° C. and a relative humidity of 50 at a distance between chucks of 50 mm and a tensile speed of 500 mm / min. The 100% modulus and 300% modulus measured in% are preferably in the following ranges.
That is, the lower limit of the 100% modulus is preferably 0.7 MPa, more preferably 0.9 MPa, still more preferably 1.0 MPa, and the upper limit is preferably 20 MPa, more preferably 10 MPa, still more preferably 5.0 MPa. . If the 100% modulus is less than the above lower limit, the solvent resistance may not be sufficient, and if it exceeds the upper limit, flexibility tends to be insufficient or handling properties such as workability tend to be impaired.
The lower limit of the 300% modulus is preferably 1.4 MPa, more preferably 2.0 MPa, still more preferably 2.5 MPa, and the upper limit is preferably 15 MPa, more preferably 9.0 MPa, and still more preferably 6.0 MPa. It is. If the 300% modulus is less than the above lower limit, the solvent resistance may not be sufficient, and if it exceeds the upper limit, flexibility tends to be insufficient, and handling properties such as workability tend to be impaired.

<2-17. Glass transition temperature>
The lower limit of the glass transition temperature of the polyurethane of the present invention is usually −70 ° C. or higher, preferably −60 ° C. or higher, more preferably −50 ° C. or higher, and further preferably −40 ° C. or higher. A temperature of −30 ° C. or higher is particularly preferable. The upper limit is usually 0 ° C. or lower, preferably −5 ° C. or lower, more preferably −10 ° C. or lower, still more preferably −15 ° C. or lower, and −20 ° C. or lower. Is particularly preferred. When the glass transition temperature of the polyurethane is not less than the above lower limit, the solvent resistance is good, and since it is not more than the above upper limit, it tends to be prevented from becoming hard at a low temperature and to improve the touch feeling.

<2-18. Application>
The polyurethane of the present invention is excellent in solvent resistance and has good flexibility and mechanical strength, so that foam, elastomer, elastic fiber, paint, fiber, pressure-sensitive adhesive, adhesive, flooring, sealant, medical material, It can be widely used for artificial leather, synthetic leather, coating agent, water-based polyurethane paint, active energy ray-curable polymer composition and the like.

  In particular, when the polyurethane of the present invention is used in applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc., solvent resistance, flexibility, mechanical strength Because it has a good balance, it is highly durable in areas where it touches human skin and where cosmetic drugs and alcohol for disinfection are used, and it is flexible enough for physical impact. A good characteristic of being strong can be imparted. Further, it can be suitably used for automotive applications that require heat resistance and outdoor applications that require weather resistance.

  The polyurethane of the present invention can be used as a cast polyurethane elastomer. Specific applications include rolling rolls, papermaking rolls, office equipment, rolls such as pre-tension rolls, forklifts, solid tires for automobile vehicles, trams, carts, etc., casters, industrial products such as conveyor belt idlers, guides There are rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, and cyclone liners. It can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, surferers, and the like.

  The polyurethane of the present invention is also applied for use as a thermoplastic elastomer. For example, it can be used for 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. Moreover, it is used for various power transmission mechanisms, spinning machines, packing equipment, printing machines and the like as belts such as round belts, V belts, and flat belts. Also, it can be used for 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. In addition, it can be used for films such as keyboard films and automobile films, curl cords, cable sheaths, bellows, transport belts, flexible containers, binders, synthetic leather, depinning products, adhesives, and the like.

  The polyurethane of 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. Moreover, it can be used for automobile repair as tar epoxy urethane.

  The polyurethane of the present invention can be used as a component of a moisture-curable one-component paint, a blocked isocyanate solvent paint, an alkyd resin paint, a urethane-modified synthetic resin paint, an ultraviolet curable paint, a water-based urethane paint, etc. Paints for plastic bumpers, strippable paints, magnetic tape coatings, floor tiles, flooring materials, overprint varnishes for paper, wood grain printing films, wood varnishes, coil coils for high processing, optical fiber protective coatings, solder resists, metals It can be applied to a top coat for printing, a base coat for vapor deposition, a white coat for food cans, and the like.

  The polyurethane of the present invention can also be applied to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. as adhesives and adhesives, and as low temperature adhesives and hot melt components Can also be used.

  The polyurethane of the present invention can be used as a binder for magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular agricultural chemicals, polymer cement mortars, resin mortars, rubber chip binders, recycled foams, glass fiber sizing, etc. It can be used.

The polyurethane of 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.
When the polyurethane of the present invention is used as an elastic fiber, the fiberizing method can be carried out without any limitation as long as it can be spun. For example, a melt spinning method in which the pellets are once pelletized, melted, and directly spun through a spinneret can be employed. When elastic fibers are obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250 ° C. or lower, more preferably 200 ° C. or higher and 235 ° C. or lower.

  The polyurethane elastic fiber of the present invention can be used as a bare yarn as it is, or can be coated with another fiber and used as a coated yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers. Among them, polyester fibers are preferably used in the present invention. The polyurethane elastic fiber of the present invention may contain a dyeing type disperse dye.

  The polyurethane of the present invention is used as a sealant caulking, such as a concrete wall, induction joint, sash area, wall-type PC (Precast Concrete) joint, ALC (Autoclaved Light-weight Concrete) joint, board joint, composite glass sealant, It can be used for heat insulating sash sealants, automotive sealants, etc.

The polyurethane of 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, a tube, a bag, and a surgical glove. It can be used for artificial kidney potting materials.
The polyurethane of the present invention can be used as a raw material for UV curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating materials, etc. by modifying the ends. it can.

