JP2018053266A - Polycarbonate diol and method for producing the same and polyurethane prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol to serve as a raw material for polyurethane excellent in the balance of physical properties such as flexibility, chemical resistance, low temperature resistance, heat resistance, and elastic recovery and a method of producing the same.SOLUTION: A polycarbonate diol has a hydroxyl number of 20-45 mg-KOH/g and a glass transition temperature of -30°C or less as measured with a differential scanning calorimeter, wherein a dihydroxy compound obtained by hydrolysis of the polycarbonate diol has an average number of carbon atoms of 3-5.5.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate diol useful as a raw material for a polycarbonate-based polyurethane, a method for producing the same, and a polyurethane containing the polycarbonate diol.

Conventionally, the raw material of the main soft segment part of polyurethane produced on an industrial scale is
It is classified into an ether type typified by polytetramethylene glycol, a polyester polyol type typified by adipate ester, a polylactone type typified by polycaprolactone, or a polycarbonate type typified by polycarbonate diol (Non-Patent Document 1).

Among these, polyurethane using ether type is said to be inferior in heat resistance and weather resistance, although it is excellent in hydrolysis resistance, flexibility and stretchability. On the other hand, polyurethane using a polyester polyol type is improved in heat resistance and weather resistance, but has low ester group hydrolysis resistance and cannot be used depending on the application.
On the other hand, polyurethanes using polylactone type are considered to be superior in hydrolysis resistance compared to polyurethanes using polyester polyol type. I can't. In addition, it has been proposed to mix these polyester polyol type, ether type and polylactone type and use them as raw materials for polyurethane.

On the other hand, polyurethane using polycarbonate type typified by polycarbonate diol is considered to be the best durability grade in heat resistance and hydrolysis resistance, such as durable film, artificial leather for automobiles, (water-based) paint, Widely used as an adhesive.
However, the polycarbonate diol that is currently widely marketed is a polycarbonate diol synthesized mainly from 1,6-hexanediol, but since this has high crystallinity, the cohesiveness of the soft segment when polyurethane is used. However, there is a problem that the low-temperature characteristics are particularly bad, and the use is limited. Furthermore, it has been pointed out that the artificial leather produced from this polyurethane as a raw material has poor chemical resistance and is hard in terms of texture, and has a “texture” worse than that of natural leather.

In order to solve the above problems, polycarbonate diols using 1,3-propanediol or 1,4-butanediol as raw materials have been proposed.
For example, polycarbonate diol copolymerized using 1,4-butanediol and 1,6-hexanediol as raw materials (Patent Document 1), polycarbonate diol copolymerized using 1,4-butanediol and 1,5-pentanediol as raw materials (Patent Document 2), polycarbonate diol (Patent Document 3) obtained by copolymerization using 1,3-propanediol and another dihydroxy compound as raw materials has been proposed.

A polycarbonate diol using only 1,4-butanediol as a raw material for a dihydroxy compound has been proposed. (Patent Documents 4 to 6)
On the other hand, as a method for producing a polycarbonate diol, a method for synthesizing a high molecular weight polycarbonate diol has been proposed. After reacting a dihydroxy compound with an alkyl carbonate to obtain a polycarbonate diol having a molecular weight of 500 to 2000, an aryl carbonate is further added. A method of producing a polycarbonate diol having a molecular weight exceeding 2000 (Patent Document 7), reacting dimethyl carbonate and an aliphatic dihydroxy compound,
A method for producing a high-quality polycarbonate diol having a hydroxyl group at the molecular end and little coloration (Patent Document 8) is described.

JP-A-5-51428 Japanese Patent Laid-Open No. 4-7327 International Publication No. 2002/070584 Pamphlet JP-A-6-206965 JP 7-41539 A JP 7-41540 A JP 2001-261811 A JP 2001-270938 A

"Basics and Applications of Polyurethane", pages 96-106, supervised by Katsuharu Matsunaga, issued by CMC Publishing Co., Ltd., November 2006

However, these conventionally known techniques, for example, the polycarbonate diols described in Patent Documents 1 to 3, have insufficient low-temperature characteristics and chemical resistance when used as polyurethane. The polycarbonate diols described in Patent Documents 4 to 6 have excellent chemical resistance when used as polyurethane, but the low temperature characteristics are inferior to polyurethanes using polycarbonate diol synthesized from 1,6-hexanediol. there were. In particular, Patent Document 4
Describes a method for producing a polytetramethylene carbonate diol having a molecular weight of 500 to 10,000, but the polycarbonate produced substantially has a low molecular weight, so that the low-temperature characteristics are insufficient.

Patent Document 7 or 8 describes a method for producing a high molecular weight polycarbonate diol, which relates to a polycarbonate diol using 1,6-hexanediol as a raw material, for example, 1,3-propanediol. As for polycarbonate diol using at least one of 1,4-butanediol and 1,5-pentanediol as a raw material, a polycarbonate diol having a substantially high molecular weight could not be synthesized.
The present invention provides a polycarbonate diol, which is a raw material for polyurethane having excellent physical property balance of flexibility, chemical resistance, low temperature characteristics, heat resistance, and elastic recovery, and a method for producing the same, which could not be achieved by the prior art. Let it be an issue.

As a result of intensive studies to solve the above problems, the present inventors have found that the hydroxyl value is 20 mg-
A polycarbonate diol having a KOH / g or more and 45 mg-KOH / g or less, wherein the polycarbonate diol has a glass transition temperature measured by a differential operation calorimeter of −30 ° C. or less, and obtained by hydrolysis of the polycarbonate diol. The polycarbonate diol having an average carbon number of 3 to 5.5 is a polycarbonate diol that is a raw material for polyurethane having a good balance of flexibility, chemical resistance, low temperature characteristics, heat resistance, and elastic recovery. As a result, they have reached the present invention.

That is, the gist of the present invention is as follows.
[1] A polycarbonate diol having a hydroxyl value of 20 mg-KOH / g or more and 45 mg-KOH / g or less, having a glass transition temperature measured by a differential operation calorimeter of the polycarbonate diol of −30 ° C. or less, and A polycarbonate diol, wherein an average number of carbon atoms of a dihydroxy compound obtained by hydrolyzing a polycarbonate diol is 3 or more and 5.5 or less.
[2] The polycarbonate diol as described in [1] above, wherein the dihydroxy compound is only an aliphatic dihydroxy compound having no substituent.
[3] The above [3] or [3], wherein the dihydroxy compound contains at least one selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. 4].
[4] Melting heat of melting peak measured by differential operation calorimeter is 5.0 J / g or more and 80 J
The polycarbonate diol according to any one of the above [1] to [3], which is / g or less.
[5] The above [1], wherein the dihydroxy compound comprises a plant-derived compound.
The polycarbonate diol according to any one of to [4].
[6] A method for producing the polycarbonate diol according to any one of [1] to [5] above, wherein one or a plurality of dihydroxy compounds and diaryl carbonates having an average carbon number of 3 or more and 5.5 or less And a transesterification reaction in the presence of a transesterification catalyst.
[7] The method for producing a polycarbonate diol according to the above [6], wherein the one or more kinds of dihydroxy compounds include a plant-derived compound.
[8] The transesterification catalyst is a compound of at least one element selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen) and long-period periodic table group 2 elements. The process for producing a polycarbonate diol as described in [6] or [7] above,
[9] A polyurethane containing the polycarbonate diol according to any one of [1] to [5] above.

Polyurethanes produced using the polycarbonate diol of the present invention have excellent balance of chemical resistance, low temperature characteristics, heat resistance, flexibility, elastic recovery, elastic fiber, synthetic or artificial leather, paint, It is suitable for high-functional elastomer applications and is extremely useful industrially.

Hereinafter, although the form of this invention is demonstrated in detail, this invention is not limited to the following embodiment, Various deformation | transformation can be implemented within the range of the summary.
Here, in this specification, “mass%” and “weight%”, “mass ppm” and “weight ppm”
And “parts by mass” and “parts by weight” have the same meaning. In addition, when “ppm” is simply described, it indicates “weight ppm”.
Hereinafter, the polycarbonate diol of the present invention will be described.

[1. Polycarbonate diol]
The polycarbonate diol of the present invention has a hydroxyl value of 20 mg-KOH / g or more and 45 mg.
An average of dihydroxy compounds obtained by hydrolyzing the polycarbonate diol having a glass transition temperature of −30 ° C. or less as measured by a differential operation calorimeter of the polycarbonate diol, wherein the polycarbonate diol is −KOH / g or less. 3 to 5 carbon atoms
. 5 or less.

<1-1. Hydroxyl value>
The polycarbonate diol of the present invention has a hydroxyl value of 20 mg-KOH / g or more and 45 mg-
KOH / g or less. The lower limit is preferably 25 mg-KOH / g, more preferably 30 m
g-KOH / g, more preferably 35 mg-KOH / g. The upper limit is preferably 42 mg-KOH / g, more preferably 40 mg-KOH / g, and still more preferably 38
mg-KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity of the polycarbonate diol becomes too high, and handling when making the polyurethane using the polycarbonate diol may be difficult. If the upper limit is exceeded, the polycarbonate diol is flexible when the polyurethane is made using the polycarbonate diol. Properties, low temperature characteristics, elastic recovery properties, etc. may be insufficient.
Within the above range, the polyurethane has excellent flexibility, low-temperature characteristics, and elastic recovery, and also has good physical properties with respect to chemical resistance and heat resistance.

<1-2. Structural features>
The polycarbonate diol of the present invention obtains good chemical resistance and heat resistance when it is made into polyurethane when the average number of carbon atoms of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol is 3 or more and 5.5 or less. Can do. The upper limit of the average carbon number is 5.5
And preferably 5.3, more preferably 5.0, particularly preferably 4.7, and most preferably 4.5. The lower limit of the average carbon number is 3, preferably 3.2, more preferably 3
. 4, particularly preferably 3.5. If it is less than the above lower limit, flexibility and low temperature characteristics may be insufficient, and if it exceeds the above upper limit, chemical resistance and heat resistance may be insufficient.

