JP2014136783A - Polycarbonate diol and method for producing the same as well as polyurethane using polycarbonate diol - Google Patents

Abstract

（式中、Ｒ^１およびＲ^２はそれぞれ独立に炭素数１〜１５の分岐を有している２価の基であり、前記炭素数の範囲でヘテロ原子を含有していてもよい。また、ｎは１以上の整数である。）
【選択図】 なしPROBLEM TO BE SOLVED: To provide a polycarbonate diol having an ether bond and a branched structure which exhibits a good balance of physical properties such as flexibility and low temperature characteristics when made into polyurethane.
A polycarbonate diol containing 5 to 50 mol% of a repeating unit represented by the following formula (1).

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms and may contain a hetero atom within the range of the carbon number. n is an integer of 1 or more.)
[Selection figure] None

Description

  The present invention relates to a novel polycarbonate diol and a method for producing the same. Further, the present invention relates to a polycarbonate-based polyurethane useful for use in elastic fibers, synthetic or artificial leather, high-performance elastomers, paints, coating agents and the like, which are produced using the polycarbonate diol of the present invention as a raw material and have excellent physical property balance.

  Conventionally, raw materials for the main soft segment parts of polyurethane resins produced on an industrial scale are ether type typified by polytetramethylene glycol, polyester polyol type typified by adipate ester, and polylactone typified by polycaprolactone. Type and polycarbonate type typified by polycarbonate diol (see Non-Patent Document 1, for example), especially polycarbonate type using polycarbonate diol is considered the best durability grade in heat resistance and hydrolysis resistance Widely used as durable films, automotive artificial leather, (water-based) paints, and adhesives.

  However, polycarbonate diols currently widely available are mainly polycarbonate diols using 1,6-hexanediol as a dihydroxy compound, and polyurethanes produced using these are soft segments when used for artificial leather and the like. The cohesiveness of the resin is high, and there is a problem that flexibility, elongation and bending at low temperatures, and elastic recovery are particularly poor, which limits the application. In addition, it has been pointed out that the artificial leather produced from this polyurethane as a raw material has a low softness and a hard texture, and has a “texture” worse than that of natural leather.

In order to solve these problems, a polycarbonate diol using a dihydroxy compound having a side chain as a raw material has been proposed.
For example, as a dihydroxy compound, a copolymerized polycarbonate diol using 1,6-hexanediol and 2,2-dialkyl-1,3-propanediol as raw materials has been proposed (see Patent Document 1).

On the other hand, in order to solve these problems, a polycarbonate diol using a dihydroxy compound having an ether bond as a raw material has been proposed.
For example, as a dihydroxy compound, a copolymer polycarbonate using 1,6-hexanediol and triethylene glycol as raw materials has been proposed (see Patent Document 2).

International Publication 2011-0774617 Pamphlet JP 2000-336139 A

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

According to a study by the present inventors, a polycarbonate diol using a dihydroxy compound having a side chain described in Patent Document 1 as a raw material does not provide sufficient flexibility when polyurethane is formed, and flexibility at low temperatures. Was not enough.
Further, according to a study by the present inventors, a polycarbonate diol using a dihydroxy compound having a linear ether bond described in Patent Document 2 as a raw material does not provide an appropriate flexibility when it is polyurethaneized. It was.

For this reason, none of the conventionally known polycarbonate diols have been well-balanced in terms of physical properties such as flexibility and low-temperature properties when made into polyurethane, and improvements have been awaited.
An object of the present invention is to provide a polycarbonate diol having an ether bond and a branched structure, which exhibits a good balance of physical properties such as flexibility and low-temperature properties when made into a polyurethane.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention. That is, it has been found that a polycarbonate diol containing a predetermined amount of a repeating unit having a specific branched structure and an ether structure can be easily produced with a desired molecular weight, and satisfies the above physical properties when made into polyurethane.
That is, the gist of the present invention is as follows.
[1] A polycarbonate diol containing 5 to 50 mol% of a repeating unit represented by the following formula (1).

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms and may contain a hetero atom within the range of the carbon number. n is an integer of 1 or more.)
[2] The polycarbonate diol according to [1], wherein the proportion of secondary hydroxyl terminal is 10 mol% or more with respect to all terminal groups of the polycarbonate diol.
[3] The polycarbonate diol as described in [1] or [2], wherein the ratio of the hydroxyl terminal to the total terminal group of the polycarbonate diol is 95 mol% or more.
[4] The polycarbonate diol according to any one of [1] to [3], wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. And n is an integer greater than or equal to 1.)
[5] In addition to the structural unit represented by the formula (1), an alkylene group having 1 to 15 carbon atoms, which may have a branched and / or ring structure, is contained as a repeating unit [1] To the polycarbonate diol according to any one of [4].
[6] A method for producing the polycarbonate diol according to any one of [1] to [5], wherein at least an ether diol having a structure represented by the following formula (3) and diphenyl carbonate are transesterified. A process for producing a polycarbonate diol characterized by comprising:

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms, and may contain a hetero atom within the range of the carbon number.)
[7] The method for producing a polycarbonate diol according to [6], wherein the ether diol represented by the formula (3) is an ether diol represented by the following formula (4).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. Nothing.)
[8] In addition to the ether diol represented by the formula (3), a diol having 1 to 15 carbon atoms which may have a branched structure, a ring structure and / or a hetero atom is reacted [6] or [7] The method for producing a polycarbonate diol according to [7].
[9] The method for producing a polycarbonate diol according to any one of [6] to [8], wherein the reaction is performed in the presence of a Group 2 metal compound of the periodic table.
[10] The method for producing a polycarbonate diol according to any one of [6] to [9], wherein the reaction temperature is 190 ° C. or lower.
[11] A polyurethane obtained by using the polycarbonate diol according to any one of [1] to [5].

When the polycarbonate diol of the present invention contains a repeating unit having a specific branched structure and ether structure, physical properties such as flexibility and low-temperature characteristics can be expressed in a well-balanced manner.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present specification, (meth) acrylate is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to the (meth) acryloyl group.

In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
[1. Polycarbonate diol]
<1-1. Polycarbonate diol>
The polycarbonate diol of the present invention is a polycarbonate diol characterized by containing 5 to 50 mol% of a repeating unit represented by the following formula (1).

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms, and may contain a hetero atom within the range of the carbon number. , N is an integer of 1 or more.)
R ¹ and R ² contained in the repeating unit represented by the formula (1) may be independently different groups or the same groups. The number of carbon atoms of these substituents is usually 1 or more, preferably 2 or more, more preferably 3 or more, in order to bring about the effects of the present invention. If the amount is too large, there is a tendency to cause a problem such as a decrease in polymerization reactivity. Therefore, it is usually 15 or less, preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less. . The repeating unit represented by the formula (1) is preferably a repeating unit represented by the following formula (2).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. And n is an integer greater than or equal to 1.)
R ³ , R ⁴ , R ⁵ and R ⁶ may be independently different groups or the same group. However, R ³ to R ⁶ are not all hydrogen atoms.

Examples of the alkyl group having 1 to 10 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. Groups; alkyl groups having a branched chain such as i-propyl group, i-butyl group, and t-butyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, and for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, and a t-butyl group are preferable.

Examples of the aryl group having 6 to 10 carbon atoms include simple aromatic ring derivatives such as phenyl group, tolyl group, benzyl group and xylyl group; and polycyclic aromatic ring derivatives such as biphenyl group, naphthyl group and anthracenyl group. Can be mentioned. Among them, an aryl group having 6 to 8 carbon atoms is preferable, and for example, a phenyl group, a tolyl group, a xylyl group, and the like are preferable.
Examples of the alkenyl group having 2 to 10 carbon atoms include an ethylene group, a propenyl group, a butenyl group, and a pentenyl group. Among them, an alkenyl group having 2 to 3 carbon atoms is preferable, and for example, an ethylene group and a propenyl group are preferable.

Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl group, propynyl group, butynyl group, and pentynyl group. Among them, an alkynyl group having 2 to 3 carbon atoms is preferable, and for example, an ethynyl group and a propynyl group are preferable.
Examples of the alkoxy group having 1 to 10 carbon atoms include linear alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, and n-butoxy group; i-propoxy group, i-butoxy group, t- Examples thereof include alkoxy groups having a branched chain such as a butoxy group. Among these, an alkoxy group having 1 to 3 carbon atoms is preferable, and for example, a methoxy group, an ethoxy group, and an n-propoxy group are preferable.

  When the hetero atom is contained within the carbon number range, examples of the substituent containing the hetero atom include a nitrile group, a nitro group, an amino group, an amide group, a methoxy group, an ethoxy group, an n-propoxy group, Substituents containing heteroatoms such as i-propoxy group, n-butoxy group, mercapto group, halogen atoms and the like can be mentioned. Of these, a nitro group and a halogen atom are preferable.

N in the formula (1) and the formula (2) is usually an integer of 1 or more. If the amount is too large, there is a tendency that the molecular weight of the polycarbonate diol increases and the viscosity increases, so that it is usually 15 or less, preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. More preferred.
Wherein ^R 3 Specific combinations of to R ^6, the combination ^{R 3} and ^{R 6} is ^{R 4} and ^{R 5} a hydrogen atom of an alkyl group, ^{R 4} and ^{R 6 R 3} and ^{R 5} are hydrogen atoms is an alkyl A combination of groups, a combination of R ⁴ and R ⁵ as a hydrogen atom, and R ³ and R ⁶ as an alkyl group, and the like. As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and the like are preferable.

  The repeating unit represented by the formula (1) (hereinafter may be referred to as “structure (1)”) may be continuously present in the polycarbonate diol, or may be present at regular intervals. Alternatively, it may exist unevenly. The content of the structure (1) in the polycarbonate diol is usually preferably 5% to 50%, more preferably 10% to 50%, and particularly preferably 20% to 40% in terms of a molar ratio.

By setting the ratio of the structure (1) in the polycarbonate diol to the lower limit or more, it is possible to obtain sufficient effects of imparting suitable flexibility and low temperature characteristics to the polyurethane, and suppressing the crystallinity of the polycarbonate diol and the polyurethane by the side chain. There is a tendency to be able to. Moreover, there exists a tendency which can suppress durability fall, such as a weather resistance, by setting it as the said upper limit or less.

The polycarbonate diol of the present invention usually has the structure (1) in at least a part of the molecular chain, but the structure different from the structure (1) in the molecular chain (hereinafter referred to as “other structure”) May have). Content of the said other structure should just be a range with which the effect of this invention is acquired, and can be suitably determined according to another structure.
As another structure, a C1-C15 alkylene group which may have a branched and / or ring structure is preferable. 2-12 are more preferable, as for carbon number of the said alkylene group, 3-12 are more preferable, and 4-10 are especially preferable.

  The content of other structures in the polycarbonate diol is usually 5% to 95% in molar ratio, preferably 25% to 95%, more preferably 50% to 90%, more preferably 50% to 90% is more preferable, and 60% to 80% is particularly preferable.

<1-2. Molecular Weight / Molecular Weight Distribution>
The lower limit of the number average molecular weight of the polycarbonate diol of the present invention is preferably 500, more preferably 1000, still more preferably 1500, and particularly preferably 2000. On the other hand, the upper limit is preferably 5000, more preferably 4000, and still more preferably 3000. By setting the number average molecular weight of the polycarbonate diol to be equal to or lower than the upper limit value, viscosity tends to be suppressed and handling during urethanization tends to be facilitated. Moreover, there exists a tendency which gives a softness | flexibility suitable for a polyurethane by making the number average molecular weight of polycarbonate diol more than a lower limit.

  The lower limit of the molecular weight distribution (Mw / Mn) of the polycarbonate diol of the present invention is preferably 1.5, and more preferably 2.0. On the other hand, the upper limit is preferably 4.0, more preferably 3.5, and particularly preferably 3.0. Here, Mw is a weight average molecular weight, and Mn is a number average molecular weight. The molecular weight distribution can be determined by, for example, measurement by gel permeation chromatography.

  When the molecular weight distribution exceeds the above upper limit, the properties of the polyurethane produced using this polycarbonate diol tend to deteriorate, such as hardening at low temperatures and poor elongation, and the molecular weight distribution is less than the above lower limit. In some cases, an advanced purification operation such as removal of oligomers may be required.

<1-3. Ratio of the number of molecular chain terminal structures being secondary hydroxyl groups>
The terminal structure of the polycarbonate diol of the present invention is usually a hydroxyl group, but at least two or more kinds selected from the group consisting of a primary hydroxyl end, a secondary hydroxyl end and a tertiary hydroxyl end depending on the structure of the formula (1). A hydroxyl terminal may be included. Since this hydroxyl group reacts with isocyanate during the polyurethane reaction, the structure of the hydroxyl group terminal affects the reactivity of the urethanization reaction. Among them, the tertiary hydroxyl terminal is low in reactivity with isocyanate, and therefore the molecular chain terminal structure is preferably composed of a primary hydroxyl terminal and / or a secondary hydroxyl terminal.