<2-19. Urethane (meth) acrylate oligomer>
A urethane (meth) acrylate oligomer can be produced by addition reaction of polyisocyanate and hydroxyalkyl (meth) acrylate using the polycarbonate polyol of the present invention. When the other raw material polyol, the chain extender, etc. are used in combination, the urethane (meth) acrylate oligomer can be produced by addition reaction of these other raw material compounds with polyisocyanate. .
In the present invention, when “(meth) acryl” is displayed like (meth) acrylate or (meth) acrylic acid, it means acrylic and / or methacrylic.

In addition, the charging ratio of each raw material compound at that time is substantially equal to or the same as the composition of the target urethane (meth) acrylate oligomer.
The amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar in theory.

  When producing urethane (meth) acrylate oligomers, the amount of hydroxyalkyl (meth) acrylate used is determined based on the amount of hydroxyalkyl (meth) acrylate, polycarbonate polyol, and other raw material compounds used as needed, and It is usually 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and usually 70 mol% or less, preferably 50 mol based on the total amount of the compound containing a functional group that reacts with isocyanate such as a chain extender. % Or less. According to this ratio, the molecular weight of the urethane (meth) acrylate oligomer obtained can be controlled. When the proportion of hydroxyalkyl (meth) acrylate is large, the molecular weight of the urethane (meth) acrylate oligomer tends to be small, and when the proportion is small, the molecular weight tends to be large.

  The amount of polycarbonate polyol used is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more with respect to the total amount of polycarbonate polyol and polyol used. It is preferable that the amount of the polycarbonate polyol used is equal to or more than the above lower limit value because the resulting cured product tends to have good hardness and stain resistance.

  Further, the amount of polycarbonate polyol used is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, particularly preferably based on the total amount of polycarbonate polyol and polyol used. Is 70% by weight or more. When the amount of the polycarbonate polyol used is not less than the above lower limit, the viscosity of the resulting composition is lowered and the workability is improved, and the mechanical strength, hardness and wear resistance of the resulting cured product tend to be improved. It is preferable.

  Furthermore, it is preferable that the usage-amount of a polycarbonate polyol shall be 25 mol% or more with respect to the total usage-amount of a polycarbonate polyol and a polyol, More preferably, it is 50 mol% or more, More preferably, it is 70 mol% or more. It is preferable that the amount of the polycarbonate polyol used is equal to or more than the lower limit because the elongation and weather resistance of the resulting cured product tend to be improved.

  Furthermore, when a chain extender is used, the amount of polyol used is preferably 70 mol% or more, more preferably 80 mol%, based on the total amount of polycarbonate polyol and the combined compound of polyol and chain extender. Above, more preferably 90 mol% or more, particularly preferably 95 mol% or more. When the amount of polyol is not less than the above lower limit, the liquid stability tends to be improved, which is preferable.

  In the production of the urethane (meth) acrylate oligomer, a solvent can be used for the purpose of adjusting the viscosity. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can be used usually in an amount of less than 300 parts by weight with respect to 100 parts by weight of the solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer, the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compound is preferably 20% by weight or more based on the total amount of the reaction system, and is 40% by weight. % Or more is more preferable. The upper limit of the total content is 100% by weight. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compound to be 20% by weight or more because the reaction rate tends to increase and the production efficiency tends to improve.

  An addition reaction catalyst can be used in the production of the urethane (meth) acrylate oligomer. Examples of the addition reaction catalyst include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. An addition reaction catalyst may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, the addition reaction catalyst is preferably dioctyltin dilaurate from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

  The addition reaction catalyst has an upper limit of usually 1000 ppm by weight, preferably 500 ppm by weight, and a lower limit of usually 10 ppm by weight, preferably relative to the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Used at 30 ppm by weight.

  Further, when the reaction system contains a (meth) acryloyl group during the production of the urethane (meth) acrylate oligomer, a polymerization inhibitor can be used in combination. Examples of such a polymerization inhibitor include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether and dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese such as manganese acetate. Examples thereof include salts, nitro compounds, and nitroso compounds. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor.

  The polymerization inhibitor has an upper limit of usually 3000 ppm, preferably 1000 ppm by weight, particularly preferably 500 ppm by weight, particularly preferably 500 ppm by weight, based on the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Usually, 50 ppm by weight, preferably 100 ppm by weight is used.

  During the production of the urethane (meth) acrylate oligomer, the reaction temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. A reaction temperature of 20 ° C. or higher is preferable because the reaction rate increases and the production efficiency tends to improve. Moreover, reaction temperature is 120 degrees C or less normally, and it is preferable that it is 100 degrees C or less. It is preferable for the reaction temperature to be 120 ° C. or lower because side reactions such as an allohanato reaction hardly occur. When the reaction system contains a solvent, the reaction temperature is preferably lower than the boiling point of the solvent. When (meth) acrylate is contained, the reaction temperature is 70 ° C. from the viewpoint of preventing the reaction of the (meth) acryloyl group. The following is preferable. The reaction time is usually about 5 to 20 hours.

  The number average molecular weight of the urethane (meth) acrylate oligomer thus obtained is preferably 500 or more, particularly preferably 1000 or more, preferably 10,000 or less, particularly 5000 or less, especially 3000 or less. When the number average molecular weight of the urethane (meth) acrylate oligomer is not less than the above lower limit, the resulting cured film has good three-dimensional workability and tends to have an excellent balance between three-dimensional workability and stain resistance. When the number average molecular weight of the urethane (meth) acrylate oligomer is not more than the above upper limit, the cured film obtained from the composition has good contamination resistance and tends to have a good balance between three-dimensional processability and contamination resistance. Therefore, it is preferable. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure, and as this distance increases, the structure becomes flexible and easily stretched, and the three-dimensional workability is superior. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

<2-20. Polyester elastomer>
The polycarbonate polyol of the present invention can be used as a polyester elastomer. The polyester elastomer is a copolymer composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of aliphatic polyether, aliphatic polyester or aliphatic polycarbonate. When the polycarbonate polyol of the present invention is used as a constituent component of the soft segment, physical properties such as heat resistance and water resistance are excellent as compared with the case where an aliphatic polyether or aliphatic polyester is used. Compared to known polycarbonate polyols, it is a polycarbonate ester elastomer with melt flowability, that is, a melt flow rate suitable for blow molding and extrusion molding, and excellent balance with mechanical strength and other physical properties. It can be suitably used for various molding materials including fibers, films and sheets, for example, molding materials such as elastic yarns and boots, gears, tubes and packings. Specifically, it can be effectively applied to applications such as joint boots such as automobiles and home appliance parts that require heat resistance and durability, and wire covering materials.