The average carbon number of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol in the present invention is determined from the result of gas chromatography analysis of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol by heating in the presence of an alkali. be able to. Specifically, it is calculated from the carbon number of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol and the molar ratio of the dihydroxy compound to the total dihydroxy compound.

The dihydroxy compound obtained by hydrolyzing the polycarbonate diol may be one kind or plural kinds. In the case of a plurality of types, it may be a copolymer or a mixture of different kinds of polycarbonate diols, but a copolymer is preferred because of low temperature characteristics and good flexibility. In the case of a copolymer, a block copolymer or a random copolymer may be used, but the polycarbonate diol of the random copolymer is more preferable because of low temperature characteristics and flexibility.

The dihydroxy compound obtained by hydrolyzing the polycarbonate diol is preferably an aliphatic dihydroxy compound. Examples of the aliphatic dihydroxy compound include 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, 1,
4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, 16-hexadecanediol,
1,18-octadecanediol, 1,20-eicosanediol and the like can be mentioned. Among them, an aliphatic dihydroxy compound having no substituent has good properties of polyurethane such as chemical resistance and heat resistance. Furthermore, 1,3-propanediol, 1,4-butanediol, and 1 as dihydroxy compounds having a small number of carbon atoms that have good chemical resistance and heat resistance properties.
It preferably contains at least one selected from the group consisting of 1,5-pentanediol,
Among these, it is more preferable to include any one of 1,3-propanediol and 1,4-butanediol. Furthermore, since the chemical resistance and heat resistance are good, the polycarbonate diol preferably has high crystallinity, and therefore the dihydroxy compound obtained by hydrolyzing the polycarbonate diol preferably contains 1,4-butanediol. .

The dihydroxy compound obtained by hydrolyzing the polycarbonate diol is preferably a plant-derived compound. The compounds applicable as plant origin include 1,3-propanediol, 1,4-butanediol, 1,5-propanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decane. Examples include diol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,20-eicosanediol.

As a plant-derived dihydroxy compound, for example, in the case of 1,4-butanediol, succinic acid, succinic anhydride, succinic acid ester, maleic acid, maleic acid anhydride, maleic acid ester, tetrahydrofuran and γ obtained by the fermentation method -1,4-butanediol may be produced by chemical synthesis from butyrolactone or the like, 1,4-butanediol may be produced directly by fermentation, or 1,3-butadiene obtained by fermentation 1,4-butanediol may be produced from Among them, a method of directly producing 1,4-butanediol by a fermentation method and a method of obtaining 1,4-butanediol by hydrogenating succinic acid with a reduction catalyst are efficient and preferable.

In the case of 1,3-propanediol, 3-hydroxypropionaldehyde is produced from glycerol, glucose, and other sugars by fermentation, and then converted to 1,3-propanediol, and then fermented from glucose and other sugars. Directly by law 1,
It is obtained by producing 3-propanediol.
1,10-decanediol can be synthesized by synthesizing sebacic acid from castor oil by alkali fusion and hydrogenating directly or after the esterification reaction.

<1-3. Glass transition temperature>
The glass transition temperature (Tg) of the polycarbonate diol of the present invention measured by a differential scanning calorimeter (hereinafter sometimes referred to as “DSC”) is −30 ° C. or lower, preferably −35.
It is below ℃. If the Tg is too high, the Tg for polyurethane is also increased, and the low temperature characteristics may be deteriorated.
In the polycarbonate diol of the present invention, the hydroxyl value is in a specific range, the glass transition temperature is in a specific range, and the average carbon number of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol is in a specific range It was found that a polycarbonate diol satisfying the above requirement is a polycarbonate diol that is a raw material of polyurethane having excellent physical properties such as flexibility, chemical resistance, low temperature characteristics, heat resistance, and elastic recovery.

<1-4. Molecular chain end>
The molecular chain terminal of the polycarbonate diol of the present invention is mainly a hydroxyl group. However,
In the case of a polycarbonate diol obtained by the reaction of a dihydroxy compound and a carbonate compound, there may be an impurity in which some molecular chain terminals are not hydroxyl groups.
As specific examples thereof, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many have a structure derived from a carbonate compound.

For example, when diphenyl carbonate is used as the carbonate compound, a phenoxy group (PhO-) as an aryloxy group, a methoxy group (MeO-) as an alkyloxy group when dimethyl carbonate is used, and an ethoxy group when diethyl carbonate is used. (EtO-), when ethylene carbonate is used, a hydroxyethoxy group (
HOCH2CH2O-) may remain as molecular chain ends (where Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group).
The molecular chain terminal other than the hydroxyl group of the polycarbonate diol of the present invention is based on the total number of terminals,
Preferably it is 10 mol% or less, More preferably, it is 5 mol% or less, More preferably, it is 3 mol% or less, Most preferably, it is 1 mol% or less.

<1-5. Molecular Weight / Molecular Weight Distribution>
The ratio of the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”) of the polycarbonate diol of the present invention to the number average molecular weight in terms of polystyrene is 1.5 to 3. 0 is preferred. The lower limit is more preferably 1.7, and still more preferably 1.8. The upper limit is more preferably 2.5, and still more preferably 2.3. When the ratio exceeds the above range, the properties of the polyurethane produced using this polycarbonate diol tend to become hard at low temperatures, decrease in elongation, etc., and try to produce a polycarbonate diol having a molecular weight distribution less than the above range. Then, an advanced purification operation such as removing the oligomer may be necessary.

Further, the number average molecular weight of the polycarbonate diol can be determined from the hydroxyl value, and the lower limit of the number average molecular weight (Mn) is preferably 2,500, more preferably 2,700,
More preferably 2,800, particularly preferably 2,900. On the other hand, the upper limit is preferably 5,500, more preferably 4,500, and still more preferably 3,500.
When Mn of the polycarbonate diol is less than the lower limit, flexibility, low temperature characteristics, and elastic recovery may not be sufficiently obtained when urethane is used. On the other hand, when the upper limit is exceeded, the viscosity increases,
There is a possibility that handling during polyurethane formation is impaired. In particular, within the above preferred range, the polyurethane is particularly excellent in flexibility, low-temperature characteristics and elastic recovery, and also has good physical properties with respect to chemical resistance and heat resistance.

<1-6. APHA value>
The polycarbonate diol of the present invention has a Hazen color number (JIS K0071-1:
In accordance with 1998) (hereinafter referred to as “APHA value”), which is 60 or less, preferably 50 or less, more preferably 30 or less, and still more preferably 20
It is as follows. When the APHA value exceeds 60, the color tone of polyurethane obtained using polycarbonate diol as a raw material is deteriorated, and the commercial value is lowered or the thermal stability is deteriorated. In order to reduce the APHA value to 60 or less, the catalyst for polycarbonate diol production, selection of additive type and amount, thermal history, concentration of monohydroxy compound during polymerization and after completion of polymerization, and concentration of unreacted monomer are integrated. Need to be controlled. Further, light shielding during and after the polymerization is effective. It is also important to set the molecular weight of the polycarbonate diol and to select the dihydroxy compound species that is a monomer. Polycarbonate diols made from aliphatic dihydroxy compounds having alcoholic hydroxyl groups as raw materials show various excellent performances such as flexibility, water resistance, and light resistance when processed into polyurethane, but aromatic dihydroxy compounds are used as raw materials. The heat history and the coloration due to the catalyst tend to be remarkably higher than in the case of the above, and it is not easy to make the APHA value 60 or less.

<1-7. Melting peak temperature, heat of fusion>
Melting peak temperature of the polycarbonate diol of the present invention measured with a differential scanning calorimeter (T
m) is 50 ° C. or higher. Preferably it is 55 degreeC or more, More preferably, it is 60 degreeC or more. The lower limit of the heat of fusion is 5.0 J / g or more, preferably 7.0 J / g or more, more preferably 9.0 J / g or more, and the upper limit is 80 J / g or less, preferably 40 J / g or less. More preferably, it is 35 J / g or less, More preferably, it is 30 J / g or less, Especially preferably, it is 2
5 J / g or less, most preferably 20 J / g or less. When the heat of fusion is less than the above lower limit, the crystallinity of the polycarbonate diol is low and may be inferior in chemical resistance and heat resistant physical properties when made into a polyurethane. The amount of heat is required, and the handleability may be poor.

[2. Production method of polycarbonate diol]
<2-1. Dihydroxy Compound>
The dihydroxy compound used as a raw material in the method for producing polycarbonate diol of the present invention includes 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2- Methyl-1,4-butanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1
, 10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, , 20-eicosanediol and the like.

In the polycarbonate diol of the present invention, the dihydroxy compound obtained by hydrolyzing the polycarbonate diol has an average carbon number of 3 or more and 5.5 or less. -It is preferable to include at least one selected from the group consisting of butanediol and 1,5-propanediol. From the chemical resistance when polyurethane is used, 1,3-propanediol and / or 1,4-butane More preferably, it contains a diol. Furthermore, since the chemical resistance and the physical properties of heat resistance are good, the polycarbonate diol preferably has high crystallinity, and preferably contains 1,4-butanediol.

The dihydroxy compound used as a raw material in the method for producing polycarbonate diol of the present invention is preferably derived from a plant from the viewpoint of reducing environmental burden. The compounds applicable as plant origin include 1,3-propanediol, 1,4-butanediol, 1,5-propanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decane. Examples include diol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,20-eicosanediol.