Primary hydroxyl group terminal to total end groups contained in the polycarbonate diol, secondary hydroxyl group-terminated and tertiary measurement of the proportion of terminal hydroxyl group of is not particularly limited as long seek its abundance, for example, of polycarbonate diol ¹ It can be easily determined from the integrated value of the H-NMR signal.
The upper limit of the ratio of secondary hydroxyl terminals to all terminal groups is not particularly limited, but is preferably 90 mol%, more preferably 80 mol%, still more preferably 70 mol%, Particularly preferred is 60 mol%. The lower limit is preferably 5 mol%, more preferably 10% mol, still more preferably 20% mol, and particularly preferably 30% mol.

  By making the above lower limit or more, physical properties such as flexibility and low temperature characteristics of urethane can be improved, and by making the above upper limit or less, a decrease in the reactivity of the urethanization reaction can be suppressed, and a sufficient reaction rate tends to be maintained. .

<1-4. Ratio of the number of molecular chain ends that are alkyloxy groups or aryloxy groups>
The terminal structure of the polycarbonate diol of the present invention is usually a hydroxyl group. However, some polycarbonate diols obtained by reaction of a dihydroxy compound and a carbonic acid diester may have a structure in which some of the ends of the polycarbonate diol are not hydroxyl groups as impurities. As specific examples of the structure, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many are structures derived from a carbonic acid diester.

For example, when diphenyl carbonate is used as a carbonic acid diester, a phenoxy group is used as an aryloxy group, a methoxy group is used as an alkyloxy group when dimethyl carbonate is used, an ethoxy group is used when diethyl carbonate is used, and ethylene carbonate is used. A hydroxyethoxy group may remain as a terminal group.
In the present invention, the lower limit of the ratio of the structure in which the terminal of the molecular chain contained in the polycarbonate diol is an alkyloxy group or an aryloxy group is not particularly limited, and is usually 0.01 mol%, and 0.001 mol % Is preferable, and 0 mol% is most preferable.

  In addition, the proportion of the structure in which the end of the molecular chain contained in the polycarbonate diol is a hydroxyl group is usually 95 mol% or more and 97 mol% or more of the total number of terminal groups. Preferably, it is 99 mol% or more, more preferably 99.5% or more, and particularly preferably 99.9% or more. If the proportion of alkyloxy or aryloxy groups at the end of the molecular chain is large, or the proportion of hydroxyl groups at the end of the molecular chain is small, the degree of polymerization will not increase when the polyurethane-forming reaction is performed. May occur.

<1-5. Hydroxyl value>
The polycarbonate diol of the present invention has a structure in which both terminal groups of the molecular chain are usually hydroxyl groups as described above, and this hydroxyl group can react with isocyanate during the polyurethane-forming reaction.
The hydroxyl value of the polycarbonate diol of the present invention is not particularly limited, but the lower limit is usually 10 mg-KOH / g, preferably 20 mg-KOH / g, more preferably 35 mg-KOH / g. The upper limit is usually 380 mg-KOH / g, preferably 230 mg-KOH / g, more preferably 160 mg-KOH / g, and particularly preferably 120 mg-KOH / g. If the hydroxyl value is less than the lower limit, the viscosity may be too high and handling during polyurethane formation may be difficult, and if it exceeds the upper limit, strength and hardness may be insufficient when polyurethane is used.
“Mg-KOH / g” is a unit expressed in mg of potassium hydroxide necessary to neutralize the amount of hydroxyl group contained in 1 g of polycarbonate diol.

<1-6. Ether structure>
The polycarbonate diol of the present invention usually has a structure in which a dihydroxy compound is polymerized by a carbonate group. However, depending on the production method, an ether bond may be formed as a by-product due to decarboxylation of the carbonate group. When the amount of by-products increases, the ether bond tends to increase excessively and cause a decrease in weather resistance and heat resistance.

  When a dihydroxy compound having an ether bond is used as a raw material in producing the polycarbonate diol of the present invention, the by-produced ether structure other than that derived from the raw material in the polycarbonate diol is reduced to ensure characteristics such as weather resistance and heat resistance. In this regard, the ratio of the ether bond and carbonate bond produced as a by-product other than that derived from the raw material contained in the molecular chain of the polycarbonate diol of the present invention is not particularly limited, but is usually 2/98 or less in molar ratio, 1/99. Or less, more preferably 0.5 / 99.5 or less.

<1-7. Impurity content>
<1-7-1. Phenols>
The content of the phenols contained in the polycarbonate diol of the present invention is not particularly limited, but is preferably less, preferably 0.1% by weight or less, more preferably 0.01% by weight or less, and 0% It is particularly preferable that the content be 0.001% by weight or less. This is because phenols are monofunctional compounds and thus may be polymerization inhibitors during polyurethane formation and are stimulating substances.

<1-7-2. Carbonic acid diester>
In the polycarbonate diol of the present invention, when a carbonic acid diester is used as a raw material during production, the carbonic acid diester may remain. The remaining amount of the carbonic acid diester in the polycarbonate diol of the present invention is not limited, but a smaller amount is preferable, usually 5% by weight or less, preferably 3% by weight or less, and preferably 1% by weight or less. Is more preferable. If the carbonic diester content of the polycarbonate diol is too large, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit thereof is not particularly limited and is usually 0.1% by weight, preferably 0.01% by weight, and most preferably 0% by weight.

<1-7-3. Dihydroxy Compound>
In the polycarbonate diol of the present invention, when a dihydroxy compound is used as a raw material during production, the dihydroxy compound may remain. The residual amount of the dihydroxy compound used as a raw material for the polycarbonate diol of the present invention is not limited, but a smaller amount is preferable, usually 10% by weight or less, preferably 5% by weight or less, preferably 3% by weight. More preferably, it is more preferably 1% by weight or less, still more preferably 0.1% by weight or less, and most preferably 0.01% by weight or less. If the residual amount of the dihydroxy compound used as a raw material in the polycarbonate diol is large, the molecular length of the soft segment portion when polyurethane is used may be insufficient.

<1-7-4. Transesterification Catalyst>
In the production of the polycarbonate diol of the present invention, as will be described later, it is possible to use a transesterification catalyst as necessary in order to accelerate the polymerization. In that case, the catalyst may remain in the obtained polycarbonate diol, but if too much catalyst remains, it becomes difficult to control the reaction during the polyurethane reaction, and the polyurethane reaction is accelerated more than expected. It is preferable that it does not remain.

  The upper limit of the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but from the viewpoint of obtaining a homogeneous polyurethane from this polycarbonate diol, the content in terms of catalyst metal is usually 100 ppm by weight, and preferably 50 ppm by weight. 30 ppm by weight is more preferable, and 10 ppm by weight is particularly preferable. Examples of the remaining metal include catalytic active component metals having transesterification ability described below.

Further, the lower limit of the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but it is usually 0.01 ppm by weight, preferably 0.1 ppm by weight, and preferably 1 ppm by weight as the content of the catalyst metal. More preferred is 5 ppm by weight.
The amount of the catalyst in the polycarbonate diol can be adjusted by the amount of catalyst used at the time of production, catalyst isolation by filtration of the product or the like, or catalyst extraction using a solvent such as water.

<1-8. Viscosity>
The polycarbonate diol of the present invention is usually a viscous liquid that is transparent at room temperature or a white solid, and its properties can be expressed by viscosity, for example. For example, the lower limit of the viscosity at 60 ° C. when measured with a cone plate viscometer is preferably 0.1 Pa · s, more preferably 1 Pa · s, and even more preferably 5 Pa · s. The upper limit is preferably 300 Pa · s, more preferably 200 Pa · s, still more preferably 100 Pa · s, particularly preferably 75 Pa · s, and preferably 50 Pa · s. Most preferred. By making the viscosity of the polycarbonate diol within the range, handling becomes easy.

<1-9. APHA value>
The polycarbonate diol of the present invention has a Hazen color number (JIS-K0071-1).
: Based on 1998) (hereinafter referred to as “APHA value”), it is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less. When the APHA value exceeds 50, the color tone of polyurethane obtained using polycarbonate diol as a raw material deteriorates, which causes a reduction in commercial value.

<1-10. Glass transition temperature>
The glass transition temperature of the polycarbonate diol of the present invention is usually −20 ° C. or lower, preferably −30 ° C. or lower, more preferably −40 ° C. or lower, for example, when measured with a differential scanning calorimeter. A temperature of −50 ° C. or lower is particularly preferable. By setting the glass transition temperature of the polycarbonate diol to be equal to or lower than the upper limit value, the obtained polyurethane tends to be prevented from becoming hard at a low temperature and to improve the touch feeling.

  Further, when a polyurethane is synthesized from a polycarbonate diol as a raw material, the glass transition temperature of the polyurethane is usually higher than that of the polycarbonate diol, but the difference in the glass transition temperature between the polycarbonate diol and the polyurethane (hereinafter, “ΔTg”). ")" Tends to be preferable to prevent polyurethane from becoming hard at low temperatures. ΔTg is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, further preferably 30 ° C. or lower, and particularly preferably 25 ° C. or lower.

[2. Reaction reagent]
The polycarbonate diol of the present invention comprises a dihydroxy compound having an ether bond that is a raw material that gives the structure (1), a dihydroxy compound such as a dihydroxy compound that is a raw material that gives another structure as necessary, and the carbonic acid diester described above. Can be produced by transesterification using a transesterification catalyst as necessary. The dihydroxy compound, carbonic acid diester and catalyst will be described below.

<2-1. Dihydroxy Compound>
Examples of the dihydroxy compound having an ether bond as a raw material that gives the structure (1) when a polycarbonate diol is used include the structure described in the following formula (3).

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms, and may contain a hetero atom within the range of the carbon number.)
Examples of the dihydroxy compound of the formula (3) include linear oxyalkylene glycols such as diethylene glycol, dibutylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrabutylene glycol, and polyethylene glycol; Oxyalkylene glycols having a side chain such as dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol; 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2 Hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy)- 3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl ) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) And compounds having an ether group bonded to an aromatic group in the main chain, such as phenyl) fluorene. These dihydroxy compounds may be used alone or in combination.

  Among these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the weather resistance of the polyurethane. The dihydroxy compound represented by the formula (3) is preferably a dihydroxy compound represented by the following formula (4).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. Nothing.)
As the structure of the alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, hetero atom of the formula (4), the alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, hetero atom of the formula (2) Those exemplified as the structure can be preferably used.

  The dihydroxy compounds having an ether bond as a raw material for providing the structure (1) may be used alone or in combination of two or more. Further, dihydroxy compounds which are isomer mixtures may be used. When dihydroxy compounds that are isomer mixtures are used, the randomness of the polycarbonate diol is increased, which is preferable in terms of suppressing the crystallinity of the polycarbonate diol and polyurethane using the polycarbonate diol as a raw material.

Examples of specific dihydroxy compounds giving other structures are usually branched structures, ring structures and / or diols having 1 to 15 carbon atoms which may have heteroatoms, preferably linear chains having 2 to 10 carbon atoms. Examples of the alkylene diol include the following.
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Dihydroxy compounds of linear hydrocarbons such as diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol; thioether diols such as bishydroxyethyl thioether; 2-methyl-1,3 -Propanediol, 2-ethyl-1,3-propanediol, 2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3 -Propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl- , 3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,2,4 , 4-tetramethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, dihydroxy compounds having a branched chain such as 2,2,9,9-tetramethyl-1,10-decanediol 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2′-bis (4-hydroxycyclohexyl) propane 1,4-dihydroxy Ethylcyclohexane, 4,4'-isopropylidene dicyclohexanol, 4,4'-isopropylidene Dihydroxy compounds having an alicyclic structure such as bis (2,2′-hydroxyethoxycyclohexane) and norbornane-2,3-dimethanol; 2,5-bis (hydroxymethyl) tetrahydrofuran, 3,4-dihydroxytetrahydrofuran, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 2- (5-ethyl-5-hydroxymethyl-1, Dihydroxy compounds containing a cyclic group having a hetero atom in the ring such as 3-dioxane-2-yl) -2-methylpropan-1-ol; nitrogen-containing diols such as diethanolamine and N-methyl-diethanolamine; Sulfur-containing dihydroxy compounds such as hydroxyethyl sulfide:
Among these dihydroxy compounds, industrial availability, and the resulting polycarbonate diol and polyurethane are excellent in physical properties. More preferable dihydroxy compounds include ethylene glycol and 1,3-propane as linear hydroxy dihydroxy compounds. Examples of dihydroxy compounds having a branched chain include diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and the like. Propanediol, 2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1, 3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl 1,5-pentanediol, 2,2,4,4-tetramethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol and the like are 1 as dihydroxy compounds having an alicyclic structure. , 3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 4,4'-isopropyl Examples of dihydroxy compounds containing a cyclic group having a heteroatom in the ring, such as lidene dicyclohexanol and norbornane-2,3-dimethanol, include 3,4-dihydroxytetrahydrofuran, 3,9-bis (1,1-dimethyl). -2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5 ] Undecane, 2- (5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl) -2-methylpropan-1-ol, and the like.