<2-21. Active energy ray-curable polymer composition>
The active energy ray-curable polymer composition containing the urethane (meth) acrylate oligomer described above (hereinafter sometimes referred to as “the active energy ray-curable polymer composition of the present invention”) will be described.
The active energy ray-curable polymer composition of the present invention preferably has a molecular weight between calculated network crosslinking points of 500 to 10,000.

  In the present specification, the molecular weight between calculated network cross-linking points of the composition is the average molecular weight between active energy ray reactive groups (hereinafter sometimes referred to as “cross-linking points”) that form a network structure in the entire composition. Represents a value. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter, sometimes referred to as “monofunctional compound”) reacts, it becomes a linear polymer, while the active energy A network structure is formed when a compound having two or more linear reactive groups (hereinafter sometimes referred to as “polyfunctional compound”) reacts.

  Therefore, the active energy ray reactive group of the polyfunctional compound is a crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound has the polyfunctional compound. The molecular weight between the crosslinking points is treated as having an effect of extending the molecular weight, and the molecular weight between the calculation network crosslinking points is calculated. In addition, the calculation of the molecular weight between the calculation network crosslinking points is performed on the assumption that all the active energy ray reactive groups have the same reactivity and that all the active energy ray reactive groups react by irradiation with the active energy ray. .

In a polyfunctional compound single-system composition in which only one type of polyfunctional compound reacts, the molecular weight between the calculated network cross-linking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. . For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1,000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.
In a polyfunctional compound mixed system composition in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition is This is the molecular weight between the calculated network crosslinking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1,000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of reactive energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2/20 = 520.

  When a monofunctional compound is included in the composition, a molecule formed by calculation and equimolar to the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound, and the monofunctional compound linked to the crosslinking point Assuming that the reaction takes place in the middle of the chain, the extension of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, and the total active energy ray reaction of the polyfunctional compound in the composition. Half of the value divided by the radix. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition.

For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1,000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the calculated network cross-linking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinking points of the composition is 1000 + 500 = 1500.
From the above, in the mixture of monofunctional compounds M _A molar molecular weight W _A, and f _B functional compound M _B mol molecular weight W _B, and f _C functional compound M _C mol molecular weight W _C, the composition The molecular weight between the calculated network cross-linking points of the product can be expressed by the following formula.

  The molecular weight between the calculated network crosslinking points of the active energy ray-curable polymer composition of the present invention calculated in this way is preferably 500 or more, more preferably 800 or more, and 1,000 or more. More preferably, it is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, and even more preferably 4,000 or less. 3,000 or less is particularly preferable.

  A molecular weight between calculated network crosslinking points of 10,000 or less is preferable because the cured film obtained from the composition has good stain resistance and tends to have a good balance between three-dimensional processability and stain resistance. Moreover, it is preferable that the molecular weight between the calculation network cross-linking points is 500 or more because the obtained cured film has good three-dimensional workability and tends to have an excellent balance between the three-dimensional workability and the stain resistance. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the three-dimensional processability is excellent. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

  The active energy ray-curable polymer composition of the present invention may further contain components other than the urethane (meth) acrylate oligomer. Examples of such other components include an active energy ray reactive monomer, an active energy ray curable oligomer, a polymerization initiator, a photosensitizer, an additive, and a solvent.

  In the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer is 40% by weight or more based on the total amount of active energy ray-reactive components including the urethane (meth) acrylate oligomer. It is preferable that it is 60% by weight or more. In addition, the upper limit of this content is 100 weight%. When the content of the urethane (meth) acrylate oligomer is 40% by weight or more, the curability is good and the three-dimensional workability tends to be improved without excessively increasing the mechanical strength of the cured product. This is preferable.

  Moreover, in the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer is preferably large in terms of elongation and film-forming property, and on the other hand, the viscosity is reduced. In terms of points, a smaller number is preferable. From such a viewpoint, the content of the urethane (meth) acrylate oligomer is preferably 50% by weight or more based on the total amount of all components including other components in addition to the active energy ray-reactive component. 70% by weight or more is more preferable. In addition, the upper limit of content of a urethane (meth) acrylate type oligomer is 100 weight%, and it is preferable that this content is less than that.

  Moreover, in the active energy ray-curable polymer composition of the present invention, the content of the total amount of the active energy ray-reactive component including the urethane (meth) acrylate oligomer depends on the curing rate and surface curability of the composition. From the viewpoint of excellent and no tack remaining, it is preferably 60% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more based on the total amount of the composition. 95% by weight or more is particularly preferable. In addition, the upper limit of this content is 100 weight%.

  Any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer. These active energy ray reactive monomers are used for the purpose of adjusting the hydrophilicity / hydrophobicity of urethane (meth) acrylate oligomers and the physical properties such as hardness and elongation of the cured product when the resulting composition is cured. Is done. An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of such active energy ray reactive monomers include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene. Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate Ester monomers; Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; Allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth) acrylamide, N, N-dimethylacrylamide N, N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine (Meth) acrylamides such as methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl , (Meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Stearyl, tetrahydrofurfuryl (meth) acrylate, (meth) a Morpholyl laurate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate , (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) Monofunctional (meth) acrylic acid such as phenyl acrylate And ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ( n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (meth) Polypropylene glycol acrylate (n = 5-14), di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid polybutylene glycol ( n = 3-16), di (meth) acrylic acid poly Li (1-methylbutylene glycol) (n = 5-20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) acrylic acid Neopentyl glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate , Propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri Black decanedimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate; and the like.