<2-2. Carbonate compound>
The usable carbonate compound is preferably diaryl carbonate from the viewpoint of reactivity. In particular, in the synthesis of a polycarbonate diol having a number average molecular weight (Mn) of 2,500 or more determined from a hydroxyl value described later, it is preferable to use diaryl carbonate.
Specific examples of the carbonate compound that can be used for the production of the polycarbonate diol of the present invention include diphenyl carbonate.

<2-3. Ratio of raw materials used>
In the production of the polycarbonate diol of the present invention, the amount of carbonate compound used is:
Although not particularly limited, the lower limit is preferably 0.90, more preferably 0.92, even more preferably 0.94, and the upper limit is preferably 1.00, in terms of a molar ratio based on a total of 1 mole of dihydroxy compounds. Preferably it is 0.98, More preferably, it is 0.97. If the amount of carbonate compound used exceeds the above upper limit, the proportion of polycarbonate diol end groups that are not hydroxyl groups may increase, or the molecular weight may not fall within a predetermined range.
If it is less than the lower limit, the polymerization may not proceed to a predetermined molecular weight.

<2-4. Transesterification Catalyst>
The polycarbonate diol of the present invention can be produced by polycondensing the dihydroxy compound and the carbonate compound by a transesterification reaction.
When the polycarbonate diol of the present invention is produced, a transesterification catalyst (hereinafter sometimes referred to as “catalyst”) can be used to promote the transesterification reaction.
In that case, if too much catalyst remains in the obtained polycarbonate diol,
When the polyurethane is produced using the polycarbonate diol, the reaction may be inhibited or the reaction may be excessively accelerated.

For this reason, the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less as the content in terms of catalyst metal.
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 and other periodic table group 14 metal compounds; Antimony, bismuth and other periodic table Group 15 metal compounds; Lanthanum, cerium, europium, ytterbium and other lanthanide metals And the like. 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, Group 9 metal compounds of the periodic table, periodic table first
A compound of Group 2 metal, a compound of Group 13 metal of the periodic table, and a compound of Group 14 metal of the periodic table are preferable, a compound of Group 1 metal of the periodic table and a compound of Group 2 metal of the periodic table are more preferable. 2
More preferred are group metal compounds. Among the compounds of Group 1 metal of the periodic table, lithium, potassium, and sodium compounds are preferable, lithium and sodium compounds are more preferable,
Sodium compounds are more preferred. 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 a salt include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonic acid, toluenesulfonic acid and trifluoro Sulfonates such as romethanesulfonic acid;
Examples thereof include phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; acetylacetonate salts. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

Among these, preferably, acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, alkoxide of at least one metal selected from Group 2 metals of the periodic table is used, More preferred are group 2 metal acetates, carbonates, and hydroxides of the periodic table, more preferred are magnesium, calcium acetates, carbonates, and hydroxides, and particularly preferred are magnesium and calcium. Acetate is used, most preferably magnesium acetate.

<2-5. Catalyst Deactivator>
As described above, when a catalyst is used in the transesterification reaction, the catalyst is usually left in the polycarbonate diol obtained, and the polyurethane formation reaction may not be controlled by the remaining catalyst. In order to suppress the influence of the remaining catalyst, it is preferable to add a substantially equimolar amount of, for example, a phosphorus compound or the like to the transesterification catalyst used to inactivate the transesterification catalyst. Further, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment or the like as described later.

Examples of the phosphorus compound used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate,
Examples thereof include organic phosphates such as triphenyl phosphate and triphenyl phosphite.
These may be used alone or in combination of two or more.
The amount of the phosphorus compound used is not particularly limited, but as described above, it may be approximately equimolar with the transesterification catalyst used. Specifically, the transesterification catalyst 1 used is
The upper limit with respect to the mole is preferably 5 moles, more preferably 2 moles, and the lower limit is preferably 0.8 moles, more preferably 1.0 moles. When a smaller amount of the phosphorus compound is used, the transesterification catalyst in the reaction product is not sufficiently deactivated. When the obtained polycarbonate diol is used as a raw material for polyurethane production, for example, the polycarbonate In some cases, the reactivity of the diol with respect to the isocyanate group cannot be sufficiently reduced. Moreover, when the phosphorus compound exceeding this range is used, the obtained polycarbonate diol may be colored.

The inactivation of the transesterification catalyst by adding a phosphorus compound can be performed at room temperature, but it is more efficient when heat-treated. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150 ° C, more preferably 120 ° C, and even more preferably 100 ° C.
The lower limit is preferably 50 ° C, more preferably 60 ° C, and even more preferably 70 ° C. When the temperature is lower than this, it takes time to inactivate the transesterification catalyst, which is not efficient, and the degree of inactivation may be insufficient. On the other hand, at temperatures exceeding 150 ° C., the obtained polycarbonate diol may be colored.
The time for reacting with the phosphorus compound is not particularly limited, but is usually 1 to 5 hours.

<2-6. Residual monomers, etc.>
When diaryl carbonate such as diphenyl carbonate is used as a raw material, phenols are by-produced during the production of polycarbonate diol. 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 diol is smaller. Specifically, the weight ratio with respect to the polycarbonate diol is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, and particularly preferably 100 ppm or less. In order to reduce the phenols in the polycarbonate diol, as described later, the pressure of the polymerization reaction of the polycarbonate diol may be set to a high vacuum of 1 kPa or less as an absolute pressure, or thin film distillation or the like may be performed after the polymerization of the polycarbonate diol. It is valid.

In the polycarbonate diol, the carbonate compound used as a raw material during production may remain. The remaining amount of the carbonate compound in the polycarbonate diol is not limited, but a smaller amount is preferable, and the upper limit of the weight ratio with respect to the polycarbonate diol 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 diol 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.

In polycarbonate diol, the dihydroxy compound used at the time of manufacture may remain. The residual amount of the dihydroxy compound in the polycarbonate diol is not limited, but a smaller amount is preferable, and the weight ratio to the polycarbonate diol is 1
% By weight or less is preferable, more preferably 0.5% by weight or less, and still more preferably 0.
1% by weight or less. If the residual amount of the dihydroxy compound in the polycarbonate diol is large, the molecular length of the soft segment portion when polyurethane is used may be insufficient, and desired physical properties may not be obtained.

In polycarbonate diol, the cyclic carbonate (cyclic oligomer) byproduced in the case of manufacture may be contained. For example, when 1,3-propanediol is used, 1,3
-Dioxane-2-one or further those in which two or more of these are converted to a cyclic carbonate may be produced and contained in the polycarbonate diol. These compounds may cause a side reaction in the polyurethane formation reaction and cause turbidity. Therefore, the pressure of the polymerization reaction of polycarbonate diol is 1 kP with an absolute pressure.
It is preferable to remove as much as possible by applying a high vacuum of a or less or performing thin film distillation after the synthesis of the polycarbonate diol. The content of these cyclic carbonates contained in the polycarbonate diol is not limited, but is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0% by weight with respect to the polycarbonate diol.
. It is 5% by weight or less, particularly preferably 0.1% by weight or less.

[3. Polyurethane]
Polyurethane can be produced using the above-described polycarbonate diol of the present invention.
The method for producing the polyurethane of the present invention using the polycarbonate diol of the present invention comprises:
Usually, known polyurethane reaction conditions for producing polyurethane are used.
For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol of the present invention with a polyisocyanate and a chain extender in the range of room temperature to 200 ° C.
In addition, the polycarbonate diol of the present invention and an excess of polyisocyanate are first reacted to produce a prepolymer having an isocyanate group at the terminal, and the degree of polymerization is increased using a chain extender to produce the polyurethane of the present invention. I can do it.

<3-1. Polyisocyanate>
Examples of the polyisocyanate used for producing a polyurethane using the polycarbonate diol of the present invention include various known polyisocyanate compounds such as aliphatic, alicyclic or aromatic.
For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2
1,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and aliphatic diisocyanates such as dimer isocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group; 1,4
-Cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4
Cycloaliphatic diisocyanates such as cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; 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, tetraalkyl Aromatic diisocyanates such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate It is done. These may be used alone or in combination of two or more.

Among these, 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) is preferable in that the balance of physical properties of the obtained polyurethane is preferable, and a large amount can be obtained industrially at low cost.
Hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred.

<3-2. 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 isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later. Usually, a polyol, a polyamine, etc. can be mentioned.

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, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2
-Diols having a branched chain such as ethyl-1,3-propanediol and dimer diol; Diols having an ether group such as diethylene glycol and propylene glycol; 1
Diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, xylylene glycol,
Diols having an aromatic group such as 1,4-dihydroxyethylbenzene and 4,4′-methylenebis (hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; N-methylethanolamine, N-ethylethanol Hydroxyamines such as amines; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxy Ethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diph Methane diamine, methylene bis (o-chloroaniline), xylylene diamine, diphenyl diamine, tolylene diamine, hydrazine, piperazine, N, N'polyamines such as diamino piperazine; and water, and the like can be listed.

These chain extenders may be used alone or in combination of two or more.
Among these, 1,4-butanediol (hereinafter sometimes referred to as 1,4BD), 1,5 is preferable in that the balance of physical properties of the obtained polyurethane is preferable, and a large amount can be obtained industrially at low cost. -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4′-diaminodicyclohexylmethane are preferred.
The chain extender in the case of producing a prepolymer having a hydroxyl group, which will be described later, is a low molecular weight compound having at least two isocyanate groups, specifically <3-1. And polyisocyanates>.

<3-3. Hardness adjuster>
When producing polyurethane, a hardness adjusting agent may be used. As the hardness adjusting agent, a dihydroxy compound that is a raw material of polycarbonate diol may be used. The reason why the hardness adjusting agent is used will be described below. For example, when a polyurethane is produced using a polycarbonate diol having a large molecular weight, if the molar composition of the polyisocyanate and the chain extender is the same as that of the polycarbonate diol having a low molecular weight, the weight ratio of the polycarbonate diol in the entire polyurethane molecule increases. As a result, the elastic modulus and hardness are reduced. Therefore, by adding a dihydroxy compound or the like, which is a raw material of polycarbonate diol, as a hardness adjuster, it becomes possible to adjust the weight ratio of polycarbonate diol in the entire polyurethane equally, which is the case when polycarbonate diols having different molecular weights are used. However, it can prevent that the elasticity modulus and hardness of the obtained polyurethane fall. This method is generally widely used.