These dihydroxy compounds may be used individually by 1 type, and may use 2 or more types together.
<2-2. Carbonic acid diester>
The carbonic acid diester that can be used is not limited as long as the effects of the present invention are not lost, and examples thereof include alkyl carbonates, aryl carbonates, and alkylene carbonates. Of these, the use of aryl carbonate has the advantage that the reaction proceeds rapidly.

Specific examples of the dialkyl carbonate, diaryl carbonate, and alkylene carbonate of the carbonic acid diester that can be used for the production of the polycarbonate diol of the present invention are as follows.
Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, ethyl isobutyl carbonate, and preferably dimethyl carbonate and diethyl carbonate.

Examples of diaryl carbonates include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di m-cresyl carbonate, and preferably diphenyl carbonate.
Examples of alkylene carbonates include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2 -Pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, neopentyl carbonate, etc. Preferably, it is ethylene carbonate.

These may be used alone or in combination of two or more.
Among these, diaryl carbonate is preferable because it is rich in reactivity and efficient in industrial production, and diphenyl carbonate that is easily available at low cost as industrial raw material is more preferable.

<2-3. Transesterification Catalyst>
Any metal that can be used as a transesterification catalyst can be used without limitation as long as it is generally considered to have transesterification ability.
Examples of catalytic metals include Group 1 metals of the periodic table such as lithium, sodium, potassium, rubidium and cesium; Group 2 metals of the periodic table such as magnesium, calcium, strontium and barium; Group 4 metals of the periodic table such as titanium and zirconium Periodic group 5 metal such as hafnium; periodic group 9 metal such as cobalt; periodic group 12 metal such as zinc; periodic group 13 metal such as aluminum; periodic group 14 metal such as germanium, tin, lead; Examples include periodic table group 15 metals such as antimony and bismuth; lanthanide metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 5 metal, periodic table group 9 metal, periodic table 12 metal, periodicity A Group 13 metal and a Group 14 metal are preferable, a Group 1 metal and a Group 2 metal are more preferable, and a Group 2 metal is more preferable. Among the periodic table group 1 metals, lithium, potassium, and sodium are preferable, lithium and sodium are more preferable, and sodium is more preferable. Among the Group 2 metals of the periodic table, magnesium, calcium and barium are preferable, calcium and magnesium are more preferable, and magnesium is more preferable. These metals may be used as a simple metal or as a metal compound such as a hydroxide or a salt. Examples of salts when used as salts include: halide salts such as chloride, bromide, iodide; carboxylates such as acetate, formate, benzoate; methanesulfonic acid, toluenesulfonic acid, trifluoro Examples thereof include sulfonates such as romethanesulfonic acid; 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, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 5 metal, periodic table group 9 metal, periodic table 12 metal, periodic table group 13 metal, periodic table Group 14 metal acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides, and alkoxides are used, and more preferably acetates or carbonates of Group 1 metals or Group 2 metals of the Periodic Table. Salts and hydroxides are used, and more preferred are group 2 metal acetates.

These metals and metal compounds may be used individually by 1 type, and may use 2 or more types together.
Specific examples of compounds using Group 1 metals of the transesterification catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate , Sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate , Lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate; disodium salt of bisphenol A, dipotassium salt, cesium salt, dilithium salt; Thorium salt, potassium salt, cesium salt, a lithium salt; and the like.

  Examples of compounds using Group 2 metals in the periodic table include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, carbonate Examples include calcium, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenyl phosphate.

  Examples of compounds using Group 4 metal, Group 12 metal, and Group 14 metal of the periodic table include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate; titanium halides such as titanium tetrachloride; Zinc salts such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate; tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin Examples include tin compounds such as dimethoxide; zirconium compounds such as zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide; lead compounds such as lead (II) acetate, lead (IV) acetate, and lead (IV) chloride.

[3. Production method]
The polycarbonate diol of the present invention comprises a dihydroxy compound having an ether bond that is a raw material that gives the structure (1), a dihydroxy compound such as a dihydroxy compound that is a raw material that gives another structure as necessary, and the carbonic acid diester described above. Can be produced by transesterification using a transesterification catalyst as necessary. The manufacturing method will be described below.

<3-1. Usage ratio of raw materials>
In the production of the polycarbonate diol of the present invention, the amount of carbonic acid diester used is not particularly limited, but usually the lower limit is preferably 0.50 and preferably 0.70 in terms of a molar ratio to a total of 1 mol of dihydroxy compounds. More preferably, 0.80 is further preferable, 0.90 is still more preferable, 0.95 is particularly preferable, and 0.98 is most preferable. The upper limit is usually 1.20, preferably 1.15, more preferably 1.10. If the amount of carbonic acid diester used exceeds the above upper limit, the proportion of the polycarbonate diol end group that is not a hydroxyl group may increase, or the molecular weight may not be within a predetermined range to produce the polycarbonate diol of the present invention, If it is less than the lower limit, polymerization may not proceed to a predetermined molecular weight.

  In the production of the polycarbonate diol of the present invention, the ratio of the amount of the dihydroxy compound used as the raw material that gives the structure (1) and the amount of the dihydroxy compound used as the raw material that gives another structure is usually 99/1 to 1 in molar ratio. 1/99, preferably 90/10 to 10/90, more preferably 80/20 to 20/80, and even more preferably 70/30 to 30/70.

  When the transesterification catalyst is used in producing the polycarbonate diol of the present invention, the amount used is preferably an amount that does not affect the performance even if it remains in the obtained polycarbonate diol, and is a dihydroxy compound as a raw material The upper limit of the weight ratio in terms of metal relative to the weight of is preferably 200 ppm by weight, more preferably 100 ppm by weight, and even more preferably 50 ppm by weight. On the other hand, the lower limit is an amount that provides sufficient polymerization activity, and is preferably 0.01 ppm by weight, more preferably 0.1 ppm by weight, and even more preferably 1 ppm by weight.

<3-2. Reaction conditions>
There are no particular restrictions on the method of charging the reaction raw material, and a method in which the entire amount of the dihydroxy compound, carbonic acid diester and transesterification catalyst is charged simultaneously, or when the carbonic acid diester is a solid, the carbonic acid diester is first charged, heated and melted. A method of adding a dihydroxy compound and a transesterification catalyst after the addition, conversely, a method in which the dihydroxy compound is first charged and melted, and a carbonic acid diester and a transesterification catalyst are added thereto, a part of the dihydroxy compound and a carbonic acid diester Alternatively, the method can be freely selected, such as a method of reacting chlorocarbonates with a remaining dihydroxy compound after synthesizing a diester carbonate derivative of a dihydroxy compound. In the polycarbonate diol of the present invention, a method of adding a part of the dihydroxy compound to be used at the end of the reaction is adopted in order to make the ratio of the number of the molecular chain terminal alkyloxy group or aryloxy group to 5% or less. It is also possible to do. In that case, the upper limit of the amount of the dihydroxy compound added last is usually 20% of the amount of the dihydroxy compound to be charged, preferably 15%, more preferably 10%, and the lower limit is usually 0.00. 1%, preferably 0.5%, and more preferably 1.0%.

The reaction temperature in the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. The temperature is not particularly limited, but is usually 100 ° C. or higher, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 160 ° C. or higher. Further, it is usually 250 ° C. or lower, preferably 230 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 190 ° C. or lower, particularly preferably 180 ° C. or lower, Most preferably, it is 170 degrees C or less.

Exceeding the upper limit may cause quality problems such as coloration of the obtained polycarbonate diol, or by-production of an ether structure due to decarboxylation of carbonate groups or dehydration condensation between diols.
Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, it is usually preferable to carry out the reaction in the latter half of the reaction while employing a reduced pressure condition while distilling off the light boiling component. Or it is also possible to make it react, distilling off the light boiling component produced | generated by reducing pressure gradually from the middle of reaction.

In particular, it is preferable to increase the degree of vacuum at the end of the reaction because the by-produced monoalcohol and phenols can be distilled off.
The reaction pressure at the end of the reaction is not particularly limited, but the upper limit is usually 10 kPa, preferably 5 kPa, and more preferably 1 kPa. In order to effectively distill off these light boiling components, the reaction can be carried out while passing a small amount of an inert gas such as nitrogen, argon or helium into the reaction system.

  When using a low-boiling carbonic acid diester or dihydroxy compound in the transesterification reaction, the reaction is initially performed near the boiling point of the carbonic acid diester or dihydroxy compound, and the temperature is gradually raised as the reaction proceeds. A method of allowing the reaction to proceed can also be employed. In this case, the unreacted carbonic acid diester can be prevented from distilling off at the beginning of the reaction, which is preferable. Furthermore, it is also possible to attach the reflux pipe to the reactor in order to prevent the raw materials from distilling off at the initial stage of the reaction, and perform the reaction while refluxing the carbonic acid diester and the dihydroxy compound. In this case, it is preferable because the charged raw materials are not lost and the amount ratio of the reagents can be accurately adjusted.

<3-3. Reaction time>
The polymerization reaction is performed while measuring the molecular weight of the produced polycarbonate diol, and is terminated when the target molecular weight is reached. The reaction time required for polymerization varies greatly depending on the use and type of dihydroxy compound, carbonic acid diester, and transesterification catalyst to be used, so it cannot be specified unconditionally, but usually the reaction time required to reach a predetermined molecular weight Is not longer than 50 hours, preferably not longer than 20 hours, more preferably not longer than 10 hours.

<3-4. Catalyst deactivator, etc.>
As described above, when a transesterification catalyst is used in the polymerization reaction, the transesterification catalyst remains in the polycarbonate diol usually obtained, and the reaction can be controlled when the polyurethane-forming reaction is performed with the transesterification catalyst remaining. It may not be possible. In order to suppress the influence of this residual catalyst, a substantially equimolar amount of, for example, a phosphorus compound may be added to the transesterification catalyst used. Furthermore, after the addition, the transesterification catalyst can be inactivated efficiently by heat treatment as described later.

Examples of phosphorus compounds used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, And organic phosphate esters such as triphenyl phosphate.
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 contained in the polycarbonate is not sufficiently deactivated. When the obtained polycarbonate diol is used as a raw material for polyurethane production, for example, the isocyanate of the polycarbonate diol is used. In some cases, the reactivity to the 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 heated. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150 ° C., more preferably 120 ° C., still more preferably 100 ° C., and the lower limit is preferably 50 ° C., more preferably 60 ° C., even more preferably. Is 70 ° C. When the temperature is lower than this, it takes time to deactivate the transesterification catalyst, which is not efficient, and the degree of deactivation may be insufficient. On the other hand, at a temperature exceeding the upper limit, the obtained polycarbonate diol may be colored.
The time for reacting with the phosphorus compound is not particularly limited, but is usually 1 to 5 hours.

<3-5. Polymerization reactor>
The polymerization reaction (polycondensation reaction) can be carried out either batchwise or continuously, but the continuous method is superior in terms of the stability of the quality such as the molecular weight of the product. The apparatus to be used may be any of a tank type, a tube type and a tower type, and a known polymerization tank equipped with various stirring blades can be used. The atmosphere during the temperature rise of the apparatus is not particularly limited, but it is preferably performed in an inert gas such as nitrogen gas under normal pressure or reduced pressure from the viewpoint of product quality.

<3-6. Purification>
After the polymerization reaction, the purpose is to remove impurities in which the terminal structure in the polycarbonate diol is an alkyloxy group, impurities that are an aryloxy group, phenols, dihydroxy compounds and carbonic acid diesters as raw materials, and added catalysts, etc. Purification can be performed with In the purification at that time, a method of distilling off a light boiling compound by distillation can be employed. The specific method of distillation is not particularly limited, such as vacuum distillation, steam distillation, thin film distillation, etc., but thin film distillation is particularly effective. Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent solution or the like. In that case, the compound dissolved in water can be selected arbitrarily.

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

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

By setting the temperature for keeping the polycarbonate diol just before the thin film distillation to the lower limit or more, there is a tendency to prevent the flowability of the polycarbonate diol just before the thin film distillation from being lowered. On the other hand, by setting it to the upper limit or less, there is a tendency to prevent the polycarbonate diol obtained after thin film distillation from being colored.

[4. Polyurethane]
<4-1. Production of polyurethane>
In the method for producing polyurethane using the polycarbonate diol of the present invention, known urethanization reaction conditions for producing polyurethane are usually used. For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol of the present invention with an organic polyisocyanate in the range of room temperature to 200 ° C.
In addition, the polycarbonate diol of the present invention can be reacted first with an excess of organic polyisocyanate to produce a terminal isocyanate polymer, and a polyurethane can be produced by increasing the degree of polymerization using a chain extender.