  Among these, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid, especially in applications where coating properties are required. Has a ring structure in the molecule, such as trimethylcyclohexyl, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. Monofunctional (meth) acrylates are preferred. On the other hand, in applications where mechanical strength of the resulting cured product is required, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid-1, 6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) Neopentyl glycol acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

  In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive monomer is selected from the viewpoints of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. It is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less, based on the total amount of the composition.

  The active energy ray-curable oligomer may be used alone or in combination of two or more. Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers.

  In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive oligomer is based on the total amount of the composition from the viewpoint of adjusting physical properties such as hardness and elongation of the obtained cured product. 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

  The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used. A polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together radical photopolymerization initiator and a photosensitizer.

  Examples of the photo radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ] 2-Methyl-propan-1-one is more preferred.

  In addition, when the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radical polymerizable group, as a polymerization initiator, a photocation together with the above-mentioned photo radical polymerization initiator. A polymerization initiator may be included. Any known cationic photopolymerization initiator can be used.

  The content of these polymerization initiators in the active energy ray-curable polymer composition of the present invention is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components, More preferably, it is 5 parts by weight or less. It is preferable for the content of the polymerization initiator to be 10 parts by weight or less because the mechanical strength is not easily lowered by the initiator decomposition product.

  The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types. As the photosensitizer, any known photosensitizer can be used as long as the effects of the present invention are obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, And 4-dimethylaminoacetophenone.

  In the active energy ray-curable polymer composition of the present invention, the content of the photosensitizer is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components. More preferably, it is 5 parts by weight or less. When the content of the photosensitizer is 10 parts by weight or less, it is preferable that the mechanical strength does not decrease due to the decrease in the crosslinking density.

  The said additive is arbitrary and can use the various materials added to the composition used for the same use as an additive. An additive may be used individually by 1 type, and 2 or more types may be mixed and used for it. Examples of such additives include glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, and metal powder. Fillers such as carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as “inorganic components”); Agent, heat stabilizer, UV absorber, HALS (hindered amine light stabilizer), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, Anti-settling agents, surfactants, thixotropy imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents and other modifiers; pigments, dyes, hue adjustments Colorants and the like; and, monomer and / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts, curing accelerators like; and the like.

  In the active energy ray-curable polymer composition of the present invention, the content of the additive is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components. It is more preferable that the amount is not more than parts by weight. It is preferable for the content of the additive to be 10 parts by weight or less because it is difficult for the mechanical strength to decrease due to a decrease in crosslink density.

  The solvent is used for the purpose of adjusting the viscosity of the active energy ray-curable polymer composition of the present invention, for example, depending on the coating method for forming the coating film of the active energy ray-curable polymer composition of the present invention. Can be used. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used as long as the effects of the present invention are obtained. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. A solvent can be normally used in less than 200 weight part with respect to 100 weight part of solid content of an active energy ray curable polymer composition.

  There are no particular limitations on the method of incorporating the active energy ray-curable polymer composition of the present invention into optional components such as the aforementioned additives, and examples thereof include conventionally known mixing and dispersion methods. In addition, in order to disperse | distribute the said arbitrary component more reliably, it is preferable to perform a dispersion | distribution process using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact Examples of the processing method include a mill, a kneader, a homogenizer, and an ultrasonic disperser.

  The viscosity of the active energy ray-curable polymer composition of the present invention can be appropriately adjusted according to the use and usage of the composition, but the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc. From the above, the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, 000 mPa · s or less is preferable, and 50,000 mPa · s or less is more preferable. The viscosity of the active energy ray-curable polymer composition can be adjusted by, for example, the content of the aforementioned urethane (meth) acrylate oligomer, the type of the optional component, the blending ratio thereof, and the like.

  As a coating method of the active energy ray-curable polymer composition of the present invention, a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll coater method Known methods such as a lip coater method, a die coater method, a slot die coater method, an air knife coater method and a dip coater method can be applied. Among them, a bar coater method and a gravure coater method are preferable.

<2-22. Cured film and laminate>
The active energy ray-curable polymer composition of the present invention can be made into a cured film by irradiating this with active energy rays.
As the active energy rays used when the composition is cured, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He—Cd lasers, solid lasers, xenon lamps, high frequency induction mercury lamps, sunlight, and the like are suitable.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when curing is performed by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. Moreover, in the case of ultraviolet irradiation, it is preferable that it is 50-1,000 mJ / cm < ² >. The atmosphere during curing may be air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

  The thickness of the cured film is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, particularly preferably 50 μm. When the film thickness is 1 μm or more, the design properties and functionality after three-dimensional processing are improved, and when it is 200 μm or less, the internal curability and the three-dimensional workability are preferable. In industrial use, the lower limit of the thickness of the cured film is preferably 1 μm, and the upper limit is preferably 100 μm, more preferably 50 μm, particularly preferably 20 μm, and most preferably 10 μm.

  A laminate having a layer made of the above cured film can be obtained on a substrate. This laminate is not particularly limited as long as it has a layer made of a cured film, and may have a layer other than the substrate and the cured film between the substrate and the cured film, or on the outside thereof. You may have. Moreover, the said laminated body may have multiple layers of a base material and a cured film.

  As a method of obtaining a laminate having a multi-layer cured film, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured. Apply a known method such as applying the upper layer and curing again with active energy rays, or applying each layer to the release film or base film and then laminating the layers in an uncured or semi-cured state. Although possible, a method of curing with an active energy ray after laminating in an uncured state is preferable from the viewpoint of improving adhesion between layers. As a method of laminating in an uncured state, a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.