As the hardness adjusting agent, it is preferable to use a dihydroxy compound which is a raw material of polycarbonate diol. 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol,
, 16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like.

<3-4. 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.

<3-5. Catalyst>
In the polyurethane formation reaction in producing the polyurethane of the present invention, an amine catalyst such as triethylamine, N-ethylmorpholine, triethylenediamine, or tin such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, etc. Known urethane polymerization catalysts typified by organic compounds such as organic metal salts such as titanium compounds and the like can also be used. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

<3-6. Polyols Other than Polycarbonate Diol of the Present Invention>
In the polyurethane formation reaction in producing the polyurethane of the present invention, the polycarbonate diol of the present invention may be used in combination with other polyols as necessary. here,
The polyol other than the polycarbonate diol of the present invention is not particularly limited as long as it is used in normal polyurethane production, and examples thereof include polyether polyols, polyester polyols, and polycarbonate polyols other than the present invention. Here, it is based on the combined weight of the polycarbonate diol of the present invention and other polyols. The weight ratio of the polycarbonate diol of the present invention is preferably 70% or more, more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is small, the balance of chemical resistance, low temperature characteristics and heat resistance, which are the characteristics of the present invention, may be lost.

In the present invention, the above-mentioned polycarbonate diol of the present invention can be modified for use in the production of polyurethane. As a modification method of the polycarbonate diol, a method of introducing an ether group by adding an epoxy compound such as ethylene oxide, propylene oxide or butylene oxide to the polycarbonate diol, a cyclic lactone such as ε-caprolactone, adipic acid, or succinic acid is used as the polycarbonate diol. 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. In the ether modification, the viscosity of the polycarbonate diol is lowered by modification with ethylene oxide, propylene oxide or the like, which is preferable for reasons such as handling. In particular, the polycarbonate diol of the present invention is modified with ethylene oxide or propylene oxide, so that the crystallinity of the polycarbonate diol is lowered and the flexibility at low temperature is improved. Since the water absorption and moisture permeability of the manufactured polyurethane are increased, the performance as artificial leather / synthetic leather may be improved. However, if the addition amount of ethylene oxide or propylene oxide increases, the physical properties such as mechanical strength, heat resistance, chemical resistance and the like of the polyurethane produced using the modified polycarbonate diol decrease. -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 diol is reduced by modification with ε-caprolactone.
The amount of ε-caprolactone added to the polycarbonate diol is 3 to 70% by weight.
Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight,
More preferably, it is 15 to 30% by weight. When the added amount of ε-caprolactone exceeds 70% by weight, the hydrolysis resistance, chemical resistance, etc. of the polyurethane produced using the modified polycarbonate diol are lowered. On the other hand, if it is less than 3% by weight, the effect of reducing viscosity is small, which is not preferable.

<3-7. 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 with which the polycarbonate diol of this invention, polydiisocyanate, and the said chain extender were mix | blended.

<3-8. 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 a method in which the polycarbonate diol of the present invention, other polyol, polyisocyanate and chain extender are mixed and reacted together (hereinafter sometimes referred to as “one-step method”). A method of reacting a polycarbonate diol, other polyol and polyisocyanate to prepare a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with a chain extender (hereinafter sometimes referred to as “two-stage method”). There is).

In the two-stage method, the polycarbonate diol of the present invention and the other polyol are reacted with one or more equivalents of a polyisocyanate in advance to prepare a step for preparing a both-end isocyanate intermediate corresponding to the soft segment of the polyurethane. 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.

<3-9. 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 diol of the present invention, other polyols, polyisocyanate and chain extender all at once.
The amount of polyisocyanate used in the one-stage method is not particularly limited, but the total number of hydroxyl groups of the polycarbonate diol 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 0.7 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 Is 2.0 equivalents, more preferably 1.5 equivalents,
Particularly preferred is 1.1 equivalent.

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 sufficient polyurethane strength will not be obtained.
The amount of chain extender used is not particularly limited, but when the number obtained by subtracting the number of isocyanate groups of the polyisocyanate from the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols is 1 equivalent, the lower limit is preferably Is 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, Preferably it is 1.5 equivalent, Most preferably, it is 1.1 equivalent. 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. Holding performance may not be obtained or heat resistance may deteriorate.

<3-10. Two-stage method>
The two-stage method is also called a prepolymer method, and mainly includes the following methods.
(A) The polycarbonate diol of the present invention and other polyols and an excess of polyisocyanate are preliminarily added to the polyisocyanate / (polycarbonate diol of the present invention and other polyols) in an amount exceeding 1 to 10. A method of producing a polyurethane by reacting at 0 or less to produce a prepolymer having a molecular chain terminal at an isocyanate group, and then adding a chain extender thereto.
(B) A polyisocyanate, an excess of a polycarbonate diol and other polyols in advance, and a reaction equivalent ratio of polyisocyanate / (polycarbonate diol of the present invention and other polyols) is from 0.1 to less than 1.0. A process for producing a polyurethane by reacting to produce a prepolymer having a molecular chain terminal at a hydroxyl group, and then reacting it with a polyisocyanate having an isocyanate group at the terminal as a chain extender.

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 diol and a polyol other than that are directly reacted to synthesize a prepolymer, and used as it is in 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, polyisocyanate, polycarbonate diol and other polyol are reacted, and then chain extension reaction is performed.
In the case of the method (1), in the chain extension reaction, the polyurethane is obtained in the form of coexisting with the solvent by dissolving the chain extender in the solvent or simultaneously dissolving the prepolymer and the chain extender in the solvent. This is very important.

The amount of polyisocyanate used in the two-stage method (a) is not particularly limited,
As the number of isocyanate groups when the number of total hydroxyl groups of the polycarbonate diol and other polyols is 1 equivalent, the lower limit is preferably an amount exceeding 1.0 equivalent, more preferably 1.2 equivalents, still more preferably 1. The upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, and even more preferably 3.0 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. 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 the number of 1 equivalent of isocyanate groups contained in the prepolymer. 0.8 equivalent, and the upper limit is preferably 5.0 equivalent, more preferably 3
. The range is 0 equivalent, more preferably 2.0 equivalent.

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-stage method (b) is not particularly limited, but the total number of hydroxyl groups of polycarbonate diol and other polyols is 1 As the number of isocyanate groups in the case of equivalent, 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 equivalent, more preferably 0.97 equivalent.

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 chain extender used is not particularly limited, but when the total number of hydroxyl groups of the polycarbonate diol and other polyols used in the prepolymer is 1 equivalent, the total of the isocyanate groups used in the prepolymer is added. As the equivalent, 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. Is in the range of 0.98 equivalents.

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 too slow, or the production time may be prolonged due to low solubility of the raw materials and 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 triethylamine, tributylamine, dibutyltin dilaurate,
Examples of the compound include stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. One type may be used alone, or two or more types may be used in combination. Examples of stabilizers include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N, N'-di-2-naphthyl-1,4-phenylenediamine, and tris (dinonylphenyl) phos. A compound such as phyto may be mentioned, 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.

<3-11. Additives>
The polyurethane of the present invention produced using the polycarbonate diol 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; Compounds containing sulfur; tin compounds such as tin malate and dibutyltin monoxide can be used.

Specific examples of hindered phenol compounds include Irganox 1010 (trade name: B
ASF Japan Co., Ltd.), Irganox 1520 (trade name: manufactured by BASF Japan Ltd.), Irganox 245 (trade name: manufactured by BASF Japan Co., Ltd.), and the like.
Examples of phosphorus compounds include PEP-36, PEP-24G, and HP-10 (all trade names:
ADEKA CORPORATION) Irgafos 168 (trade name: manufactured by BASF Japan Ltd.) and the like.

Specific examples of compounds containing sulfur include dilauryl thiopropionate (DLTP),
And thioether compounds such as distearyl thiopropionate (DSTP).
Examples of light stabilizers include benzotriazole-based compounds, benzophenone-based compounds, and the like. Specifically, “TINUVIN622LD”, “TINUVIN765”
Specialty Chemicals Co., Ltd.), “SANOL LS-2626”, “SA
"NOL LS-765" (manufactured by Sankyo Co., Ltd.) or the like can be used.

Examples of ultraviolet absorbers include “TINUVIN 328”, “TINUVIN 234” (
As mentioned above, Ciba Specialty Chemicals Co., Ltd.) etc. are mentioned.
Colorants 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 inorganic fillers include short glass fibers, carbon fibers, alumina, talc,
Examples include graphite, melamine, and white clay.
Examples of the flame retardant include addition of phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, 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 addition 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.

<3-12. 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 thickness of the film is too thick, it tends to be difficult to remove the solvent, and if it is too thin, pinholes are formed or the film tends to be easily blocked and difficult to handle.

<3-13. 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 50 as a polystyrene-reduced weight average molecular weight (Mw) measured by GPC.
It is preferably 10,000, more preferably 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.

<3-14. Chemical 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 the chemical with respect to the weight of the polyurethane test piece before being immersed in the chemical. ) Is preferably 30% or less, more preferably 25% or less, and 20%
The following is more preferable, 15% or less is particularly preferable, and 10% or less is most preferable.
If the weight change rate exceeds the upper limit, desired chemical resistance may not be obtained.

<3-15. Oleic acid 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 60% or less, more preferably 50% or less, further preferably 45% or less, particularly preferably 40% or less, and most preferably 35% or less.
If the weight change rate exceeds the above upper limit, sufficient oleic acid resistance may not be obtained.