<4-1-1. Organic Diisocyanate>
Examples of the organic diisocyanate used for producing polyurethane using the polycarbonate diol of the present invention include various known diisocyanate compounds such as aliphatic, alicyclic or aromatic.

For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimerized isocyanate in which the carboxyl group of dimer acid is converted to an isocyanate group Aliphatic diisocyanates; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,3-bis (Isocyanatomethyl) cycloaliphatic diisocyanates such as cyclohexane; xylylene diisocyanate, 4,4′-dipheni Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4 ' -Dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethyl Representative examples include aromatic diisocyanates such as xylylene diisocyanate alone or mixtures of two or more. .

Among these, preferred organic diisocyanates are 4,4′-diphenylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, hexamethylene in terms of the balance of physical properties of the resulting polyurethane and the availability of a large amount at an industrially low cost. Diisocyanates and isophorone diisocyanates.

<4-1-2. Chain extender>
The chain extender used in producing the polyurethane of the present invention is a low molecular weight compound having at least two active hydrogens that react with an isocyanate group, and usually includes polyols and polyamines.

Specific examples include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4-heptanediol, 1,8-octane. Linear diols such as diol, 1,4-dimethylolhexane, 1,9-nonanediol, 1,12-dodecanediol and dimer diol; 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-ethyl-1,3-hexanediol, 2,2, 4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol and 2-butyl-2-ethyl Diols having a branched chain such as ru-1,3-propanediol; Diols having a cyclic group such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane; Xylylene Glycol, 1,4-dihydroxyethylbenzene and 4,4′-methylenebis (
Diols having aromatic groups such as hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diamino Propane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2-
Hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis (o-chloroaniline) ), Polyamines such as xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine and N, N′-diaminopiperazine, and water.

  Among these, preferred chain extenders are preferably 1,4-butanediol, 1,5-pentanediol, 1,5-butanediol, and the like because the balance of physical properties of the obtained polyurethane is preferable, and a large amount can be obtained industrially at low cost. Examples include 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, and 1,3-diminopropane. . These chain extenders can be used alone or in combination of two or more.

<4-1-3. Chain terminator>
Further, for the purpose of controlling the molecular weight of the obtained polyurethane, a chain terminator having one active hydrogen group can be used as necessary. Examples of the chain terminator include aliphatic monools such as ethanol, propanol, butanol and hexanol having a hydroxyl group; and aliphatic monoamines such as diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having an amino group. Can be mentioned. These may be used alone or in combination of two or more.

<4-1-4. Catalyst>
In these polyurethane-forming reactions, tin-based compounds such as amine-based catalysts such as triethylamine, N-ethylmorpholine and triethylenediamine or tin-based catalysts such as trimethyltin laurate and dibutyltin dilaurate, and organic metals such as titanium-based compounds Known urethane polymerization catalysts represented by salts and the like can also be used.

<4-1-5. Polyol>
In addition to the polycarbonate diol of the present invention, a known polyol may be used in combination as necessary. Known polyols that can be used in this case include, for example, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol (PTMG); ethylene oxide adducts and propylene adducts of bisphenol A or glycerin. Examples include alkylene oxide adducts of polyalcohols; polyester polyols, polycaprolactone polyols and polycarbonate polyols.

  Examples of the polyester polyol include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, maleic acid, succinic acid, and fumaric acid, and ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, Examples include polyester polyols obtained from glycols such as 1,5-pentanediol, 1,6-hexanediol, and trimethylolpropane.

  Further, as the polycarbonate diol, for example, homopolycarbonate diol and copolymer produced from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol and 2-methylpropanediol. Examples of the polycarbonate diol that can be used include polycarbonate diol.

<4-1-6. Solvent>
A solvent may be used for the polyurethane forming reaction. Preferred solvents include amide solvents such as dimethylformamide, diethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran and dioxane; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; acetic acid And ester solvents such as methyl, ethyl acetate and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene.

These solvents can be used alone or as a mixed solvent of two or more. Among these, methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like are preferable.
A polyurethane resin in an aqueous dispersion can also be produced from the polyurethane resin composition in which the polycarbonate diol of the present invention, the organic diisocyanate, and the low molecular weight compound having at least two hydrogen atoms that react with the isocyanate group are blended. .

<4-1-7. Manufacturing method>
In order to produce polyurethane using the reaction reagent, all production methods generally used experimentally / industrially can be used.
Examples thereof include a method in which the polycarbonate diol of the present invention, an organic polyisocyanate, and a chain extender are reacted together (hereinafter referred to as a one-step method). There is a method in which a prepolymer of a group is prepared and then the prepolymer is reacted with a chain extender (hereinafter referred to as a two-stage method).

Among these, the two-stage method is a process in which a polycarbonate diol is reacted with one or more equivalents of an organic polyisocyanate in advance to prepare a both-end isocyanate intermediate corresponding to the soft segment of the polyurethane.
Once the prepolymer is prepared and reacted with the chain extender, it has the advantage of easy adjustment of the molecular weight of the soft segment part, and the phase separation of the soft segment and hard segment can be performed firmly, and the performance as a polyurethane It is easy to give out.

<4-1-7-1. One-step method>
The one-stage method is also called a one-shot method, and is a method in which a reaction is carried out by charging polycarbonate diol, organic polyisocyanate and chain extender all at once.
The amount of the organic polyisocyanate compound used in the one-step method is, when the total number of hydroxyl groups of the polycarbonate diol and the number of hydroxyl groups and amino groups of the chain extender is 1 equivalent, the lower limit is
Usually, it is preferably 0.7 equivalent, more preferably 0.8 equivalent, still more preferably 0.9 equivalent, and particularly preferably 0.95 equivalent. The upper limit is usually preferably 3.0 equivalents, more preferably 2.0 equivalents, still more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

By making the usage-amount of the said polyisocyanate below the said upper limit, it exists in the tendency which prevents that an unreacted isocyanate group raise | generates an unfavorable reaction and obtains a desired physical property easily. Moreover, by setting it as the said minimum or more, there exists a tendency which can fully increase the molecular weight of a polyurethane and a polyurethane urea, and can express desired performance.
The amount of the chain extender used is not particularly limited, but when the number obtained by subtracting the number of isocyanates from the number of hydroxyl groups in the polycarbonate diol is defined as 1 equivalent, the lower limit is usually preferably 0.7 equivalents. It is more preferably 8 equivalents, still more preferably 0.9 equivalents, and particularly preferably 0.95 equivalents. The upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, still more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

  By setting the amount of the chain extender to be not more than the above upper limit, it is possible to prevent the obtained polyurethane and polyurethane urea from becoming too hard, to obtain desired characteristics, and to be easily soluble in a solvent and easy to process. . Moreover, by setting it as the said lower limit or more, there exists a tendency which can prevent becoming too soft, can obtain sufficient intensity | strength, elastic recovery performance, and elastic retention performance, and can improve a high temperature characteristic.

<4-1-7-2. Two-stage method>
The two-stage method is also called a prepolymer method. In the two-stage method, a prepolymer having an isocyanate group at the terminal obtained by reacting an organic polyisocyanate compound and a polycarbonate diol at a reaction equivalent ratio of 1.0 to 10.00 in advance is produced. Next, a polyurethane is produced by adding a chain extender having active hydrogen such as a polyhydric alcohol and an amine compound thereto.

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 compound and a polycarbonate diol are directly reacted to synthesize a prepolymer, and the prepolymer is used as it is in the subsequent chain extension reaction.

(2) A prepolymer is synthesized by the method of (1), and the prepolymer is then dissolved in a solvent and used in the subsequent chain extension reaction.
(3) The polyisocyanate and the polycarbonate diol are reacted from the beginning using a solvent, and then a chain extension reaction is performed in the solvent.
In the case of (1), when the chain extender is allowed to act on the chain extender, the polyurethane is allowed to coexist with the solvent by dissolving the chain extender in the solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is important to get.

The amount of the organic polyisocyanate used in the two-stage method is preferably 1.05 as the lower limit, usually 1.05, as the number of isocyanate groups when the number of hydroxyl groups in the polycarbonate diol is 1 equivalent. More preferably, the upper limit is usually preferably 10.0, more preferably 5.0, and even more preferably in the range of 3.0.
By setting the amount of the organic polyisocyanate to be not more than the above upper limit, there is a tendency to prevent excessive isocyanate groups from causing side reactions and undesirably affecting the physical properties of the polyurethane. Moreover, by setting it as the said lower limit or more, there exists a tendency for the molecular weight of the obtained polyurethane to rise sufficiently and to obtain sufficient intensity | strength and thermal stability.

The amount of the chain extender used is not particularly limited, but the lower limit is usually preferably 0.1, more preferably 0.5, more preferably 0,0 with respect to the equivalent of the isocyanate group contained in the prepolymer. More preferably, it is 8. Moreover, it is preferable that an upper limit is 5.0 normally, It is more preferable that it is 3.0, It is still more preferable that it is 2.0.
In addition, a monofunctional organic amine or alcohol may coexist for the purpose of adjusting the molecular weight during the chain extension reaction.

  In the chain extension reaction, it is usually preferable to react each component at 0 to 250 ° C. The temperature of the chain extension reaction varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, etc., and is not particularly limited. By setting the temperature of the chain extension reaction to the above lower limit or more, the reaction proceeds sufficiently, the solubility of the raw materials and the polymer is sufficient, and the productivity tends to be improved. Moreover, there exists a tendency to suppress a side reaction and decomposition | disassembly of a polyurethane resin by setting it as the said upper limit or less. The chain extension reaction may be performed while degassing under reduced pressure.

In the chain extension reaction, a catalyst, a stabilizer and the like can be added as necessary.
Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid.
Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-betanaphthylphenylenediamine, and tri (dinonylphenyl) phosphite.

However, when the chain extender is highly reactive such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.
<4-1-8. Water-based polyurethane emulsion>
It is also possible to produce an aqueous polyurethane emulsion using the polycarbonate diol of the present invention.

In that case, when preparing a prepolymer by reacting polycarbonate diol and organic polyisocyanate, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is mixed to form a prepolymer. This is reacted with a chain extender to form a polyurethane emulsion.
The hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is a group that can be neutralized with an alkaline group, such as a carboxylic acid group and a sulfonic acid group. Etc.

The isocyanate-reactive group is a group that generally reacts with an isocyanate such as a hydroxyl group, a primary amino group, and a secondary amino group to form a urethane bond or a urea bond, and these are the same in the same molecule. It does not matter if they are mixed.
Specifically, 2,2′-dimethylolpropionic acid, 2,2-methylolbutyric acid and 2
2,2'-dimethylol valeric acid and the like. Also, diaminocarboxylic acids, such as
Examples include lysine, cystine and 3,5-diaminocarboxylic acid.

  In the case of actually using the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups, amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine are used. And neutralized with an alkaline compound such as sodium hydroxide, potassium hydroxide and ammonia.

  When an aqueous polyurethane emulsion is produced, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is used in order to increase the dispersion performance in water. It is usually preferably 1%, more preferably 5%, still more preferably 10% based on the weight of the polycarbonate diol.

On the other hand, in order to maintain the characteristics of the polycarbonate diol of the present invention, the upper limit is usually preferably 50%, more preferably 40%, and further preferably 30%.
In addition, in the synthesis or storage of water-based polyurethane emulsions, representatives include higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonates, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oil, and sulfosuccinate esters. Cationic surfactants such as anionic surfactants, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts and pyridinium salts, or ethylene oxide and long chain fatty alcohols or phenols The emulsion stability may be maintained by using a nonionic surfactant or the like typified by a known reaction product.

When the prepolymer is reacted with a chain extender to form a polyurethane emulsion, the prepolymer may be neutralized as necessary and then dispersed in water.
The water-based polyurethane emulsion thus produced can be used for various applications. In particular, recently, there has been a demand for chemical raw materials with a small environmental load, and it is possible to substitute conventional products for the purpose of not using an organic solvent.

As specific applications, for example, use in water-based paints, adhesives, synthetic leather and artificial leather is suitable. In particular, the synthetic leather and artificial leather produced using the polycarbonate diol of the present invention have a structure in which the terminal of the polycarbonate diol is HOCH ₂ C (CH ₃ ) _2- , and thus flexibility, elasticity and low-temperature stretchability are obtained. And the texture of leather is improved, so that it can be used more advantageously than the conventional polycarbonate diol.

<4-1-9. Other additives>
The polyurethane produced using the polycarbonate diol of the present invention includes a heat stabilizer and a light stabilizer, a colorant, a filler, a stabilizer, an ultraviolet absorber, an antioxidant, an anti-tacking agent, a flame retardant, an anti-aging agent, and Additives such as inorganic fillers can be added or mixed as long as the properties of the polyurethane of the present invention are not impaired.