Examples of the base material include various shapes such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate, and (meth) acrylic resin, or plates formed of metal. The article is mentioned.
The cured film can be a film excellent in stain resistance and hardness against general household contaminants such as ink and ethanol, and the laminate using the cured film as a coating on various substrates has a design property and surface. It can be excellent in protection.

In addition, the active energy ray-curable polymer composition of the present invention is capable of following deformation during three-dimensional processing, taking into account the molecular weight between the calculation network cross-linking points, elongation at break, mechanical strength, contamination resistance. A cured film having both properties and hardness can be provided.
Moreover, it is expected that the active energy ray-curable polymer composition of the present invention can easily produce a thin film-like resin sheet by single-layer coating.

  The breaking elongation of the cured film was determined by cutting the cured film to a width of 10 mm and using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100) at a temperature of 23 ° C., a tensile speed of 50 mm / min, between chucks. The value measured by performing a tensile test under the condition of a distance of 50 mm is preferably 50% or more, more preferably 75% or more, still more preferably 100% or more, and 120% or more. Is particularly preferred.

  The above-mentioned cured film and laminate can be used as a coating substitute film, and can be effectively applied to, for example, interior / exterior building materials, various members of automobiles, home appliances, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.

[Evaluation method]
The conditions of the polycondensation step in the following examples and comparative examples, and the evaluation methods of the obtained polycarbonate polyol and polyurethane are as follows.

[Polycondensation step]
<Dioxane generation amount>
The polycarbonate polyol-containing composition produced by the polycondensation reaction and the distillate were quantitatively analyzed by gas chromatography (GC), and the ratio (% by weight) relative to the charged diethylene glycol was calculated.

[Evaluation of polycarbonate polyol]
<Quantification of carbonate terminal amount, diol, branched alcohol content and phenol content>
Polycarbonate polyol was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) was measured. From the signal position of each component, the terminal amount of carbonate such as phenoxy group, diol, branched alcohol and phenol were determined. Each content was calculated from the integrated value. In this case, the detection limit is 100 ppm as the weight of phenol with respect to the weight of the whole sample, and the compound represented by the formula (A) and the dihydroxy compound such as the compound represented by the formula (B) are 0.1% by weight. is there. Further, the proportion of the carbonate terminal amount such as phenoxy group is obtained from the ratio of the integral value of one proton of the carbonate terminal amount of phenoxy group and the integral value of one proton of the whole terminal. The detection limit is 0.1 mol% with respect to the whole terminal. When diethyl carbonate was used, ethoxy group (EtO-) was calculated, and when ethylene carbonate was used, hydroxyethoxy group (HOCH ₂ CH ₂ O-) was calculated in the same manner.

<Content (% by weight) of oxyalkylene glycol (A1)>
The content ratio (% by weight) of the oxyalkylene glycol (A1) in the diol (A) is determined as follows by performing GC analysis after hydrolysis of the polycarbonate polyol.
0.5 g of polycarbonate polyol was precisely weighed and placed in a 100 mL Erlenmeyer flask, and 5 mL of tetrahydrofuran was added and dissolved. Next, 45 mL of methanol and 5 mL of a 25 wt% aqueous sodium hydroxide solution were added. A condenser was set in a 100 mL Erlenmeyer flask and heated in a water bath at 75 to 80 ° C. for 30 minutes for hydrolysis. After allowing to cool at room temperature, 5 mL of 6N hydrochloric acid was added to neutralize sodium hydroxide, and the pH was adjusted to 2-4. The whole amount was transferred to a 100 mL volumetric flask, the inside of the Erlenmeyer flask was washed twice with an appropriate amount of methanol, and the washing solution was also transferred to the 100 mL volumetric flask. After adding an appropriate amount of methanol to 100 mL, the liquid was mixed in a volumetric flask. The supernatant was collected, filtered through a filter, and then analyzed by GC. For the concentration of each diol contained in the diol (A), a calibration curve was prepared from the standard substance, and the weight percentage was calculated from the area ratio obtained by GC.

<Molar ratio of structural unit derived from oxyalkylene glycol (A1) and structural unit derived from branched alcohol (B)>
Was dissolved polycarbonate polyols ^{_{CDCl 3, 400MHz, 1 H-}} NMR was measured (JEOL Ltd. AL-400), from the signal position of each component, branched alcohol structural unit derived from the oxyalkylene glycol (A1) The molar ratio with the structural unit derived from (B) was determined. The molar ratio between the terminal derived from the oxyalkylene glycol (A1) and the terminal derived from the branched alcohol (B) was determined in the same manner.

<Hydroxyl value>
Based on JIS K1557-1, the hydroxyl value of the polycarbonate polyol was measured by a method using an acetylating reagent.

<Measurement of APHA value>
In accordance with JIS K0071-1 (1998), the measurement was performed in comparison with a standard solution in which a polycarbonate polyol was placed in a colorimetric tube. As a reagent, a chromaticity standard solution of 1000 degrees (1 mg Pt / mL) (Kishida Chemical) was used.

[Evaluation of polyurethane]
<Solvent resistance>
The polyurethane solution was applied on a fluororesin sheet (fluorine tape nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) with a 9.5 mil applicator, and 5 hours at 50 ° C., 0.5 hours at 100 ° C., It dried in order of 0.5 hour at 100 degreeC of vacuum conditions, and 15 hours at 80 degreeC. A 3 cm × 3 cm test piece was cut out from the obtained polyurethane film, put into a glass petri dish with an inner diameter of 10 cmφ containing 50 mL of the test solvent, and the weight of each test solvent after immersion for the following time at the following temperature was measured. The weight change rate (%) between the weight of the test piece before immersion and the weight of the test piece after immersion (= (weight of the test piece after immersion−weight of the test piece before immersion) / test before immersion) The weight of the piece × 100) was calculated. Here, the closer the weight change rate is to 0%, the better the oleic acid resistance.
Resistance to oleic acid: The test piece was immersed in oleic acid at 80 ° C. for 16 hours.
Ethyl acetate resistance: The test piece was immersed in ethyl acetate at room temperature for 20 minutes.
Ethanol resistance: The test piece was immersed in ethanol at room temperature for 1 hour.