<3-16. Ethanol resistance>
In the evaluation of the polyurethane of the present invention by, for example, the method of immersing in ethanol at room temperature for 1 week, 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 25% or less, more preferably 20% or less, further preferably 18% or less, particularly preferably 16% or less, and most preferably 14% or less.
If the weight change rate exceeds the upper limit, sufficient ethanol resistance may not be obtained.

<3-17. 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 lower limit of the tensile elongation at break is preferably 50%, more preferably 100%, still more preferably 150%, and the upper limit is preferably 900%, more preferably 850%, and still more preferably 800%. If the tensile elongation at break is less than the above lower limit, handling properties such as workability tend to be impaired, and if the upper limit is exceeded, sufficient chemical resistance may not be obtained.

<3-18. Young's modulus>
Using polycarbonate diol of the present invention, H12MDI and IPDA, HS content%
15% to 30% by weight of a polyurethane having a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of 140,000 to 210,000 (hereinafter, referred to as “specific polyurethane” in some cases). The Young's modulus at 23 ° C. measured by the same method as the above-described tensile break elongation measurement is preferably 0.02 or more, more preferably 0.04 or more, and still more preferably 0.
. 06 or more. Further, it is preferably 2 or less, more preferably 1 or less, and still more preferably 0.
5 or less. If the Young's modulus is too low, chemical resistance may be insufficient. If the Young's modulus is too high, flexibility may be insufficient, or handling properties such as workability may be impaired. Further, the Young's modulus measured by the same method as the above tensile break elongation measurement except that the specific polyurethane is set to −10 ° C. is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more. Especially preferably, it is 0.05 or more. Further, it is preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less, and particularly preferably 0.3 or less. −
If the Young's modulus at 10 ° C is less than the above lower limit, chemical resistance may be insufficient. If the Young's modulus at −10 ° C. exceeds the above upper limit, flexibility at low temperatures may be insufficient, and handling properties such as workability may be impaired.

Here, the Young's modulus is a stress value at an elongation of 1% as the slope of the stress value at the initial elongation, and is specifically measured by the method described in the section of Examples described later. .
The HS (hard segment) content% can be calculated by the following equation.
HS content (% by weight) = [Polyisocyanate charge weight (g) + Chain extender charge weight (g) + Hardness modifier (g)] / [Polyisocyanate charge weight (g) + Polycarbonate diol charge weight (g) + Other polyol charge weight (g) + chain extender charge weight (g) + hardness modifier (g)]
Each term of the above formula is a numerical value related to the raw material used at the time of urethane production.

<3-19. 100% modulus>
When the polyurethane of the present invention is obtained by reacting 2 equivalents of 4,4′-dicyclohexylmethane diisocyanate with the polycarbonate diol of the present invention and further performing chain extension reaction with isophoronediamine to obtain a polyurethane by a two-stage method, the width is 10 mm, For a strip-shaped sample having a length of 100 mm and a thickness of about 50 to 100 μm, a distance between chucks of 50 mm and a tensile speed of 50
The lower limit of 100% modulus measured at 0 mm / min at a temperature of 23 ° C. and a relative humidity of 50% is preferably 0.1 MPa or more, more preferably 0.5 MPa or more, and even more preferably 1 MP.
The upper limit is preferably 20 MPa or less, more preferably 10 MPa or less, and still more preferably 5 MPa or less. If the 100% modulus is less than the above lower limit, chemical 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. Furthermore, 100% of specific polyurethane at -10 ° C
The modulus is preferably 0.5 or more, more preferably 1.0 or more, and still more preferably 1.
5 or more, particularly preferably 2.0 or more. Also preferably 15 or less, more preferably 10
Hereinafter, it is more preferably 7 or less, particularly preferably 5 or less. If the 100% modulus at −10 ° C. is less than the above lower limit, chemical resistance may be insufficient. When the 100% modulus at −10 ° C. exceeds the above upper limit, flexibility at low temperatures may be insufficient, and handling properties such as workability may be impaired.

<3-20. Elastic recovery>
The polyurethane of the present invention has a width of 10 mm in an environment of a temperature of 23 ° C. and a relative humidity of 50%.
, Stretched to 300% at a chuck distance of 50 mm and a tensile speed of 500 mm / min with respect to a strip-shaped polyurethane test piece having a length of 100 mm and a thickness of about 50 to 100 μm, and subsequently contracted at the same speed to the original length. By repeating this twice, the elastic recovery rate at a temperature of 23 ° C. and a relative humidity of 50% was calculated.

At this time, the ratio of the stress at the time of 150% elongation at the time of the first contraction to the stress at the time of 150% elongation at the time of the first elongation is preferably close to 1, preferably 0.1 or more, more preferably 0. 11 or more, more preferably 0.14 or more, and most preferably 0.15 or more.
Further, the ratio of the stress at the time of 150% extension at the time of the second extension to the stress at the time of 150% extension at the time of the first extension is better as close to 1, preferably 0.5 or more, more preferably 0.6. More preferably, it is 0.7 or more, and most preferably 0.8 or more.

Furthermore, the point at which stress at the time of the second elongation occurs is defined as% SET (permanent strain), and this value should be close to 0, preferably 70 or less, more preferably 60 or less, still more preferably 40 or less, and most preferably Is 20 or less.
In addition, the polyurethane of the present invention has a width of 10 mm and a length of 1 in an environment at a temperature of −10 ° C.
A strip-shaped polyurethane test piece having a thickness of about 50 to 100 μm is stretched to 300% at a chuck distance of 50 mm and a tensile speed of 500 mm / min, and then contracted at the same speed to the original length. The elastic recovery rate at −10 ° C. was calculated by repeating the process. At this time, 2 at the time of the first contraction with respect to the stress at the time of 250% elongation at the first extension.
The ratio of stress at 50% elongation is better as close to 1, preferably 0.06 or more, more preferably 0.10 or more, still more preferably 0.12 or more, and most preferably 0.13 or more. In addition, 2 at the time of the second extension with respect to the stress at the time of 250% extension at the first extension.
The stress at 50% elongation is better as it is closer to 1, preferably 0.50 or more, more preferably 0.8.
55 or more, more preferably 0.60 or more. Further, the point at which stress at the time of the second elongation occurs is set as% SET (permanent strain), and this value is better as close to 0, preferably 130% or less,
More preferably, it is 120% or less, more preferably 110% or less, and most preferably 105% or less.

<3-21. Low temperature characteristics>
The polyurethane of the present invention has good low temperature characteristics, but the low temperature characteristics in this patent are -10.
It can be evaluated by tensile elongation at break, Young's modulus, and 100% modulus in a tensile test at a low temperature such as ° C. Moreover, it can evaluate by the stress ratio in a cycle test at low temperature, such as -10 degreeC, and a permanent set. Specifically, it refers to flexibility at low temperature, elastic recovery, impact resistance, flex resistance, and durability.

<3-22. Heat resistance>
In the polyurethane of the present invention, a urethane film having a width of 100 mm, a length of 100 mm, and a thickness of about 50 to 100 μm is heated in a gear oven at a temperature of 120 ° C. for 400 hours, and the weight average molecular weight (Mw) of the heated sample is heated. The lower limit is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, particularly preferably 85% or more, and the upper limit is preferably 120% or less with respect to the previous weight average molecular weight (Mw). , More preferably 110%
Hereinafter, it is more preferably 105% or less.

<3-23. Glass transition temperature>
Using the polycarbonate diol of the present invention, H12MDI, and IPDA, the weight-average molecular weight (Mw) in terms of polystyrene measured by GPC, which is manufactured by a one-stage method with an HS content of 15% to 30%, is 140,000 to 210,000 specific polyurethane glass transition temperature (T
The lower limit of g) is preferably -50 ° C, more preferably -45 ° C, still more preferably -40 ° C.
The upper limit is preferably 10 ° C, more preferably 0 ° C, and even more preferably -10 ° C. If Tg is less than the above lower limit, chemical resistance may not be sufficient, and if it exceeds the upper limit, low temperature characteristics may not be sufficient.

<3-24. Application>
The polyurethane of the present invention is excellent in chemical resistance and has good low-temperature properties. It can be widely used for synthetic leather, coating agents, water-based polyurethane paints, active energy ray-curable resin compositions, and the like.
In particular, when the polyurethane of the present invention is used for applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc., the chemical resistance and low-temperature characteristics are good. Because it has a balance, it is highly durable in areas where it touches human skin and where cosmetic drugs and alcohol for disinfection are used. A good characteristic of being strong can be imparted. Further, it is also suitable for an intermediate coating material for automobile exteriors that require more stringent flexibility at low temperatures.

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, etc., industrial products such as conveyor belt idlers, guides, etc. 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, pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment, tubes and hoses for industrial robots used in food and medical fields, spiral tubes,
Can be used for fire hose etc. 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. In addition, automobile parts include oil stoppers, gear boxes, spacers, chassis parts, interior parts,
Examples include tire chain substitutes. 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 used as a solvent-based two-component paint,
It can be applied to wood products such as 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 2
It is 00 degreeC or more and 235 degrees C or less.

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 can be used as a sealant caulking for concrete wall, induction joint, sash area, wall PC joint, ALC joint, board joint, composite glass sealant, heat insulation sash sealant, automotive sealant, 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.

<3-25. Urethane (meth) acrylate oligomer>
Moreover, you may manufacture a urethane (meth) acrylate type oligomer by making addition reaction of polyisocyanate and droxyalkyl (meth) acrylate using the polycarbonate diol of this 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 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 diol, and other raw material compounds used as needed, and Usually 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, based on the total amount of the compound containing a functional group that reacts with isocyanate such as a chain extender,
Usually, it is 70 mol% or less, preferably 50 mol% 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 diol used is preferably 25 mol% or more, more preferably 50 mol% or more, based on the total amount of polycarbonate diol and polyol used.
More preferably, it is 70 mol% or more. When the usage-amount of polycarbonate diol is larger than the said lower limit, there exists a tendency for the hardness and stain resistance of the hardened | cured material obtained to become favorable, and it is preferable.