  Compounds that can be used as thermal 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 the hindered phenol compound include Irganox 1010 (trade name: manufactured by Ciba Geigy) and Irganox 1520 (trade name: manufactured by Ciba Geigy). Examples of the phosphorus compound include PEP-36, PEP-24G, HP-10 [all trade names: manufactured by Asahi Denka Co., Ltd.] and Irgafos 168 (trade names: manufactured by Ciba-Gaigi Co., Ltd.).

Specific examples of the sulfur-containing compound include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).
Examples of the light stabilizer include benzotriazole and benzophenone compounds. Specifically, for example, “TINUVIN 622LD”, “TINUVIN 765” (manufactured by Ciba Specialty Chemicals), “SANOL LS-2626” and “SANOL LS-765” (manufactured by Sankyo) are used. Is possible.

Examples of the ultraviolet absorber include “TINUVIN 328” and “TINUVIN 234” (manufactured by Ciba Specialty Chemicals).
Examples of the colorant include direct dyes, acid dyes, basic dyes and metal complex dyes, inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; and coupling azo-based, condensed azo And organic pigments such as those based on anthraquinone, thioindigo, dioxazone and phthalocyanine.

Examples of the inorganic filler include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, and clay.
Examples of the flame retardant include addition of a phosphorus and halogen-containing organic compound, bromine or chlorine-containing organic compound, ammonium polyphosphate, aluminum hydroxide, and antimony oxide, and a reactive flame retardant.

These additives may be used alone or in combination of two or more.
The additive amount of these additives is% by weight with respect to the polyurethane, and the lower limit is preferably 0.01%, more preferably 0.05%, still more preferably 0.1%. . Further, the upper limit is preferably 10%, more preferably 5%, and even more preferably 1%.

<4-2. Polyurethane film and plate>
When a polyurethane film is produced using the polyurethane of the present invention, the lower limit of the thickness of the film is usually preferably 10 μm, more preferably 20 μm, still more preferably 30 μm. Moreover, it is preferable that an upper limit is 1000 micrometers normally, It is more preferable that it is 500 micrometers, It is still more preferable that it is 100 micrometers.

By setting the thickness of the polyurethane film to the upper limit or less, sufficient moisture permeability tends to be obtained. Moreover, by setting it as more than a minimum, generation | occurrence | production of a pinhole is suppressed, there exists a tendency which prevents a film blocking and is easy to handle.
The polyurethane film can be preferably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. The film may be applied to a support such as a cloth or a non-woven fabric. In this case, the thickness of the polyurethane film itself may be even thinner than 10 μm.

It is also possible to produce a polyurethane plate using the polyurethane of the present invention. In that case, the upper limit of the thickness of the plate is not particularly limited, and the lower limit is usually preferably 0.5 mm, more preferably 1 mm, still more preferably 3 mm.
The polyurethane according to the present invention has a tensile elongation at break at room temperature of a strip-shaped sample having a width of 10 mm, a length of 100 mm and a thickness of 40 μm, a distance between chucks of 50 mm, a tensile speed of 500 mm / min, a temperature of 23 ° C. and a relative humidity of 55. When measured in%, the lower limit is usually preferably 400%, more preferably 500%, still more preferably 550%, 600%
It is particularly preferred that The upper limit is usually preferably 1200%, more preferably 1000%, still more preferably 900%, and particularly preferably 800%.

By setting the tensile elongation at break of the polyurethane to the lower limit value or more, the urethane obtained becomes more flexible, and there is a tendency that the texture can be improved when a synthetic leather or the like is used. Moreover, there exists a tendency which can suppress that the urethane obtained becomes rubbery by making tensile fracture elongation into the said upper limit or less.
Regarding the tensile strength of the polyurethane of the present invention at room temperature, it is a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm, a distance between chucks of 50 mm, a tensile speed of 500 mm / min, a temperature of 23 ° C., and a relative humidity of 55%. The lower limit is usually preferably 1 MPa or more, more preferably 2 MPa or more, further preferably 3 MPa or more, and more preferably 4 MP or more. Is particularly preferred.

  Further, the upper limit is usually preferably 10 MPa or less, more preferably 8 MPa or less, still more preferably 6 MPa or less, and particularly preferably 5 MPa or less. By setting the tensile strength of the polyurethane to the upper limit value or less, sufficient flexibility can be obtained and the tactile sensation tends to be improved. Moreover, there exists a tendency which can give a moderate elasticity feeling to the polyurethane obtained by making tensile strength more than the said lower limit.

  Further, regarding the tensile rupture stress at room temperature of the polyurethane of the present invention, a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm, a distance between chucks of 50 mm, a tensile speed of 500 mm / min, a temperature of 23 ° C., When measured at a humidity of 55%, the lower limit is usually preferably 30 MPa, more preferably 40 MPa, and even more preferably 50 MPa. The upper limit is usually preferably 100 MPa, more preferably 90 MPa, still more preferably 80 MPa, and particularly preferably 70 MPa.

  The tensile elongation at break of the polyurethane of the present invention at low temperature was measured at a temperature of −10 ° C. with a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm at a distance between chucks of 50 mm and a tensile speed of 500 mm / min. In this case, the lower limit is usually preferably 300%, more preferably 400%, still more preferably 450%, and particularly preferably 500%. Further, the upper limit is usually preferably 1200%, more preferably 1000%, and still more preferably 800%.

By setting the tensile breaking elongation at −10 ° C. of the polyurethane to the lower limit value or more, the obtained urethane tends to maintain flexibility even at a low temperature.
Regarding the low-temperature tensile strength of the polyurethane of the present invention, it was measured at a temperature of −10 ° C. using a strip-shaped sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm at a chuck distance of 50 mm and a tensile speed of 500 mm / min. When evaluated by stress at 300% elongation, the lower limit is usually preferably 1 MPa or more, more preferably 3 MPa or more, further preferably 5 MPa or more, and particularly preferably 10 MPa or more.

  Further, the upper limit is usually preferably 50 MPa or less, more preferably 40 MPa or less, still more preferably 30 MPa or less, and particularly preferably 25 MPa or less. By making the tensile strength of the polyurethane not more than the upper limit value, the obtained urethane tends to be prevented from becoming hard at a low temperature and the touch feeling can be improved.

Further, regarding the tensile breaking stress at low temperature of the polyurethane of the present invention, a strip-shaped sample having a width of 10 mm, a length of 100 mm and a thickness of 40 μm, a distance between chucks of 50 mm, and a tensile speed of 50
When measured at 0 mm / min at a temperature of −10 ° C., the lower limit is usually preferably 30 MPa, more preferably 40 MPa, still more preferably 50 MPa, and particularly preferably 60 MPa. Moreover, it is preferable that an upper limit is 100 MPa normally, It is more preferable that it is 90 MPa, It is still more preferable that it is 80 MPa.

  Regarding the elastic retention rate, the elastic retention rate defined by the ratio of the stress at 150% elongation at the first contraction to the stress at 150% elongation at the first elongation in the 300% elongation-shrinkage repetition test at 23 ° C. (Hr1 / H1) is usually preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, and particularly preferably 40% or more.

Similarly, the elastic retention (Hr5 / H5) defined by the ratio of the stress at 150% elongation at the time of the fifth contraction to the stress at 150% elongation at the time of the fifth elongation (Hr5 / H5) is usually preferably 30% or more. It is more preferably 50% or more, further preferably 70% or more, and particularly preferably 85% or more.
Also, in a 300% elongation-shrinkage repetition test at 23 ° C., the elastic retention rate (H2 / H1) defined by the ratio of the stress at 150% elongation at the second elongation to the stress at 150% elongation at the first elongation. ) Is usually preferably 20% or more, more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more.

  The lower limit of the glass transition temperature of the polyurethane of the present invention is usually −70 ° C. or higher, preferably −60 ° C. or higher, more preferably −50 ° C. or higher, and further preferably −40 ° C. or higher. A temperature of −30 ° C. or higher is particularly preferable. The upper limit is usually 0 ° C. or lower, preferably −5 ° C. or lower, more preferably −10 ° C. or lower, still more preferably −15 ° C. or lower, and −20 ° C. or lower. Is particularly preferred. By setting the glass transition temperature of the polyurethane to the upper limit value or less, it is possible to prevent the resulting urethane from becoming hard at a low temperature and to improve the touch feeling.

  Regarding the solution viscosity at 25 ° C. of the polyurethane of the present invention, for example, when a dimethylformamide solution having a solid content concentration of 30% by weight is measured with a cone plate viscometer, the lower limit is usually 10 Pa · s or more, and 20 Pa · s ° C. It is preferable that it is above, and it is more preferable that it is 30 Pa · s ° C. or higher. The upper limit is usually 200 Pa · s or less, preferably 150 Pa · s or less, more preferably 100 Pa · s ° C. or less, and particularly preferably 50 Pa · s or less. By setting the solution viscosity of the polyurethane to the upper limit value or less, operability when forming urethane such as film formation tends to be improved.

<4-3. Polyurethane moldings and applications>
The polyurethane and the urethane prepolymer solution of the present invention can express various properties, such as foam, elastomer, paint, fiber, adhesive, flooring, sealant, medical material, artificial leather, coating agent, and water-based polyurethane. It can be widely used for paints and the like.

<4-3-1. Cast polyurethane elastomer>
The polyurethane and the urethane prepolymer solution of the present invention can be used for cast polyurethane elastomers. Examples thereof include rolls such as rolling rolls, papermaking rolls, office equipment and pretension rolls, solid tires such as forklifts, automobile vehicle neutrals, trolleys and transporters, and casters. Industrial products include conveyor belt idlers, guide rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones and cyclone liners. Furthermore, it can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, and surface rollers.

<4-3-2. Thermoplastic elastomer>
The polyurethane and its urethane prepolymer solution of the present invention are also applied for use as a thermoplastic elastomer. For example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment and industrial robots used in the food and medical fields.

Further, it is used as a belt such as a round belt, a V belt, and a flat belt in various transmission mechanisms, spinning machines, packing equipment, printing machines, and the like.
It can also be used for equipment parts such as footwear heel tops and shoe soles, couplings, packings, pole joints, bushes, gears and rolls, sports equipment, leisure goods and watch belts.

  Furthermore, examples of the automobile parts include oil stoppers, gear boxes, spacers, chassis parts, interior parts, tire chain substitutes, and the like. In addition, it can be used for films such as keyboard films and automobile films, curl cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leather, depinning products and adhesives.

<4-3-3. Solvent-based two-component paint>
The polyurethane and its urethane prepolymer solution of the present invention can also be applied as a solvent-based two-component paint, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood and sports equipment. Moreover, it can be used for automobile repair as tar epoxy urethane.

The polyurethane of the present invention and its urethane prepolymer solution are used as components of moisture-curable one-component paints, blocked isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet curable paints, water-based urethane paints, and the like. Is possible.
For example, plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring, paper, wood-printed film and other overprint varnishes, wood varnishes, high processing coil coats, optical fiber protective coatings, solder resists It can be applied to top coats for metal printing, base coats for vapor deposition, and white coats for food cans.

<4-3-4. Adhesive>
The polyurethane and its urethane prepolymer solution produced in the present invention can be applied as adhesives to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood and structural members, etc. It can also be used as a component of a melt.
When the polyurethane of the present invention is used as an adhesive, the obtained polyurethane is dissolved in a solvent and used as a solvent-type adhesive, or it can be used as a hot-melt adhesive without using a solvent. Is also possible.

  The solvent that can be used in the case of using a solvent is not particularly limited as long as it is suitable for the properties of the urethane to be obtained, and both aqueous and organic solvents can be used. In particular, recently, there has been an increasing demand for an aqueous adhesive in which an aqueous polyurethane emulsion is dissolved or dispersed in an aqueous solvent in order to reduce the burden on the environment, and the polyurethane of the present invention can be suitably used for that purpose.

  Furthermore, in the adhesive produced using the polyurethane of the present invention, additives and auxiliaries used in ordinary adhesives can be mixed without limitation if necessary. Examples of additives include pigments, solvents, anti-blocking agents, dispersion stabilizers, viscosity modifiers, leveling agents, anti-gelling agents, light stabilizers, antioxidants, ultraviolet absorbers, heat resistance improvers, inorganic and Examples include organic fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, and catalysts.

  As a method for blending the additive, a known method such as stirring and dispersion can be employed. The adhesive of the present invention thus obtained is made of metal materials such as iron, copper, aluminum, ferrite and plated steel plate, resin materials such as acrylic resin, polyester resin, ABS resin, polyamide resin, polycarbonate resin and vinyl chloride resin. In addition, inorganic materials such as glass and ceramic can be efficiently bonded.