<Room temperature tensile test>
In accordance with JIS K6301, a polyurethane test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm was chucked using a tensile tester [product name “Tensilon UTM-III-100” manufactured by Orientec Co., Ltd.]. A tensile test was conducted at a distance of 50 mm and a tensile speed of 500 mm / min at a temperature of 23 ° C. (relative humidity 55%), and the stress at each elongation until the test piece broke was measured. The stress at 100% and 300% elongation is assumed to be 100% modulus (100% M) and 300% modulus (300% M).

[Raw materials]
The raw materials used for the production of polycarbonate polyol (hereinafter sometimes abbreviated as PCP) and polyurethane are as follows.
Diethylene glycol (hereinafter sometimes abbreviated as DEG): Triethylene glycol (hereinafter sometimes abbreviated as TEG) manufactured by Mitsubishi Chemical Corporation: Trimethylolpropane (hereinafter abbreviated as TMP) manufactured by Mitsubishi Chemical Corporation :) Mitsubishi Gas Chemical Co., Ltd. 1,6-hexanediol (hereinafter sometimes abbreviated as 16HD): BASF diphenyl carbonate (hereinafter sometimes abbreviated as DPC): Mitsubishi Chemical Corporation diethyl Carbonate (hereinafter sometimes abbreviated as DEC): Wako Pure Chemical Industries, Ltd. Ethylene carbonate (hereinafter sometimes abbreviated as EC): Mitsubishi Chemical Corporation magnesium acetate tetrahydrate (hereinafter, Mg ( OAc) may be abbreviated as :) Wako Pure Chemical Industries, Ltd. Rabtoxide (hereinafter sometimes abbreviated as Ti (OBu)): Wako Pure Chemical Industries, Ltd. Sodium ethoxide (hereinafter sometimes abbreviated as NaOEt): Wako Pure Chemical Industries, Ltd. 1,4- Butanediol: Mitsubishi Chemical Corporation diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI): Nippon Polyurethane Industry Co., Ltd. Urethane catalyst Neostane U-830: Nitto Kasei Co., Ltd. Dehydrated N, N-dimethylformamide: Sum Made by Kojun Pharmaceutical Co., Ltd.

[Production and evaluation of polycarbonate polyol]
<Example I-1>
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 231.8 g, triethylene glycol (TEG): 219.6 g, trimethylolpropane (TMP): 7. 5 g, diphenyl carbonate (DPC): 741.2 g, magnesium acetate tetrahydrate aqueous solution: 1.9 mL (concentration: 8.4 g / L) were added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. The reaction was continued for 15 hours (18.5 hours in total). Thereafter, 0.85% phosphoric acid aqueous solution: 0.45 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC.

The obtained polycarbonate polyol-containing composition was fed to a thin film distillation apparatus at a flow rate of 20 g / min, and thin film distillation (temperature: 200 ° C., pressure: 53 to 67 Pa) was performed. As a thin-film distillation apparatus, an internal condenser having a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m ² and a jacketed Shibata Kagaku Co., Ltd. molecular distillation apparatus MS-300 special type were used.
The evaluation results of the properties and physical properties of the polycarbonate polyol obtained by thin film distillation are shown in Tables 1A and 1B together with the production conditions.

<Example I-2>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 786.1 g, triethylene glycol (TEG): 744.7 g, trimethylolpropane (TMP): 25. 5 g, diphenyl carbonate (DPC): 2525.0 g, magnesium acetate tetrahydrate aqueous solution: 6.3 mL (concentration: 8.4 g / L) were added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. The mixture was reacted for 2 hours (total 5.5 hours) to obtain a polycarbonate polyol-containing composition. 0.85% phosphoric acid aqueous solution: 1.4 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. Then, the same thin film distillation as Example 1 was performed.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 1A and 1B together with the production conditions.

<Example I-3>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 1081.3 g, triethylene glycol (TEG): 383.5 g, trimethylolpropane (TMP): 47. 5 g, diphenyl carbonate (DPC): 2687.8 g, magnesium acetate tetrahydrate aqueous solution: 6.7 mL (concentration: 8.4 g / L) were added, and the nitrogen gas was replaced. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. The mixture was reacted for 2 hours (total 5.5 hours) to obtain a polycarbonate polyol-containing composition. 0.85% phosphoric acid aqueous solution: 1.4 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. Then, the same thin film distillation as Example 1 was performed.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 1A and 1B together with the production conditions.

<Example I-4>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 490.2 g, triethylene glycol (TEG): 462.4 g, diphenyl carbonate (DPC): 1547.4 g Magnesium acetate tetrahydrate aqueous solution: 4.3 mL (concentration: 8.4 g / L) was added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. The mixture was reacted for 2 hours (total 5.5 hours) to obtain a polycarbonate polyol-containing composition. 0.85% phosphoric acid aqueous solution: 1.1 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. Then, the same thin film distillation as Example 1 was performed.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 1A and 1B together with the production conditions.

<Example I-5>
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 166.8 g, trimethylolpropane (TMP): 3.2 g, diphenyl carbonate (DPC): 330.0 g Magnesium acetate tetrahydrate aqueous solution: 0.8 mL (concentration: 8.4 g / L) was added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. Then, after reacting for 2 hours (total 5.5 hours), 0.85% phosphoric acid aqueous solution: 0.45 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 1A and 1B together with the production conditions.