Further, the amount of polycarbonate diol used is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably based on the total amount of polycarbonate diol and polyol used. Is 70% by mass or more. If the amount of polycarbonate diol used is greater than the lower limit, the viscosity of the resulting composition will decrease and workability will improve, and the mechanical strength, hardness and abrasion resistance of the resulting cured product will tend to improve. preferable.

Further, the amount of polycarbonate diol 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 diol and polyol used. When the usage-amount of polycarbonate diol is larger than the said lower limit, it will become the tendency for the elongation of a hardened | cured material obtained and a weather resistance to improve, and is preferable.

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 compounds used in combination of polycarbonate diol and polyol and chain extender. The mol% or more, more preferably 90 mol% or more, particularly preferably 95 mol% or more. When the amount of polyol is larger than the above lower limit value, 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 at less than 300 parts by mass with respect to 100 parts by mass 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 the raw material compounds thereof is preferably 20% by mass or more, based on the total amount of the reaction system, and 40% by mass. % Or more is more preferable. In addition, the upper limit of this total content is 100 mass%. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compound to be 20% by mass 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 or less, preferably 500 ppm or less, and a lower limit of usually 10 ppm or more, preferably 30 ppm or more, with respect to the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Used.
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 polymerization inhibitors include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, 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 or less, preferably 1000 ppm or less, particularly preferably 500 ppm or less, and a lower limit usually based on the total content of the urethane (meth) acrylate oligomer and raw material compounds to be produced. It is used at 50 ppm or more, preferably 100 ppm or more.
During the production of urethane (meth) acrylate oligomers, the reaction temperature is usually 20 ° C.
It is above, it is preferable that it is 40 degreeC or more, and it is more preferable that it is 60 degreeC or more.
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 5-20.
It is about time.

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.

<3-26. Polyester elastomer>
Further, the polycarbonate diol of the present invention may 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 diol 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 of using an aliphatic polyether or aliphatic polyester. Compared to known polycarbonate diols, it has a melt flow rate, that is, a melt flow rate suitable for blow molding and extrusion molding, and a polycarbonate ester elastomer with an excellent balance between 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.

Moreover, you may use the above-mentioned urethane (meth) acrylate type oligomer by making it contain in an active energy ray-curable polymer composition.
The active energy ray-curable polymer composition has a molecular weight between the calculated network crosslinking points of 500 of the composition.
It is preferable that it is -10,000.
The molecular weight between calculated network cross-linking points of the composition represents an average value of molecular weights between active energy ray reactive groups (hereinafter sometimes referred to as “cross-linking points”) that form a network structure in the entire composition. 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, for a bifunctional compound with a molecular weight of 1,000, (1000/2) × 2 = 10
For a trifunctional compound having 00 and a molecular weight of 300, (300/3) × 2 = 200.
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, and the molecular weight between calculated network crosslinking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2 / 20 = 5
20

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, 40 mol of a monofunctional compound having a molecular weight of 100 and a bifunctional compound having a molecular weight of 1,000
In a composition composed of a mixture with mol, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4.
= 8, so the extension by the monofunctional compound in the molecular weight between the calculated network crosslinking points is 100 × 4
0/8 = 500. That is, the molecular weight between calculated network crosslinks of the composition is 1000 + 500 = 1.
500.
From the above, in the case of a mixture of the monofunctional compound MA having a molecular weight WA, the fB functional compound MB mole having a molecular weight WB, and the fC functional compound MC mole having a molecular weight WC, the molecular weight between the calculated network crosslinking points of the composition Can be expressed by the following formula.

The molecular weight between calculated network crosslinking points of the active energy ray-curable polymer composition calculated in this manner is preferably 500 or more, more preferably 800 or more,
It is more preferable that it is 000 or more, and it is preferable that it is 10,000 or less,
It is more preferably 8,000 or less, further preferably 6,000 or less, still more preferably 4,000 or less, and particularly preferably 3,000 or less.

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.

Furthermore, the active energy ray-curable polymer composition may further contain other 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, the content of the urethane (meth) acrylate oligomer is 40% by mass or more based on the total amount of active energy ray-reactive components including the urethane (meth) acrylate oligomer. Is preferable, and it is more preferable that it is 60 mass% or more. In addition, the upper limit of this content is 100 mass%. When the content of the urethane (meth) acrylate oligomer is 40% by mass 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, the content of the urethane (meth) acrylate oligomer is preferably higher in terms of elongation and film-forming property, and, on the other hand, in terms of lowering the viscosity, Less is preferable. From such a viewpoint, the content of the urethane (meth) acrylate oligomer is preferably 50% by mass or more based on the total amount of all components including other components in addition to the active energy ray-reactive component. 70% by mass or more is more preferable. In addition, the upper limit of content of a urethane (meth) acrylate type oligomer is 100 mass%, and it is preferable that this content is less than that.

In addition, in the active energy ray-curable polymer composition, the total content of the active energy ray-reactive component including the urethane (meth) acrylate oligomer is excellent in the curing speed and surface curability as the composition, and is tacky. From the aspect of not remaining, for the total amount of the composition,
It is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass.
The content is more preferably at least mass%, and even more preferably at least 95 mass%. In addition, the upper limit of this content is 100 mass%.

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. Specifically, for example,
Aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide,
Vinyl ester monomers such as N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; diallyl phthalate, trimethylolpropane diallyl ether, allyl glycidyl ether Allyl compounds such as; (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) acrylamides such as (meth) acryloylmorpholine and methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Acrylic acid-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 , Stearyl (meth) acrylate, Tet (meth) acrylate Tetrahydrofurfuryl (meth) morpholyl acrylate, (
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meta ) Diethylaminoethyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) acrylic Dicyclopentenyloxyethyl acid, dicyclopentanyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, etc. Monofunctional (meth) acrylate; and di (meta) Ethylene glycol acrylate, di (meth) acrylate diethylene glycol di (meth) triethylene glycol acrylate, di (meth) tetraethylene glycol acrylate, di (meth) polyethylene glycol acrylate (n = 5
-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene (di (meth) acrylate) Glycol (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 to 3).
16), poly (1-methylbutylene glycol) di (meth) acrylate (n = 5 to 20)
, Di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-
Nonanediol, di (meth) acrylate neopentyl glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, trimethylol Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (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 (meta)
Polyfunctional (meth) acrylates such as acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, and bisphenol F epoxy di (meth) acrylate; It is done.

Among these, particularly in applications where coating properties are required, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, (meth)
Cyclohexyl acrylate, trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. of,
A monofunctional (meth) acrylate having a ring structure in the molecule is preferable. 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, neopentyl glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

In the active energy ray-curable polymer composition, the content of the active energy ray-reactive monomer is the total amount of the composition from the viewpoint of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. On the other hand, it is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further more preferably 10% by mass or less.

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, the content of the active energy ray-reactive oligomer is 50 mass with respect to the total amount of the composition from the viewpoint of adjusting physical properties such as hardness and elongation of the obtained cured product. % Or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 10% by mass 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, methylorthobenzoylbenzoate, 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, methylbenzoyl formate, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1-
ON, 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, because the curing speed is fast and the crosslinking density can be sufficiently increased,
2-hydroxy-2-methyl-1-phenylpropan-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 preferred,
-Hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2
More preferred is -methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one.

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 is preferably 10 parts by mass or less with respect to 100 parts by mass in total of the active energy ray reactive components. The following is more preferable. It is preferable for the content of the photopolymerization initiator to be 10 parts by mass 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,
Examples include N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone.

In the active energy ray-curable polymer composition, the content of the photosensitizer is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray reactive components. It is more preferable that the amount is not more than parts. It is preferable for the content of the photosensitizer to be 10 parts by mass or less, since it is difficult for mechanical strength to decrease due to a decrease in crosslink 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 beads,
Silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder and other fillers; carbon fiber, carbon black, graphite, carbon nanotube, Carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as “inorganic components”); antioxidants, heat stabilizers, ultraviolet absorbers, HALS (hindered amine light stabilizers) ), Anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, antisettling agent, surfactant, thixotropy imparting agent, lubricant, flame retardant , Modifiers such as flame retardant aids, polymerization inhibitors, fillers, silane coupling agents; colorants such as pigments, dyes, hue modifiers; and monomers or / and oligomers thereof, or Curing agent required for the synthesis of the machine component, the catalyst, curing accelerators like; and the like.

In the active energy ray-curable polymer composition, the content of the additive is preferably 10 parts by mass or less, preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the active energy ray reactive components. It is more preferable that It is preferable for the content of the additive to be 10 parts by mass or less, since it is difficult for 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 mass parts with respect to 100 mass parts 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 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 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 mill , A kneader, a homogenizer, an ultrasonic disperser and the like.

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

The coating method of the active energy ray-curable polymer composition includes 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, and a lip coater. Known methods such as a 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.

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.
Below, the evaluation method of each physical property value is as follows.

[Evaluation method: Polycarbonate diol]
<Quantification of phenoxy group content, dihydroxy compound content and phenol content>
Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) was measured, phenoxy group, dihydroxy compound, and phenol were identified from the signal position of each component, and each integrated value was determined. The content of was calculated. In this case, the detection limit is 100 ppm as the weight of phenol relative to the weight of the entire sample, and the dihydroxy compound such as the compound represented by the formula (A) and the compound represented by the formula (B) is 0.
1% by weight. The ratio of the phenoxy group is determined from the ratio of the integral value of one proton of the phenoxy group to the integral value of one proton of the whole terminal, and the detection limit of the phenoxy group is 0.05% with respect to the whole terminal. .