<4-3-5. Binder>
The polyurethane of the present invention and its urethane prepolymer solution are used as binders 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. And glass fiber sizing.

<4-3-6. Textile finishing agent>
The polyurethane and the urethane prepolymer solution of the present invention can be used as a component of a fiber processing agent for shrink-proofing, anti-molding and water-repellent finishing.
<4-3-7. Elastic fiber>
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, it is possible to employ a melt spinning method in which the pellet is once melted and then melted and directly spun through a spinneret.

When the polyurethane elastic fiber of the present invention is obtained by melt spinning, the spinning temperature is preferably 250 ° C. or lower, more preferably 235 ° C. or lower. Moreover, it is preferable that it is 200 degreeC or more.
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 these, polyester fibers are preferably used in the present invention.

The polyurethane elastic fiber of the present invention may contain a dyeing type disperse dye.
As specific application fields of the polyurethane elastic fiber of the present invention, for example, clothing (for) such as swimwear, ski wear, cycling wear, leotard, lingerie, foundation, underwear, hat, gloves, pantyhose and socks Non-clothing items such as products, medical products such as bandages and supporters, and tennis racket guts, monolithic car seat ground yarns and metallized yarns for robot arms.

<4-3-8. Sealant Caulking>
The polyurethane of the present invention and its urethane prepolymer solution are used as a sealant caulking for concrete wall, induction joint, sash area, wall PC joint, ALC joint, board joint, composite glass sealant, heat insulating sash sealant and automobile. It can be used for sealants.

<4-3-9. Medical Materials>
The polyurethane and its urethane prepolymer solution of the present invention can be used as medical materials. For example, it can be used as blood compatible materials such as tubes, catheters, artificial hearts, artificial blood vessels and artificial valves, and disposable materials such as catheters, tubes, bags, surgical gloves and artificial kidney potting materials.

<4-3-10. Active energy ray-curable resin composition, etc.>
The polyurethane, polyurethaneurea and urethane prepolymer solution of the present invention are modified by modifying the terminal to form a UV curable coating, an electron beam curable coating, a photosensitive resin composition for flexographic printing plates, and a photocurable optical fiber coating. It can be used as a raw material for a material composition or the like.

  In particular, the active energy ray-curable resin composition obtained by modifying the terminal of the urethane compound of the present invention with a radical polymerization group can be widely used in various surface processing fields and cast molding applications. Among them, the active energy ray-curable resin composition containing a urethane (meth) acrylate oligomer whose radical polymerizable group is (meth) acrylate is excellent in stain resistance and handling properties when cured to form a cured film. Has characteristics.

The urethane (meth) acrylate-based oligomer can be produced by adding a polyisocyanate, a hydroxyalkyl (meth) acrylate and, if necessary, other compounds in addition to the polycarbonate diol of the present invention.
Examples of the polyisocyanate that can be used for producing the urethane (meth) acrylate oligomer include polyisocyanates such as tris (isocyanatohexyl) isocyanurate in addition to the organic diisocyanate.

Further, usable hydroxyalkyl (meth) acrylate is a compound having both one or more hydroxyl groups and one or more (meth) acryloyl groups as represented by 2-hydroxyethyl (meth) acrylate. If there is no particular limitation.
Furthermore, in addition to the polycarbonate diol of the present invention, if necessary, a compound having at least two active hydrogens such as other polyols and / or polyamines may be added, and these may be used in any combination.

  The active energy ray-curable resin composition containing the urethane (meth) acrylate oligomer produced using the polycarbonate diol of the present invention as a raw material includes other than the urethane (meth) acrylate oligomer produced using the polycarbonate diol of the present invention as a raw material. Active energy ray-reactive monomers, active energy ray-curable oligomers, polymerization initiators and photoincreasing agents, and other additives may be mixed.

The cured film of the active energy ray-curable resin composition containing the urethane (meth) acrylate oligomer produced using the polycarbonate diol of the present invention as a raw material is resistant to contamination and protection against general household contaminants such as ink and ethanol. An excellent film can be obtained.
A laminate using the cured film as a coating on various substrates is excellent in design and surface protection, and can be used as a coating substitute film, for example, interior or exterior building materials and automobiles. It can be effectively applied to various members such as home appliances.

  The polycarbonate diol of the present invention is a polyester elastomer, that is, a polyether mainly composed of a hard segment mainly composed of an aromatic polyester and a soft segment mainly composed of an aliphatic polyether, aliphatic polyester or aliphatic carbonate. It can be used as a carbonate component of a polyester or polycarbonate ester block copolymer.

  When the polycarbonate diol of the present invention is used as a raw material, the soft segment is excellent in physical properties such as heat resistance and water resistance as compared with the case where an aliphatic polyether or aliphatic polyester is used. Compared with known polycarbonate diols, polycarbonate ester elastomers having a fluidity at the time of melting, that is, a melt flow rate suitable for blow molding and extrusion molding, and excellent balance with mechanical strength and other physical properties Become. Therefore, it can be suitably used for various molding materials including fibers, films and sheets, for example, molding materials such as elastic yarns, boots, gears, tubes and packings.

  Specifically, for example, it can be effectively applied to uses such as joint boots such as automobiles and home appliance parts, and electric wire covering materials that require heat resistance and durability.

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]
<Number average molecular weight, ratio of structures derived from dihydroxy compounds>
The ratio of the number average molecular weight (Mn) and the structure derived from the dihydroxy compound in the polycarbonate diol was measured by measuring ¹ H-NMR (AVANCE400 manufactured by BRUKER) at 400 MHz by dissolving the polycarbonate diol in CDCl ₃ (deuterated chloroform) Calculated from the value.

<Ratio of secondary hydroxyl terminal>
The proportion of secondary hydroxyl terminal was calculated from the integral value obtained by dissolving polycarbonate diol in CDCl ₃ (deuterated chloroform) and measuring ¹ H-NMR (AVANCE400 manufactured by BRUKER) at 400 MHz. The ratio of the secondary hydroxyl terminal is obtained from the ratio of the integral value of one proton at the secondary hydroxyl terminal to the total of the integral values of one proton for all hydroxyl terminals and phenoxide terminals of the polycarbonate diol. The detection limit of the secondary hydroxyl terminal is 1.0 mol% with respect to the total structure of the polycarbonate diol terminal.

<Residual phenol content>
LC measurement (column (manufactured by Shiseido Co., Ltd.): CAPCELLPAK 3 μm 75 mmL × 4.6 mm ID, eluent; water / acetonitrile mixed solvent, column temperature; 40 ° C., flow rate; 0 mL / min, injection volume; 10 μL), and the content was calculated from the quantitative value. In this case, the lower limit of detection is 100 ppm as the weight of phenol relative to the weight of the entire sample.

<Residual diphenyl carbonate amount>
Polycarbonate diol was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AVANCE400 manufactured by BRUKER) was measured, and the integrated value was calculated. In this case, the detection limit is 0.01 mol of diphenyl carbonate with respect to 1 mol of polycarbonate diol.

<Ratio of phenoxide terminal>
Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (AVANCE 400 manufactured by BRUKER) was measured, and calculated from the integrated value of the signal of each component. The ratio of the phenoxide terminal is obtained from the ratio of the integral value of one proton at the phenoxide terminal and the terminal structure of the polycarbonate diol and the phenoxide terminal and the sum of the integral values of each proton, and the detection limit of the phenoxide terminal is It is 0.05 mol% with respect to the whole structure of a polycarbonate diol terminal.

<Glass transition temperature>
About 10 mg of polycarbonate diol is enclosed in an aluminum pan, and using a differential scanning calorimeter (EXSTAR DSC6200, manufactured by Seiko Instruments Inc.), at a rate of 20 ° C. per minute at a rate of 20 ° C. per minute at a rate of 30 ° C. per minute. The temperature was raised and lowered from 150 ° C. to −120 ° C. at a rate of 40 ° C. and from −120 ° C. to 120 ° C. at a rate of 20 ° C. per minute, and the inflection point at the second temperature rise was defined as the glass transition temperature (Tg). .

<Hydroxyl value>
A 1 L separable flask equipped with an oil bath and a stirrer (heated to 80 ° C. in an oven before examination) was dried with nitrogen, and then under a nitrogen stream, polycarbonate diol (200 g) and a tin-based catalyst: U-830 (0.04 g) Put. Then, a separable flask was attached to an oil bath heated to 80 ° C., and stirring (60 rpm) was started after the internal temperature rose to about 70 ° C. After the internal temperature rose to 75-80 ° C., 2.1 equivalents of isophorone diisocyanate was added to the polycarbonate diol. After the addition, the temperature of the oil bath was raised to 110 ° C. Thereafter, starting from the time when the internal temperature rose to 100 to 105 ° C., the reaction was carried out for 3 hours, and then 1 to 2 g of the reaction solution was extracted. The extracted reaction solution was put into 20 mL of a mixed solution of di-n-butylamine / toluene (weight ratio: 2/25) and stirred at room temperature for 30 minutes. Then, it diluted with 90 mL of acetone, and titrated with 0.5 N hydrochloric acid aqueous solution to analyze the amount of remaining amine (this measurement). Further, 20 mL of a di-n-butylamine / toluene mixed solution to which no reaction solution was added was similarly diluted with 90 mL of acetone and then titrated with a 0.5 N aqueous hydrochloric acid solution (blank measurement). The hydroxyl value was determined by the following formula from the volume of the obtained hydrochloric acid aqueous solution.

Hydroxyl value (mg-KOH / g) = 56100 * A / S
S: Polycarbonate diol (g) placed in a separable flask
A: Isocyanate group consumed by reaction with hydroxyl group (mol)
A = (BC) x2-D / ExF
B: Isophorone diisocyanate (mol) placed in a separable flask
C: Moisture (mol) contained in the reaction solution in the separable flask
D: Isocyanate group (mol / g) remaining in the sample used in this measurement
E: Sample used for this measurement (g)
F: Total amount of isophorone diisocyanate and polycarbonate diol in a separable flask (g)
D = (HG) x0.5 / 1000xf
G: Amount of 0.5N aqueous hydrochloric acid solution required for this measurement (mL)
H: Amount of 0.5N hydrochloric acid aqueous solution required for blank measurement (mL)
f: Potency of aqueous hydrochloric acid solution

<Thin film distillation device>
An internal condenser having a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m 2 and a jacketed Shibata Kagaku Co., Ltd. molecular distillation apparatus MS-300 special type were used.

[Evaluation method Polyurethane]
<Molecular weight>
A GPC apparatus manufactured by Shimadzu Corporation (column TSKgelSuperHZM-N, the solvent is dimethylacetamide with lithium bromide) was used, and the number average molecular weight (Mn) in terms of standard polystyrene was defined as the molecular weight.

<Viscosity>
The viscosity of the obtained polyurethane solution was measured at 25 ° C. using a TV-22 viscometer (cone plate type) manufactured by Toki Sangyo Co., Ltd.
<Film tensile properties (room temperature)>
Using a tensile tester (Tensilon RTC-1210A manufactured by Orientec Co., Ltd.) according to JIS K6301 for a strip-shaped polyurethane sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm, the tensile breaking elongation and 100% · 300 The stress at% elongation was measured. The distance between chucks was 50 mm, the tensile speed was 500 mm / min, and the temperature was 23 ° C. (relative humidity 55%).

<Tensile physical properties of film (-10 ° C)>
A tensile tester (Autograph AG-X 5 manufactured by Shimadzu Corporation) was applied to a strip-shaped polyurethane sample having a width of 10 mm, a length of 100 mm, and a thickness of 40 μm according to JIS K6301.
kN) was used to measure the tensile elongation at break and the stress at 100% / 300% elongation. The distance between chucks was 50 mm, the tensile speed was 500 mm / min, and the temperature was −10 ° C.

<Glass transition temperature>
About 5 mg of a film piece of polyurethane having a thickness of 40 μm is sealed in an aluminum pan, and a differential scanning calorimeter (EXSTAR DSC6200 manufactured by Seiko Instruments Inc.) is used, and the temperature is −100 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere. From 250 ° C., 250 ° C. to −100 ° C., and −100 ° C. to 250 ° C., and the inflection point at the second temperature rise was defined as the glass transition temperature (Tg).

[Example 1-1]
In a 1 LSUS reaction vessel equipped with an oil circulation tank, a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol (278.3 g), dipropylene glycol (43.1)
g) After adding diphenyl carbonate (528.6 g), 1.7 mL of an aqueous solution of magnesium acetate tetrahydrate (210 mg / 25 mL) was added with a syringe. Thereafter, nitrogen substitution in the reactor was repeated three times. After the nitrogen replacement, the oil circulation tank was first heated (190 to 200 ° C.) until the internal temperature reached 165 ° C., and the contents were heated and dissolved. When the temperature was raised and dissolved, stirring was started, and then the pressure was lowered to 130 torr in 5 minutes. Thereafter, polymerization was advanced while distilling phenol at an internal temperature of 165 ° C. and pressure of 130 torr for 90 minutes. Then, the polymerization was advanced while distilling out phenol and unreacted diol while gradually reducing the pressure in the reaction vessel to 60 torr over 90 minutes and then to 2 torr over 60 minutes. Finally, the internal temperature was raised to 170 ° C., and the reaction was carried out at an internal temperature of 170 ° C. and a pressure of 2 torr for 120 minutes. The obtained polycarbonate diol was 347 g, and the yield was 90%.