<Example I-6>
Diethylene glycol (DEG): 753.0 g, 1,6-hexanediol (16HD): 462.2 g, trimethylolpropane (TMP) in a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator : 22.5 g, diphenyl carbonate (DPC): 2262.3 g, magnesium acetate tetrahydrate aqueous solution: 5.7 mL (concentration: 8.4 g / L), and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. Then, after reacting for 2 hours (total 5.5 hours), 0.85% phosphoric acid aqueous solution: 1.1 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. Then, the same thin film distillation as Example 1 was performed.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 1A and 1B together with the production conditions.

<Comparative Example I-1>
Diethylene glycol (DEG): 231.7 g, triethylene glycol (TEG): 202.5 g, trimethylol in a 1 L glass separable flask equipped with a stirrer, packed fractionator, distillate trap, and pressure regulator Propane (TMP): 6.9 g, diethyl carbonate (DEC): 577.9 g, titanium tetrabutoxide: 0.23 g were added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 100 ° C., and the contents were dissolved by heating. Thereafter, the reaction was carried out for 20 hours under normal pressure at an internal temperature of 100 to 130 ° C. while removing ethanol and diethyl carbonate (DEC) out of the system. Next, the pressure was decreased to 9.3 kPa over 240 minutes, and the reaction was further performed at 160 ° C. for 10 hours. Furthermore, after continuing the reaction by lowering to 5.0 kPa over 60 minutes, the temperature was raised to 170 ° C., and the reaction was carried out for 10 hours (total 45 hours) while removing ethanol and unreacted dihydroxy compound out of the system. A composition was obtained. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 2A and 2B together with the production conditions.

<Comparative Example I-2>
Diethylene glycol (DEG): 231.7 g, triethylene glycol (TEG): 202.5 g, trimethylol in a 1 L glass separable flask equipped with a stirrer, packed fractionator, distillate trap, and pressure regulator Propane (TMP): 6.9 g, diethyl carbonate (DEC): 577.9 g, sodium ethoxide: 0.19 g were added, and the nitrogen gas was replaced. Under stirring, the internal temperature was raised to 100 ° C., and the contents were dissolved by heating. Thereafter, the reaction was carried out for 20 hours under normal pressure at an internal temperature of 100 to 130 ° C. while removing ethanol and diethyl carbonate (DEC) out of the system. Next, the pressure was decreased to 9.3 kPa over 240 minutes, and the reaction was further performed at 160 ° C. for 10 hours. Furthermore, after continuing the reaction by lowering to 5.0 kPa over 60 minutes, the temperature was raised to 170 ° C., and the reaction was carried out for 10 hours (total 45 hours) while removing ethanol and unreacted dihydroxy compound out of the system. A composition was obtained. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 2A and 2B together with the production conditions.

<Comparative Example I-3>
Diethylene glycol (DEG): 231.7 g, triethylene glycol (TEG): 202.5 g, trimethylol in a 1 L glass separable flask equipped with a stirrer, packed fractionator, distillate trap, and pressure regulator Propane (TMP): 6.9 g, ethylene carbonate (EC): 376.9 g, titanium tetrabutoxide: 1.0 g were added, and the nitrogen gas was replaced. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Then, after heating for 3 hours at an internal temperature of 160 ° C. under normal pressure, the pressure was reduced to 10 kPa, and the reaction was carried out for 20 hours while removing ethylene glycol and ethylene carbonate out of the system. Next, the pressure was lowered to 5.0 kPa over 60 minutes, and the reaction was further carried out at 160 ° C. for 10 hours. Further, the reaction was continued by lowering to 2.0 kPa over 60 minutes, and then the temperature was raised to 170 ° C. and reacted for 10 hours while removing ethanol and unreacted dihydroxy compound out of the system to obtain a polycarbonate polyol-containing composition. (Total 45 hours). The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 2A and 2B together with the production conditions.

<Comparative Example I-4>
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 211.4 g, triethylene glycol (TEG): 200.2 g, trimethylolpropane (TMP): 6. 8 g, diphenyl carbonate (DPC): 690.6 g, magnesium acetate tetrahydrate aqueous solution: 1.7 mL (concentration: 8.4 g / L) were added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. For 30 minutes (4 hours in total). Thereafter, 0.85% phosphoric acid aqueous solution: 0.45 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC. Then, the same thin film distillation as Example 1 was performed. The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 2A and 2B together with the production conditions.

<Comparative Example I-5>
In a 1 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, diethylene glycol (DEG): 231.8 g, triethylene glycol (TEG): 219.6 g, trimethylolpropane (TMP): 7. 5 g, diphenyl carbonate (DPC): 741.2 g, magnesium acetate tetrahydrate aqueous solution: 1.9 mL (concentration: 8.4 g / L) were added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 130 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure was lowered to 9.3 kPa over 90 minutes, further lowered to 0.7 kPa over 30 minutes, and the reaction was continued. Then, phenol and unreacted dihydroxy compounds were removed from the system while maintaining the temperature at 130 ° C. The reaction was carried out for 7 hours (10.5 hours in total). Thereafter, 0.85% phosphoric acid aqueous solution: 0.45 mL was added to deactivate the catalyst to obtain a polycarbonate polyol-containing composition. The amount of dioxane contained in the distillate trap and the polycarbonate polyol-containing composition was quantified using GC.
The evaluation results of the properties and physical properties of the obtained polycarbonate polyol are shown in Tables 2A and 2B together with the production conditions.

[Production and evaluation of polyurethane]
<Example II-1 and Comparative Example II-4>
Polyurethanes were respectively synthesized using the polycarbonate polyol produced in Example I-1 (Example II-1) and the polycarbonate polyol produced in Comparative Example I-4 (Comparative Example II-4) by the following methods. The physical properties were evaluated.

