JP2015143216A - Polycarbonate diol containing carbonate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol composition which is suitable as a material for a coating material or an adhesive, or a raw material for a thermoplastic elastomer, to provided a polycarbonate diol composition which, when used as a constitutional material of coating material, can provide a smooth coating film without impairing chemical resistance, and to provide a polycarbonate diol composition which, when used as a raw material for polyurethane, can provide polyurethane excellent in oil resistance without impairing mechanical strength.SOLUTION: The polycarbonate diol composition contains: polycarbonate diol containing a repeating unit represented by a specific formula and a terminal hydroxyl group; and 0.05 to 5 wt.% of a polycarbonate compound represented by a specific formula.

Description

  The present invention relates to a polycarbonate diol.

  Polycarbonate diol is known as a material excellent in hydrolysis resistance, light resistance, oxidation degradation resistance, heat resistance and the like as a soft segment such as polyurethane and thermoplastic elastomer. However, when polycarbonate diol is used as a constituent material of a paint, the interaction between the polycarbonate diol bonds is strong, so that the smoothness of the coating film surface may be impaired.

  On the other hand, various additives having a cyclic carbonate structure are disclosed. For example, an additive having a cyclic carbonate structure that reduces the viscosity of an epoxy resin without significantly deteriorating mechanical properties and / or solvent resistance is disclosed (for example, see Patent Document 1). Further, a novel cyclic carbonate useful as a solvent such as an electrolytic solution, a polymer material precursor, and an additive is disclosed (for example, see Patent Document 2). Further, a polycarbonate diol containing 5-methyl-1,3-dioxan-2-one is disclosed (for example, see Patent Document 3).

Special table 2013-528885 gazette JP 2011-84512 A International Publication No. 2006-088152

  However, when the cyclic carbonates described in Patent Documents 1 and 2 are used as constituent materials for paints, the addition of a small amount cannot improve the smoothness of the coating film, and if added in a large amount, the cyclic carbonate may bleed out. There is room for improvement. Further, when the polycarbonate diol described in Patent Document 3 is used as a constituent material of a paint, there is no room for improvement in the smoothness of the coating film, although there is no decrease in mechanical strength and oil resistance.

  As described above, the polycarbonate diol that can obtain a smooth coating film without lowering the mechanical strength and chemical resistance has not been developed by the conventional techniques.

  Accordingly, an object of the present invention is to provide a polycarbonate diol composition capable of obtaining a smooth coating film without impairing chemical resistance when used as a constituent material of a paint, for example. Another object of the present invention is to provide a polycarbonate diol composition capable of obtaining a polyurethane excellent in oil resistance without impairing mechanical strength, for example, when used as a raw material for polyurethane.

  As a result of intensive studies to solve the above problems, the present inventor has found that the object can be achieved by using a polycarbonate diol composition containing a carbonate compound having a specific structure, and has reached the present invention.

（式（Ａ）中、Ｒは、炭素数２〜１５の二価の脂肪族又は脂環族炭化水素を表す。）
下記式（Ｂ）で表されるカーボネート化合物を０．０５〜５重量％含む、ポリカーボネートジオール組成物。

（式（Ｂ）中、ｌ及びｍは、２〜１５の整数を表し、ｌ≠ｍである。）
［２］
上記式（Ｂ）で表されるカーボネート化合物が、下記式（Ｃ）で表されるカーボネート化合物である、上記［１］に記載のポリカーボネートジオール組成物。

（式（Ｃ）中、ｌ及びｍは、４〜６の整数を表し、ｌ≠ｍである。）
［３］
前記ポリカーボネートジオールにおける末端ＯＨ基割合が９５．０〜９９．９％である、上記［１］又は［２］に記載のポリカーボネートジオール組成物。
［４］
ＩＣＰにより測定した際の、チタン、イッテルビウム、スズ及びジルコニウムからなる群より選ばれる少なくとも１種の金属元素の含有量が０．０００１〜０．０２重量％である、上記［１］〜［３］のいずれかに記載のポリカーボネートジオール組成物。
［５］
ＩＣＰにより測定した際の、チタン、イッテルビウム、スズ及びジルコニウムの総含有量が０．０００１〜０．０２重量％である、上記［１］〜［４］のいずれかに記載のポリカーボネートジオール組成物。
［６］
ＩＣＰにより測定した際のリン元素の含有量が０．０００１〜０．０２重量％である、上記［１］〜［５］のいずれかに記載のポリカーボネートジオール組成物。
［７］
下記式（Ｈ）で表されるカーボネート化合物を０．０３〜５重量％含む、上記［１］〜［６］のいずれかに記載のポリカーボネートジオール組成物。