Further, the obtained polycarbonate diol product was subjected to thin film distillation (temperature: 160 ° C., pressure: 0.027 kPa) at a flow rate of 20 g / min.
The property of the polycarbonate diol product after this thin-film distillation is a white solid at room temperature, the OH value is 43.4, the number average molecular weight (Mn) determined from the OH value analysis is 2586, and the glass transition temperature is −46 ° C. Met. Further, the ratio of the structure derived from dipropylene glycol and the structure derived from 16-hexanediol contained in the polycarbonate diol was 14/86 (formula (1
) Repeat unit 14 mol%) The ratio of secondary hydroxyl terminal was 29 mol%, and the ratio of hydroxyl terminal was 99 mol% or more. Furthermore, the phenol content was 0.05% by weight, and no diphenyl carbonate or phenoxide terminated polymer was detected.

[Example 2-1]
In a 1 LSUS reaction vessel equipped with an oil circulation tank, a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol (232.9 g) and dipropylene glycol (113.
3 g) and diphenyl carbonate (553.8 g) were added, and then 1.8 mL of an aqueous solution of magnesium acetate tetrahydrate (210 mg / 25 mL) was added by syringe. Thereafter, nitrogen substitution in the reactor was repeated three times. After the nitrogen replacement, the oil circulation tank was first heated (190 to 200 ° C.) until the internal temperature reached 165 ° C., and the contents were heated and dissolved. When the temperature was raised and dissolved, stirring was started, and then the pressure was lowered to 130 torr in 5 minutes. Thereafter, polymerization was advanced while distilling phenol at an internal temperature of 165 ° C. and pressure of 130 torr for 90 minutes. Then, the polymerization was advanced while distilling out phenol and unreacted diol while gradually reducing the pressure in the reaction vessel to 60 torr over 90 minutes and then to 2 torr over 60 minutes. Finally, the internal temperature was raised to 170 ° C., and the reaction was carried out at an internal temperature of 170 ° C. and a pressure of 2 torr for 120 minutes. The obtained polycarbonate diol was 376 g and the yield was 91%.

Furthermore, the obtained polycarbonate diol was thin-film distilled at a flow rate of 20 g / min (
Temperature: 160 ° C., pressure: 0.027 kPa).
The properties of the polycarbonate diol after the thin-film distillation were a transparent liquid at normal temperature, the OH value was 38.8, the number average molecular weight (Mn) obtained from the OH value analysis was 2890, and the glass transition temperature was −42 ° C. It was. The ratio of the structure derived from dipropylene glycol and the structure derived from 16-hexanediol contained in the polycarbonate diol is 28/72 (28 mol% of the repeating unit of the formula (1)), and the ratio of the secondary hydroxyl terminal is 47. The ratio of mol% and hydroxyl terminal was 99 mol% or more. Furthermore, the phenol content was 0.02% by weight, and diphenyl carbonate and a polymer having a phenoxide terminal were not detected.

[Comparative Example 1-1]
In a 5 L glass reaction vessel equipped with an oil circulation tank, a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol (310.0 g) and neopentyl glycol (409.
9 g) and diphenyl carbonate (1280.1 g) were added, and 3.4 mL of an aqueous solution of magnesium acetate tetrahydrate (210 mg / 25 mL) was added by syringe. Thereafter, nitrogen substitution in the reactor was repeated three times. After the nitrogen substitution, the oil circulation tank was first heated to an internal temperature of 160 ° C. to heat and dissolve the contents, and then the pressure was reduced to 170 mmHg over 5 minutes. Thereafter, polymerization was carried out while distilling phenol at an internal temperature of 160 ° C. and a pressure of 170 torr for 90 minutes. Then, the polymerization was carried out while distilling out phenol and unreacted diol while gradually reducing the pressure in the reaction vessel to 90 torr over 90 minutes and then to 3 torr over 60 minutes. Finally, the reaction was performed at an internal temperature of 160 ° C. and a pressure of 3 torr for 120 minutes. The obtained polycarbonate diol was 778 g and the yield was 89%.

Furthermore, the obtained polycarbonate diol was thin-film distilled at a flow rate of 20 g / min (
Temperature: 160 ° C., pressure: 0.027 kPa).
The properties of the polycarbonate diol after the thin-film distillation is a transparent liquid at room temperature, the number average molecular weight (Mn) is 2013, the OH number estimated from the number average molecular weight is 55.7, and the glass transition temperature is -29 ° C. there were. The ratio between the structure derived from neopentyl glycol and the structure derived from 16-hexanediol contained in the polycarbonate diol was 55/45 (formula (1
The proportion of secondary hydroxyl terminals was less than 1 mol%, and the ratio of hydroxyl groups was 99 mol% or more. Furthermore, the phenol content was 0.01% by weight, and no diphenyl carbonate or phenoxide terminated polymer was detected.

[Comparative Example 2-1]
In a 5 L glass reaction vessel equipped with an oil circulation tank, a stirrer, a distillate trap, and a pressure regulator, 1,6-hexanediol (1020.5 g), neopentyl glycol (158
. 7 g) and diphenyl carbonate (2070.8 g) were added, and 5.2 mL of an aqueous solution of magnesium acetate tetrahydrate (210 mg / 25 mL) was added by syringe. Thereafter, nitrogen substitution in the reactor was repeated three times. After the nitrogen substitution, the oil circulation tank was first heated to an internal temperature of 160 ° C. to heat and dissolve the contents, and then the pressure was reduced to 170 mmHg over 5 minutes. Thereafter, polymerization was carried out while distilling phenol at an internal temperature of 160 ° C. and a pressure of 170 torr for 90 minutes. Then, the polymerization was carried out while distilling out phenol and unreacted diol while gradually reducing the pressure in the reaction vessel to 90 torr over 90 minutes and then to 3 torr over 60 minutes. Finally, the internal temperature was raised to 170 ° C., and the reaction was carried out at an internal temperature of 170 ° C. and a pressure of 3 torr for 120 minutes. The polycarbonate diol obtained was 1288 g and the yield was 90%.

Furthermore, the obtained polycarbonate diol was thin-film distilled at a flow rate of 20 g / min (
(Temperature: 180 ° C. for the first time, 160 ° C. for the second time, pressure: 0.027 kPa)).
The properties of the polycarbonate diol after this thin-film distillation were white at room temperature, the number average molecular weight (Mn) was 3044, the OH number estimated from the number average molecular weight was 36.9, and the glass transition temperature was -44 ° C. It was. The ratio of the structure derived from neopentyl glycol and the structure derived from 16-hexanediol contained in the polycarbonate diol is 14/86 (less than 1 mol% of the repeating unit of the formula (1)), and the ratio of the secondary hydroxyl terminal is Less than 1 mol%, the ratio of hydroxyl terminal was 99 mol% or more. Furthermore, the phenol content was less than 0.01% by weight, and diphenyl carbonate and phenoxide terminated polymer were not detected.

[Example 1-2]
The polycarbonate diol (84.4 g) produced in Example 1-1 was heated to a temperature equal to or higher than the melting point (for example, 120 ° C.) in a 1 L separable flask that had been heated at 60 to 70 ° C. and then substituted with nitrogen and dried. In addition, dimethylformamide (250 g) was added and dissolved while the flask was immersed in an oil bath set at 55 ° C. and heated. Stirring was started at about 60 rpm, 1,4-butanediol (3.8 g) was further added, and tin stearate (0.038 g) was added dropwise. Next, diphenylmethane diisocyanate (18.8 g) was added dropwise at a rate such that the liquid temperature did not exceed 70 ° C. Thereafter, the temperature of the oil bath was raised to 70 ° C. and reacted for 70 minutes to obtain a polyurethane solution having a solid content concentration of 30% by weight. The obtained polyurethane had a weight average molecular weight (Mw) of 172,000 and a viscosity (25 ° C.) of 77.7 Pa · s. Further, the polyurethane solution was applied onto the polyethylene film with a doctor blade with a uniform film thickness, The polyurethane film was obtained by drying with a dryer.

  When the film physical properties were measured, the tensile elongation at break at room temperature was 597%, the tensile strength at break was 69 MPa, the stress at 100% elongation was 1.9 MPa, and the stress at 300% elongation was 7.3 MPa. It was. The tensile elongation at -10 ° C. was 469%, the tensile strength at break was 93 MPa, the stress at 100% elongation was 5.1 MPa, and the stress at 300% elongation was 35 MPa. Furthermore, the glass transition temperature was −19 ° C.

[Example 2-2]
The polycarbonate diol (79.7 g) produced in Example 2-1 was heated to a temperature equal to or higher than the melting point (for example, 120 ° C.) in a 1 L separable flask heated at 60 to 70 ° C. and then substituted with nitrogen and dried. In addition, dimethylformamide (233 g) was added and dissolved while the flask was immersed in an oil bath set at 55 ° C. and heated. Stirring was started at about 60 rpm, 1,4-butanediol (3.5 g) was further added, and tin stearate (0.020 g) was added dropwise. Subsequently, diphenylmethane diisocyanate (17.1 g) was added dropwise at such a rate that the liquid temperature did not exceed 70 ° C. Then, after raising the temperature of the oil bath to 70 ° C. and reacting for 80 minutes, 0.36 g of MDI was gradually dropped until the weight average molecular weight measured by GPC reached 160,000 to 180,000, and the solid content concentration was 30 A weight percent polyurethane solution was obtained. The obtained polyurethane had a weight average molecular weight (Mw) of 167,000 and a viscosity (25 ° C.) of 45.9 Pa · s.

Furthermore, the polyurethane solution was applied onto the polyethylene film with a doctor blade so as to have a uniform film thickness, and dried with a dryer to obtain a polyurethane film.
When the film physical properties were measured, the tensile elongation at break at room temperature was 673%, the tensile strength at break was 52 MPa, the stress at 100% elongation was 1.7 MPa, and the stress at 300% elongation was 4.1 MPa. It was. The tensile elongation at -10 ° C was 520%, the tensile strength at break was 74 MPa, the stress at 100% elongation was 5.0 MPa, and the stress at 300% elongation was 25 MPa. Furthermore, the glass transition temperature was −19 ° C.

[Comparative Example 1-2]
The polycarbonate diol (99.6 g) produced in Comparative Example 1-1 was heated to a temperature equal to or higher than the melting point (for example, 120 ° C.) in a 1 L separable flask heated at 60 to 70 ° C. and then substituted with nitrogen and dried. In addition, dimethylformamide (226 g) was added and dissolved while the flask was immersed in an oil bath set at 55 ° C. and heated. Stirring was started at about 60 rpm, 1,4-butanediol (2.5 g) was further added, and tin stearate (0.045 g) was added dropwise. Subsequently, diphenylmethane diisocyanate (18.5 g) was added dropwise at such a rate that the liquid temperature did not exceed 70 ° C. Then, after raising the temperature of the oil bath to 70 ° C. and reacting for 90 minutes, 1.67 g of MDI was gradually dropped until the weight average molecular weight measured by GPC reached 160,000 to 180,000, and the solid content concentration was 30 A weight percent polyurethane solution was obtained. The obtained polyurethane had a weight average molecular weight (Mw) of 164,000 and a viscosity (25 ° C.) of 41.9 Pa · s.

Furthermore, the polyurethane solution was applied onto the polyethylene film with a doctor blade so as to have a uniform film thickness, and dried with a dryer to obtain a polyurethane film.
When the film physical properties were measured, the tensile elongation at break at room temperature was 521%, the tensile strength at break was 61 MPa, the stress at 100% elongation was 3.6 MPa, and the stress at 300% elongation was 9.5 MPa. It was. In the tensile test at −10 ° C., the yield point was observed at an elongation of about 20%, the tensile elongation at break was 325%, the tensile strength at break was 49 MPa, and the stress at 100% elongation was 33 MPa, 300% elongation. The stress at the time was 52 MPa. Furthermore, the glass transition temperature was −2 ° C.