In a separable flask equipped with a thermocouple and equipped with a stirrer, 81.4 g of polycarbonate polyol preheated to 80 ° C., 2.8 g of 1,4-butanediol, and 232.2 g of dehydrated N, N-dimethylformamide And 22.2 mg of a urethanization catalyst (Neostan U-830), immerse the separable flask in an oil bath set at 55 ° C., and heat the separable flask in a nitrogen atmosphere while heating at 1 at 60 rpm. Stir for about an hour. After the polycarbonate polyol was dissolved in the solvent, diphenylmethane diisocyanate (MDI) was added little by little over 3 hours, and when a total of 15.0 g of MDI was added, a polyurethane solution was obtained. From the obtained polyurethane solution, a test film was prepared by the above-described method, and physical properties were evaluated.
The results are shown in Table 3.

As described above, the smaller the value of the weight change rate in the solvent resistance evaluation, the higher the solvent resistance, which is preferable as the polyurethane.
Moreover, the one where 100% M and 300% M are small has a high softness | flexibility, and is preferable as a polyurethane. Moreover, the one where breaking elongation and breaking strength are larger has high mechanical strength and is preferable as polyurethane.

[Discussion]
In Examples I-1 to 6, it was possible to obtain a polycarbonate polyol having a dioxane generation amount of 0.1% by weight or less and a small carbonate terminal amount.

In Comparative Examples I-1 to 1-3, since a carbonate source other than diphenyl carbonate was used, the reaction rate was low and the reaction was conducted for a long time, but the amount of carbonate ends was large. A large amount of dioxane was generated. Further, the APHA value was high, and the polycarbonate polyol was colored.
In Comparative Example I-4, the reaction time was short, so the amount of carbonate ends was large.
In Comparative Example I-5, since the reaction temperature was low, the amount of carbonate ends was large.
From the urethane evaluation results of Example II-1 and Comparative Example II-4, the polyurethane synthesized from the polycarbonate polyol of Example I-1 having a small amount of carbonate terminal is superior in solvent resistance and breaking elongation / breaking strength. Furthermore, it turns out that it is compatible with flexibility.

Claims (10)

A method for producing a polycarbonate polyol comprising a step of polycondensing a polyhydric alcohol and a carbonate compound,
The polycarbonate polyol has a hydroxyl value of 20 mgKOH / g or more and 450 mgKOH / g or less,
The polyhydric alcohol contains a diol (A),
The diol (A) includes an oxyalkylene glycol (A1) represented by the following formula (1),
The content ratio of the oxyalkylene glycol (A1) in the diol (A) is 60% by weight or more, the oxyalkylene glycol (A1) contains diethylene glycol,
The terminal derived from the carbonate compound contained in the polycarbonate polyol is 1.0 mol% or less in the total terminal,
A method for producing a polycarbonate polyol, wherein the amount of dioxane generated in the polycondensation step is controlled to 1.0% by weight or less with respect to the amount of diethylene glycol added.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)   The method for producing a polycarbonate polyol according to claim 1, wherein the carbonate compound is diaryl carbonate.   3. The method for producing a polycarbonate polyol according to claim 1, wherein in the polycondensation step, a metal salt of Group 2 of the long-period periodic table is used as a catalyst.   The method for producing a polycarbonate polyol according to any one of claims 1 to 3, wherein a reaction temperature in the polycondensation step is 150 ° C or higher and 180 ° C or lower.   The method includes a step of removing unreacted monomers of the polyhydric alcohol after the polycondensation step, and adding a phosphate-based quenching agent before the step of removing the unreacted monomers. The manufacturing method of the polycarbonate polyol of any one of 1-4. The polyhydric alcohol further includes a trivalent to hexavalent branched alcohol (B) having 3 to 12 carbon atoms,
The structural unit derived from the branched alcohol (B) in the polycarbonate polyol is 0.005 mol% or more and 5.0 mol% or less with respect to the total of the structural units derived from the polyhydric alcohol in the polycarbonate polyol. It exists, The manufacturing method of the polycarbonate polyol of any one of Claims 1-5 characterized by the above-mentioned.   The polycarbonate polyol according to any one of claims 1 to 6, wherein the value of Hazen color number of the polycarbonate polyol (APHA value: based on JIS K0071-1 (1998)) is 50 or less. Production method.   The manufacturing method of the polyurethane using the polycarbonate polyol manufactured by the manufacturing method of the polycarbonate polyol of any one of Claims 1-7. A polycarbonate polyol which is a polycondensation reaction product of a polyhydric alcohol and a carbonate compound,
The hydroxyl value is 20 mgKOH / g or more and 450 mgKOH / g or less,
The terminal derived from the carbonate compound is 1.0 mol% or less in all terminals, and the value of Hazen color number (APHA value: conforming to JIS K0071-1 (1998)) is 50 or less,
The polyhydric alcohol includes a diol (A) and a trivalent to hexavalent branched alcohol (B) having 3 to 12 carbon atoms,
The diol (A) contains an oxyalkylene glycol (A1) represented by the following formula (1), and the content ratio of the oxyalkylene glycol (A1) in the diol (A) is 60% by weight or more. A polycarbonate polyol, wherein the oxyalkylene glycol (A1) contains diethylene glycol.

(In the formula (1), m represents an integer of 2 to 4, and R ^A represents a carbon chain which may contain a branch having 2 to 5 carbon atoms. M R ^A included in the formula (1). May be the same or different.)   The structural unit derived from the branched alcohol (B) in the polycarbonate polyol is 0.005 mol% or more and 5.0 mol% or less with respect to the total of the structural units derived from the polyhydric alcohol in the polycarbonate polyol. 10. Polycarbonate polyol according to claim 9, characterized in that it is.