<Hydroxyl value>
Based on JIS K1557-1 (2007), the hydroxyl value of polycarbonate diol was measured by a method using an acetylating reagent.
<Measurement of APHA value>
According to JIS K0071-1 (1998), the APHA value was measured in comparison with a standard solution in which a polycarbonate diol was placed in a colorimetric tube. Reagent is chromaticity standard solution 1000 degrees (1 mg
Pt / mL) (Kishida Chemical) was used.

<Measurement of melt viscosity>
After the polycarbonate diol is heated to 80 ° C. and melted, an E-type viscometer (BROOKF)
The melt viscosity was measured at 80 ° C. using IELD DV-II + Pro, cone: CPE-52).
<Measurement of glass transition temperature (Tg), melting peak temperature, heat of fusion>
About 10 mg of polycarbonate diol is enclosed in an aluminum pan, EXSTAR
DSC6200 (manufactured by Seiko Instruments Inc.) is used at 20 ° C. per minute in a nitrogen atmosphere.
30 ° C. to 150 ° C. at a rate of 150 ° C. to −120 ° C. at a rate of 40 ° C. per minute, 20 ° C. per minute
The temperature was raised and lowered from −120 ° C. to 120 ° C. at the rate of, and the melting peak temperature and the heat of fusion were determined from the glass transition temperature (Tg) at the inflection point at the second temperature rise, and the melting peak.

<Molar ratio of dihydroxy compound after hydrolysis>
About 0.5 g of polycarbonate diol 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. 6N after cooling at room temperature
Hydrochloric acid (5 mL) was added to neutralize the sodium hydroxide to bring the pH to 7. Transfer the entire volume to a 100 mL volumetric flask and wash the Erlenmeyer flask twice with an appropriate amount of methanol.
Transferred to L 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 analyzed by gas chromatography (GC). For the concentration of each dihydroxy compound, a calibration curve was prepared in advance from each known dihydroxy compound as a standard substance, and the weight percentage was calculated from the area ratio obtained by gas chromatography (GC).

(Analysis conditions)
Apparatus: Agilent 6850 (manufactured by Agilent Technologies)
Column: Agilent J & W GC column DB-WAX
Inner diameter 0.25mm, length 60m, membrane pressure 0.25mm
Detector: Hydrogen flame ionization detector (FID)
Temperature rising program: 150 ° C. (2 minutes), 150 ° C. → 280 ° C. (10 ° C./min, 9 minutes),
240 ° C (10 minutes)
The molar ratio of the dihydroxy compound was calculated from the weight% obtained by gas chromatography and the molecular weight of each dihydroxy compound.

[Evaluation method: Polyurethane]
<Isocyanate group concentration measurement>
20 ml of a mixed solution of di-n-butylamine / toluene (weight ratio: 2/25) was added to acetone 9
After diluting with 0 mL, titration was performed with 0.5 N aqueous hydrochloric acid, and the amount of aqueous hydrochloric acid required for neutralization was measured to obtain a blank value. Thereafter, 1 to 2 g of the reaction solution was extracted, 20 mL of a mixed solution of di-n-butylamine / toluene was added, and the mixture was stirred at room temperature for 30 minutes, and then diluted with 90 mL of acetone in the same manner as in the blank measurement. The amount of hydrochloric acid aqueous solution required for neutralization was measured by titration with, and the amount of remaining amine was quantified. The concentration of the isocyanate group was determined from the volume of the aqueous hydrochloric acid solution required for neutralization by the following formula.
Isocyanate group concentration (% by weight) = A * 42.02 / D
A: Isocyanate group (mol) contained in the sample used in this measurement
A = (B−C) × 0.5 / 1000 × f
B: Amount of 0.5N hydrochloric acid aqueous solution required for blank measurement (mL)
C: Amount of 0.5N hydrochloric acid aqueous solution required for this measurement (mL)
D: Sample used for this measurement (g)
f: Potency of aqueous hydrochloric acid solution

<Measurement of solution viscosity>
Add VISC to a solution of polyurethane in dimethylformamide (concentration: 30% by weight).
OMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) installed a rotor of 3 ° × R14,
The solution viscosity of the polyurethane solution was measured at 25 ° C.

<Molecular weight measurement>
Prepare a dimethylacetamide solution so that the polyurethane has a molecular weight of 0.14% by weight. A GPC apparatus [product name “HLC-8220” (manufactured by Tosoh Corporation) (
Column: Tskel GMH-XL, 2)], and the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Oleic acid resistance evaluation method>
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 then 0.5 hours at 100 ° C. for 1 hour at 60 ° C. Let dry for hours. Furthermore, in a vacuum state of 100 ° C., 0.5 hours, 8
After drying at 0 ° C. for 15 hours, the sample was allowed to stand for 12 hours or more at a constant temperature and humidity of 23 ° C. and 55% RH. For 1 week in a thermostat in a nitrogen atmosphere at 80 ° C. or 1
It was left for 6 hours. After the test, after lightly wiping the front and back of the test piece with a paper wiper, the weight was measured and the weight increase ratio from before the test was calculated. A weight change rate closer to 0% indicates better oleic acid resistance.

<Polyurethane ethanol resistance evaluation method>
A urethane film was prepared in the same manner as described in the above <Method for evaluating resistance to oleic acid>, and then a urethane film test piece cut out in 3 cm × 3 cm was cut out. After measuring the weight of the test piece with a precision balance, it was placed in a glass petri dish having an inner diameter of 10 cmφ containing 50 ml of a test solvent and immersed at room temperature of about 23 ° C. for 1 hour. After the test, the test piece was taken out and lightly wiped with a paper wiper, and then the weight was measured to calculate the weight increase ratio from before the test.

<Method of measuring glass transition temperature (Tg)>
About 5 mg of a polyurethane film piece prepared in the same manner as in the oleic acid resistance evaluation is enclosed in an aluminum pan, and EXSTAR DSC6200 (manufactured by Seiko Instruments Inc.) is used, and it is −100 ° C. at a rate of 10 ° C. per minute in a nitrogen atmosphere. To 250 ° C, 250 ° C to -10
The temperature was raised and lowered from 0 ° C. to −100 ° C. to 250 ° C., and the inflection point at the second temperature rise was defined as the glass transition temperature (Tg).

<Room temperature tensile test method>
According to JIS K6301 (2010), width 10mm, length 100mm, thickness about 50μ
Using a tensile tester (product name “Tensilon UTM-III-100” manufactured by Orientec Co., Ltd.), a distance between chucks of 50 mm and a tensile speed of 5
A tensile test was performed at a temperature of 23 ° C. (relative humidity 55%) at 00 mm / min.
The stress at the time of% elongation was measured. The Young's modulus is the slope of the stress value at the initial elongation,
Specifically, the stress value at an elongation of 1% was used.

<Low temperature tensile test method>
According to JIS K6301 (2010), width 10mm, length 100mm, thickness about 50μ
The polyurethane test piece in the shape of a strip of m is a tensile tester [manufactured by Shimadzu Corporation, product name “
Autograph AG-X 5kN "], constant temperature bath set to -10 ° C [manufactured by Shimadzu Corporation, product name" THERMOTATIC CHAMBER TCR2W-200T "
]], A film was installed at a distance between chucks of 50 mm. Then, after leaving still at -10 degreeC for 3 minute (s), the tension test was implemented at the tension speed of 500 mm / min, and the stress at the time of test piece extending | stretching 100% was measured. The Young's modulus is the slope of the stress value at the initial elongation. Specifically, the elongation is 1
% Stress value.

<Polyurethane low temperature cycle test method>
According to JIS K6301 (2010), width 10mm, length 100mm, thickness about 90μ
The polyurethane test piece in the shape of a strip of m is a tensile tester [manufactured by Shimadzu Corporation, product name “
Autograph AG-X 5kN ”, load cell 100N], constant temperature bath set to −10 ° C. [manufactured by Shimadzu Corporation, product name“ THERMOTATIC CHAMBER ”
TCR2W-200T "] was installed with a chuck distance of 50 mm. Next,-
After standing at 10 ° C. for 3 minutes, the film was stretched to 300% at a pulling speed of 500 mm / min, then contracted to the original length at the same speed, and this was repeated twice. 250 at the first extension
The ratio of the stress at 250% elongation during the first contraction to the stress at the time of% elongation (hereinafter referred to as “
It may be referred to as “ratio 1”. ) Further, the stress at the time of 250% elongation at the time of the second elongation (hereinafter sometimes referred to as “ratio 2”) was obtained with respect to the stress at the time of 250% elongation at the first elongation.

<Heat resistance evaluation>
A polyurethane film prepared in the same manner as in the oleic acid resistance evaluation was 100 mm wide and 10 mm long.
The strip was 0 mm in thickness and about 50 μm thick, heated in a gear oven at a temperature of 120 ° C. for 400 hours, and the weight average molecular weight (Mw) of the heated sample was measured by the method described in <Molecular weight measurement>.

<Raw materials>
The raw materials used for the production of the polycarbonate diol of this example are as follows.
1,4-butanediol (hereinafter sometimes abbreviated as 1,4BD): manufactured by Mitsubishi Chemical Corporation 1,3-propanediol (hereinafter sometimes abbreviated as 1,3PDO): manufactured by Dupont Corporation 1, 6-hexanediol (hereinafter sometimes abbreviated as 1,6HD): BASF 1,10-decanediol (hereinafter sometimes abbreviated as 1,10DD): Toyokuni Oil Co., Ltd. 1,12-dodecane Diol (hereinafter abbreviated as 1,12 DDD): 2-methyl-1,3-propanediol (hereinafter abbreviated as 2M1,3PDO) manufactured by Wako Pure Chemical Industries, Ltd .: Tokyo Chemical Industry Co., Ltd. Company-made diphenyl carbonate (hereinafter sometimes abbreviated as DPC): Mitsubishi Chemical Corporation ethylene carbonate (hereinafter sometimes abbreviated as EC): Made by Mitsubishi Chemical Corporation Magnesium acetate tetrahydrate: Wako Pure Chemical Industries, Ltd.