[Comparative Example 2-2]
The polycarbonate diol (120.9 g) produced in Comparative Example 2-2 was heated to a temperature equal to or higher than the melting point (for example, 120 ° C.) in a 1 L separable flask heated at 60 to 70 ° C. and then substituted with nitrogen and dried. In addition, dimethylformamide (353 g) was added and dissolved while the flask was immersed in an oil bath set at 55 ° C. and heated. Stirring was started at about 60 rpm, 1,4-butanediol (5.3 g) was further added, and tin stearate (0.0273 g) was added dropwise. Subsequently, diphenylmethane diisocyanate (24.4 g) was added dropwise at such a rate that the liquid temperature did not exceed 70 ° C. Then, after raising the temperature of the oil bath to 70 ° C. and reacting for 70 minutes, 0.79 g of MDI was gradually added dropwise until the weight average molecular weight measured by GPC reached 160,000 to 180,000, and the solid content concentration was 30 A weight percent polyurethane solution was obtained. The obtained polyurethane had a weight average molecular weight (Mw) of 17,000 and a viscosity (25 ° C.) of 85.1 Pa · s.

Furthermore, the polyurethane solution was applied onto the polyethylene film with a doctor blade so as to have a uniform film thickness, and dried with a dryer to obtain a polyurethane film.
When the film physical properties were measured, the tensile elongation at break at room temperature was 605%, the tensile strength at break was 84 MPa, the stress at 100% elongation was 2.0 MPa, and the stress at 300% elongation was 8.4 M.
Pa. The tensile elongation at -10 ° C was 375%, the tensile strength at break was 60 MPa, the stress at 100% elongation was 5.4 MPa, and the stress at 300% elongation was 38 MPa. Furthermore, the glass transition temperature was −22 ° C.

[Comparative Example 3-2]
T6002 (polycarbonate diol using 1,6-hexanediol as a raw material) heated to 60 ° C to 70 ° C and then heated to a temperature equal to or higher than the melting point (eg, 120 ° C) in a 1 L separable flask that has been purged with nitrogen and dried. Chemicals, less than 1 mol% of repeating unit of formula (1), the ratio of secondary hydroxyl terminal is less than 1 mol%) (79.7 g), and the flask is immersed in an oil bath set at 55 ° C. and heated. Dimethylformamide (241 g) was added and dissolved. Stirring was started at about 60 rpm, and 1,4-butanediol (3.6 g) was further added, and tin stearate (0.017 g) was added dropwise. Subsequently, diphenylmethane diisocyanate (19.6 g) was added dropwise at such a rate that the liquid temperature did not exceed 70 ° C. Then, after raising the temperature of the oil bath to 70 ° C. and reacting for 60 minutes, 0.11 g of MDI was gradually dropped until the weight average molecular weight measured by GPC reached 160,000 to 180,000, and the solid content concentration was 30 A weight percent polyurethane solution was obtained. The obtained polyurethane had a weight average molecular weight (Mw) of 18,000 and a viscosity (25 ° C.) of 142.8 Pa · s. Further, a polyurethane solution was applied on a polyethylene film with a doctor blade to a uniform film thickness, The polyurethane film was obtained by drying with a dryer.

  When the film physical properties were measured, the tensile breaking elongation at room temperature was 597%, the tensile breaking strength was 75 MPa, the stress at 100% elongation was 2.6 MPa, and the stress at 300% elongation was 11.1 MPa. It was. The tensile elongation at -10 ° C was 486%, the tensile strength at break was 85 MPa, the stress at 100% elongation was 4.2 MPa, and the stress at 300% elongation was 41 MPa. Furthermore, the glass transition temperature was −23 ° C.

[Comparative Example 4-2]
1,6-hexanediol (37.8 g), diethylene glycol (33.6 g), and diphenyl carbonate (128.4 g) were placed in a 300 mL reaction tube equipped with a stirrer, a distillate trap, an oil bath, and a pressure regulator. Thereafter, 6.0 mg of magnesium acetate tetrahydrate was added. Thereafter, nitrogen substitution in the reaction tube was repeated three times. After the nitrogen substitution, the oil bath was first heated to 160 ° C., and the contents were heated and dissolved. When the temperature was raised and dissolved, stirring was started and the reaction was allowed to proceed at normal pressure for 30 minutes. Next, the pressure was lowered to 100 torr over 5 minutes, and then the polymerization was carried out while distilling phenol and unreacted diol while lowering the pressure to 5 torr over 150 minutes. Finally, the reaction was performed at an oil bath temperature of 160 ° C. and a pressure of 5 torr for 60 minutes.

The property of the obtained polycarbonate diol was a transparent liquid at room temperature, and the number average molecular weight (Mn) determined from NMR analysis was 2010. The ratio of the structure derived from diethylene glycol and the structure derived from 16-hexanediol contained in the polycarbonate diol was 51
/ 49 The ratio of secondary hydroxyl terminal was less than 1 mol%, and the ratio of hydroxyl terminal was 99 mol% or more. Furthermore, the phenol content was 0.3% by weight, and diphenyl carbonate and phenoxide terminated polymer were not detected.

In addition, except that the polycarbonate diol produced in Example 1-1 was used in place of the polycarbonate diol produced from 1,6-hexanediol / diethylene glycol, the solid content was 30%. A polyurethane solution was obtained. This polyurethane solution was applied onto a polyethylene film with a doctor blade so as to have a uniform film thickness (50 μm) and dried with a dryer to obtain a polyurethane film. When the film physical properties were measured, the tensile breaking elongation at room temperature was 949%, the tensile breaking strength was 30 MPa, the stress at 100% elongation was 2.0 MPa, and the stress at 300% elongation was 2.9 MPa. It was.

<Summary of physical properties of polycarbonate diol and polyurethane>
Table 1 shows the properties, molecular weight, glass transition temperature of polycarbonate diols obtained in Examples 1-1 and 2-1 and Comparative Examples 1-1 and 2-1, and Examples 1-2 and 2-2 and Comparative Examples. The analysis results of molecular weight, tensile breaking strength, tensile breaking elongation, stress at 100% / 300% elongation, glass transition temperature, and solution viscosity of polyurethane obtained in 1-2, 2-2, and 3-2 are summarized. .

<Comparison of polyurethane properties>
Table 2 shows polyurethanes obtained in Examples 1-2, 2-2 and Comparative Examples 1-2, 2-2, 3-2-2, and 4-2. Tensile strength at break and elongation at break of polyurethane at room temperature The stress at 100% / 300% elongation is shown in an organized manner.

Polyurethanes obtained from the polycarbonate diol having ether bonds and side chains obtained in Examples 1-2 and 2-2 as raw materials are polycarbonate diols having side chains obtained in Comparative Examples 1-2 and 2-2. Compared to the polyurethane obtained from the modified polyurethane and the straight-chain polycarbonate diol obtained in Comparative Example 3-2, the stress at 300% elongation is low, the tensile elongation at break is the same or high, and the property is rich in flexibility. You can see that. On the other hand, from Comparative Example 4-2, the polycarbonate diol using a linear diethylene glycol having an ether bond as in Patent Document 2 has a stress at 300% elongation, and the tensile breaking strength is too low, so that the artificial leather is used. It is conceivable that there may be problems such as an appropriate resilience not being obtained and easy elongation. The results of Comparative Example 4-2 are shown in Examples 1-2 to 2-2 and Comparative Example 1-2.
Since the film thickness is thicker than the result of ˜3-2, when the film thickness is combined, it is considered that the stress at 300% elongation and the tensile strength at break are lower.

  Table 3 shows the polyurethanes obtained in Examples 1-2 and 2-2 and Comparative Examples 1-2, 2-2, and 3-2. The tensile breaking strength and tensile breaking elongation of the polyurethane at −10 ° C. The stress at 100% / 300% elongation is shown in an organized manner.

  Usually, polyurethane having poor low-temperature characteristics loses elasticity at low temperatures and becomes brittle, so that the stress at the time of elongation increases and the elongation at break decreases. On the other hand, the polyurethane obtained in Examples 1-2 and 2-2 has a lower stress at 300% elongation than the polyurethane obtained in Comparative Examples 1-2, 2-2, and 3-2. In addition, it can be seen that the tensile elongation at break tends to be high and the low temperature characteristics are excellent. The reason is considered that the polyurethane obtained in Examples 1-2 and 2-2 also improved the flexibility of the polyurethane at a low temperature by an ether bond.

<Comparison of reactivity of polyurethane polymerization>
Table 4 shows the weight average molecular weight of Example 1-2 and Comparative Example 3-2 after reacting for 60 to 70 minutes after adding diphenylmethane diisocyanate by polyurethane polymerization and raising the oil bath temperature to 70 ° C.

  The polycarbonate diol T6002 used in Comparative Example 3-2 is a polycarbonate diol using a primary terminal diol as a raw material, and the secondary hydroxyl terminal is present only at 1% or less. On the other hand, the polycarbonate diol (synthesized in Example 1-1) used in Example 1-2 contains 29 mol% of secondary hydroxyl terminal. It has been described in prior art documents (for example, Japanese Patent No. 3874664, International Publication No. 2009-063767 pamphlet) that the reactivity of PU polymerization is lowered when a secondary hydroxyl terminal is included. The reactivity of polyurethane polymerization is stabilized by making it more than mol%. On the other hand, a polycarbonate diol containing dihydroxyl glycol synthesized as a raw material and having a secondary hydroxyl terminal has a reactivity equivalent to that of a polycarbonate diol containing 99% mol or more of the primary hydroxyl terminal. The reason why the high reactivity is maintained regardless of having a secondary hydroxyl terminal may be that the ether group of dipropylene glycol electronically increased the reactivity of the hydroxyl group and the isocyanate group.

<Reactivity of polycarbonate diol polymerization>
A polycarbonate diol using an alcohol having a secondary hydroxyl group has low reactivity and a low yield. For example, in JP 2012-46659 A, a polycarbonate diol using 1,3-butanediol as a raw material is synthesized, but a product is obtained only in a yield of 50-60%. On the other hand, the polycarbonate diol using dipropylene glycol synthesized in Examples 1-1 and 2-1 as a raw material has a high yield of 90% or more. The reason for the high reactivity is the use of diphenyl carbonate, in which the phenoxy group is easily removed and polycondensation is easy to proceed, and the reaction temperature and pressure are adjusted to suppress the coloring of the product and the distillation of the raw material as much as possible. Is maintained.

The polycarbonate diol of the present invention contains an ether bond and a secondary hydroxyl terminal in an appropriate range, so that when a polyurethane is produced, it has moderate flexibility and excellent low-temperature characteristics, which are characteristics as a polyurethane derived from a conventional polycarbonate diol. Give features.
Due to this feature, for example, it is considered that the artificial leather manufactured using polyurethane made from the polycarbonate diol of the present invention has high flexibility and good texture.

  Moreover, the fall of the reactivity of the polymerization reaction of a polycarbonate diol and a polyurethane-ized reaction can be suppressed by controlling the ratio of the structure of characteristics, such as a secondary hydroxyl terminal. As a result, it has excellent characteristics in polyurethane physical properties such as handleability and flexibility when used as a raw material for producing polyurethane. From these points, it is expected to be extremely useful industrially.

Claims (11)

A polycarbonate diol containing 5 to 50 mol% of a repeating unit represented by the following formula (1).

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms and may contain a hetero atom within the range of the carbon number. n is an integer of 1 or more.)   2. The polycarbonate diol according to claim 1, wherein the ratio of secondary hydroxyl terminal to the total terminal group of the polycarbonate diol is 10 mol% or more.   The polycarbonate diol according to claim 1 or 2, wherein the ratio of the hydroxyl terminal to the total terminal group of the polycarbonate diol is 95 mol% or more. The polycarbonate diol according to any one of claims 1 to 3, wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (2).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. And n is an integer greater than or equal to 1.)   In addition to the structural unit represented by the formula (1), a C1-C15 alkylene group which may have a branched and / or ring structure is contained as a repeating unit. 5. The polycarbonate diol according to any one of 4 above. It is a manufacturing method which manufactures the polycarbonate diol of any one of Claim 1 to 5, Comprising: At least ether diol and diphenyl carbonate which have a structure shown by following formula (3) are transesterified. A method for producing a polycarbonate diol, which is characterized.

(In the formula, R ¹ and R ² are each independently a divalent group having 1 to 15 carbon atoms, and may contain a hetero atom within the range of the carbon number.) The method for producing a polycarbonate diol according to claim 6, wherein the ether diol represented by the formula (3) is an ether diol represented by the following formula (4).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, It is an alkynyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and may contain heteroatoms within the range of the carbon number, provided that all of R ³ to R ⁶ are hydrogen atoms. Nothing.)   The diol having 1 to 15 carbon atoms which may have a branched structure, a ring structure and / or a hetero atom in addition to the ether diol represented by the formula (3) is reacted. A process for producing a polycarbonate diol.   The method for producing a polycarbonate diol according to any one of claims 6 to 8, wherein the reaction is carried out in the presence of a Group 2 metal compound of the periodic table.   The method for producing a polycarbonate diol according to any one of claims 6 to 9, wherein the reaction temperature is 190 ° C or lower.   A polyurethane obtained by using the polycarbonate diol according to any one of claims 1 to 5.