[Example 1]
<Production and evaluation of polycarbonate diol>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 1,4-butanediol (1,4BD): 975.8 g, 1,10-decanediol (1, 10DD): 414.2 g, diphenyl carbonate: 2709.9
g, Magnesium acetate tetrahydrate aqueous solution: 6.7 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 55 mg) was added, and the atmosphere was replaced with nitrogen gas. 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. The pressure is then increased to 9.3 kPa to 9
The reaction was continued over a period of 30 minutes by lowering to 0 kPa and then 30 minutes to 0.7 kPa.
The temperature was raised to 70 ° C. and reacted for 60 minutes while removing phenol and unreacted dihydroxy compound out of the system to obtain a polycarbonate diol-containing composition.

The obtained polycarbonate diol-containing composition was fed to a thin film distillation apparatus at a flow rate of 20 g / min, and thin film distillation (temperature: 180 to 190 ° C., pressure: 40 to 67 Pa) was performed. As the thin-film distillation apparatus, an internal condenser having a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m2, a special model of molecular distillation apparatus MS-300 manufactured by Shibata Kagaku Co., Ltd. with a jacket was used.
The same applies to the following examples and comparative examples.
Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

<Manufacture and evaluation of polyurethane>
Using the polycarbonate diol obtained by the above method, a specific polyurethane was produced by the following operation.

(Prepolymer (PP) reaction)
In a separable flask equipped with a thermocouple and a condenser tube, 90.57 g of the above polycarbonate diol heated to 80 ° C. was put in advance, and the flask was immersed in an oil bath at 60 ° C., and then 4,4′-dicyclohexylmethane. Diisocyanate (hereinafter, H12MDI, manufactured by Tokyo Chemical Industry Co., Ltd.) (22.69 g) and triisooctyl phosphite (hereinafter, TiOP, manufactured by Tokyo Chemical Industry Co., Ltd.) (0.332 g) as a reaction inhibitor are added, and the flask is filled with a nitrogen atmosphere. The temperature was raised to 80 ° C. in about 1 hour while stirring at 60 rpm. After raising the temperature to 80 ° C., 9.3 mg of Neostan U-830 (hereinafter U-830, manufactured by Nitto Kasei Co., Ltd.) as a urethanization catalyst (81.
9 wtppm) was added, and after the exotherm subsided, the oil bath was heated to 100 ° C. and further stirred for about 2 hours. The concentration of the isocyanate group was analyzed, and it was confirmed that the theoretical amount of the isocyanate group was consumed.

(Chain extension reaction)
106.62 g of the obtained prepolymer (PP) was diluted with 11.46 g of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.). Subsequently, dehydrated N, N-dimethylformamide (hereinafter DMF,
237.36 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the flask was immersed in an oil bath at 55 ° C., and the prepolymer was dissolved while stirring at about 200 rpm. After analyzing the concentration of isocyanate groups in the prepolymer solution, the flask was immersed in an oil bath set at 35 ° C.
While stirring at pm, 6.06 g of the required amount of isophoronediamine (hereinafter referred to as IPDA, manufactured by Tokyo Chemical Industry Co., Ltd.) calculated from the residual isocyanate was added in portions. After stirring for about 1 hour, 0.623 g of morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a terminal terminator, and the mixture is further stirred for 1 hour to obtain a polyurethane solution having a viscosity of 125 Pa · s and a weight average molecular weight of 151,000. It was. Table 3 shows the evaluation results of the properties and physical properties of this polyurethane.

[Examples 2 to 7]
<Production and evaluation of polycarbonate diol>
In the production of the polycarbonate diol of Example 1, all the reactions were carried out under the same conditions and methods except that the types and amounts of PCD polymerization raw materials were changed to the types and amounts of raw materials shown in Table 1. A containing composition was obtained.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Example 1. Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

<Manufacture and evaluation of polyurethane>
In the production of the polyurethane of Example 1, the polycarbonate diol (PCD) used
) And the charged amount of each raw material were changed to the charged amounts shown in Table 3, and the reaction was carried out under the same conditions and methods to obtain a polyurethane solution. Table 3 shows the properties and physical properties of this polyurethane.

[Comparative Examples 1 to 2]
<Production and evaluation of polycarbonate diol>
In the production of the polycarbonate diol of Example 1, the reaction was carried out under the same conditions and methods except that the types and amounts of the PCD polymerization raw materials were changed to the raw materials and the amounts of raw materials shown in Table 2. A containing composition was obtained.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Example 1.
Table 2 shows the evaluation results of properties and physical properties of polycarbonate diol obtained by thin film distillation.

<Manufacture and evaluation of polyurethane>
In the production of the polyurethane of Example 1, the polycarbonate diol (PCD) used
), And the amount of each raw material was changed to the amount shown in Table 3, and the reaction was carried out under the same conditions and methods to obtain a polyurethane solution. Table 3 shows the evaluation results of the properties and physical properties of this polyurethane.

In “Stress at −10 ° C./100% elongation” in Table 3, the value of the example is smaller than that of the comparative example, indicating that the flexibility at low temperature is good. Moreover, since the values of “80 ° C. oleic acid weight change rate” and “room temperature ethanol resistance change rate” are small, it can be seen that the chemical resistance is good. Furthermore, “Ratio 1, Ratio 2” shows that the low temperature characteristics are good. Therefore, it can be seen that the polycarbonate diol of the present invention is a polycarbonate diol as a raw material of polyurethane having an excellent balance of physical properties such as chemical resistance and low temperature characteristics as compared with the conventional polycarbonate diol.

The meanings of the abbreviations in Tables 1 and 2 are as follows.
1,4BD ... 1,4-butanediol 1,3PDO ... 1,3-propanediol 1,6HD ... 1,6-hexanediol 1,10DD ... 1,10-decanediol 1,12DDD ... 1,12-dodecanediol 2M1,3PDO ... 2-methyl-1,3-propanediol 2M1,8OD ... 2-methyl-1,8-octanediol DPC ... diphenyl carbonate

That is, the gist of the present invention is as follows.
[1] A polycarbonate diol having a hydroxyl value of 20 mg-KOH / g or more and 42 mg-KOH / g or less measured by a method using an acetylating reagent in accordance with JIS K1557-1 (2007), glass transition temperature measured by differential scanning calorimetry of the diol is not less -30 ° C. or less, Ri average 5.5 der less number 3 or more carbon atoms of the dihydroxy compounds obtained and hydrolyzing the polycarbonate diol, the dihydro
The xyl compounds are 1,3-propanediol, 1,4-butanediol and 2-methyl-1,
Polycarbonate diol, wherein at least one Tanedea Rukoto selected from the group consisting of 3-propanediol.
[2] The polycarbonate diol as described in [1] above, wherein the dihydroxy compound is only an aliphatic dihydroxy compound having no substituent.
[ 3 ] Melting heat of melting peak measured by differential scanning calorimeter is 5.0 J / g or more and 80 J
The polycarbonate diol as described in [1] or [2] above, which is / g or less.
[ 4 ] The above [1], wherein the dihydroxy compound includes a plant-derived compound.
The polycarbonate diol according to any one of to [ 3 ].
[ 5 ] A method for producing the polycarbonate diol according to any one of [1] to [ 4 ] above, wherein one or a plurality of dihydroxy compounds and diaryl carbonates having an average carbon number of 3 or more and 5.5 or less. And a transesterification reaction in the presence of a transesterification catalyst.
[ 6 ] The method for producing a polycarbonate diol according to the above [ 5 ], wherein the one or more kinds of dihydroxy compounds include a plant-derived compound.
[ 7 ] The transesterification catalyst is a compound of at least one element selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen) and long-period periodic table group 2 elements. The method for producing a polycarbonate diol as described in [ 5 ] or [ 6 ] above,
[ 8 ] Polyurethane using the polycarbonate diol according to any one of [1] to [ 4 ] above.

Claims (9)

A polycarbonate diol having a hydroxyl value of 20 mg-KOH / g or more and 45 mg-KOH / g or less, having a glass transition temperature measured by a differential operation calorimeter of the polycarbonate diol of −30 ° C. or less, and A polycarbonate diol, wherein the dihydroxy compound obtained by hydrolysis has an average carbon number of 3 or more and 5.5 or less. The polycarbonate diol according to claim 1, wherein the dihydroxy compound is only an aliphatic dihydroxy compound having no substituent. The dihydroxy compound is 1,3-propanediol, 1,4-butanediol and 1
The polycarbonate diol according to claim 2, comprising at least one selected from the group consisting of 1,5-pentanediol. The polycarbonate diol according to any one of claims 1 to 3, wherein the melting peak has a heat of fusion of 5.0 J / g or more and 80 J / g or less as measured by a differential operation calorimeter. The polycarbonate diol according to any one of claims 1 to 4, wherein the dihydroxy compound contains a plant-derived compound. A method for producing the polycarbonate diol according to any one of claims 1 to 5, wherein one or a plurality of dihydroxy compounds having an average carbon number of 3 or more and 5.5 or less and a diaryl carbonate are transesterified. A process for producing a polycarbonate diol, which comprises transesterification in the presence of The method for producing a polycarbonate diol according to claim 6, wherein the one or plural kinds of dihydroxy compounds contain a plant-derived compound. The transesterification catalyst is a compound of at least one element selected from the group consisting of long-period periodic table group 1 elements (excluding hydrogen) and long-period periodic table group 2 elements. The manufacturing method of the polycarbonate diol of Claim 7 or 8. A polyurethane comprising the polycarbonate diol according to claim 1.