（式（Ｈ）中、ｉ及びｋは、２〜１５の整数を表し、ｉ≠ｋである。）
［８］
テトラヒドロフラン、テトラヒドロピラン及びオキセパンからなる群より選ばれる少なくとも１種の環状エーテル化合物の含有量が０．０１〜５０ｐｐｍである、上記［１］〜［７］のいずれかに記載のポリカーボネートジオール組成物。
［９］
テトラヒドロフラン、テトラヒドロピラン及びオキセパンの総含有量が０．０１〜５０ｐｐｍである、上記［１］〜［８］のいずれかに記載のポリカーボネートジオール組成物。
［１０］
下記式（Ｉ）で表されるカーボネート化合物を０．０１〜３重量％含む、上記［１］〜［９］のいずれかに記載のポリカーボネートジオール組成物。

（式（Ｉ）中、ｒは、２〜１５の整数を表す。）
［１１］
水分量が１〜５００ｐｐｍである、上記［１］〜［１０］のいずれかに記載のポリカーボネートジオール組成物。
［１２］
色数が５〜１００である、上記［１］〜［１１］のいずれかに記載のポリカーボネートジオール組成物。
［１３］
上記［１］〜［１２］のいずれかに記載のポリカーボネートジオール組成物と有機ポリイソシアネートとを含む、コーティング組成物。
［１４］
上記［１］〜［１２］のいずれかに記載のポリカーボネートジオール組成物と有機ポリイソシアネートとを反応させて得られるウレタンプレポリマーを含み、該ウレタンプレポリマーが末端イソシアネート基を持つ、コーティング組成物。
［１５］
上記［１］〜［１２］のいずれかに記載のポリカーボネートジオール組成物、有機ポリイソシアネート及び鎖伸長剤を反応させて得られるポリウレタン樹脂を含む、コーティング組成物。
［１６］
水、上記［１］〜［１２］のいずれかに記載のポリカーボネートジオール組成物、有機ポリイソシアネート及び鎖伸長剤を反応させて得られるポリウレタンを含む、水系コーティング組成物。
［１７］
上記［１］〜［１２］のいずれかに記載のポリカーボネートジオール組成物と有機ポリイソシアネートとを用いて得られる、熱可塑性ポリウレタン。 That is, the configuration of the present invention is as follows.
[1]
A polycarbonate diol containing a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and

(In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)
A polycarbonate diol composition comprising 0.05 to 5% by weight of a carbonate compound represented by the following formula (B).

(In formula (B), l and m represent an integer of 2 to 15, where l ≠ m.)
[2]
The polycarbonate diol composition according to the above [1], wherein the carbonate compound represented by the formula (B) is a carbonate compound represented by the following formula (C).

(In formula (C), l and m represent an integer of 4 to 6, where l ≠ m.)
[3]
The polycarbonate diol composition according to the above [1] or [2], wherein the terminal OH group ratio in the polycarbonate diol is 95.0 to 99.9%.
[4]
[1] to [3], wherein the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin and zirconium when measured by ICP is 0.0001 to 0.02 wt% The polycarbonate diol composition according to any one of the above.
[5]
The polycarbonate diol composition according to any one of the above [1] to [4], wherein the total content of titanium, ytterbium, tin and zirconium as measured by ICP is 0.0001 to 0.02% by weight.
[6]
The polycarbonate diol composition according to any one of the above [1] to [5], wherein the phosphorus element content as measured by ICP is 0.0001 to 0.02 wt%.
[7]
The polycarbonate diol composition according to any one of [1] to [6] above, containing 0.03 to 5% by weight of a carbonate compound represented by the following formula (H).

(In formula (H), i and k represent an integer of 2 to 15, and i ≠ k.)
[8]
The polycarbonate diol composition according to any one of [1] to [7] above, wherein the content of at least one cyclic ether compound selected from the group consisting of tetrahydrofuran, tetrahydropyran, and oxepane is 0.01 to 50 ppm.
[9]
The polycarbonate diol composition according to any one of the above [1] to [8], wherein the total content of tetrahydrofuran, tetrahydropyran and oxepane is 0.01 to 50 ppm.
[10]
The polycarbonate diol composition according to any one of [1] to [9] above, containing 0.01 to 3% by weight of a carbonate compound represented by the following formula (I).

(In formula (I), r represents an integer of 2 to 15)
[11]
The polycarbonate diol composition according to any one of the above [1] to [10], wherein the water content is 1 to 500 ppm.
[12]
The polycarbonate diol composition according to any one of [1] to [11], wherein the number of colors is 5 to 100.
[13]
The coating composition containing the polycarbonate diol composition in any one of said [1]-[12], and organic polyisocyanate.
[14]
The coating composition which contains the urethane prepolymer obtained by making the polycarbonate diol composition and organic polyisocyanate in any one of said [1]-[12] react, and this urethane prepolymer has a terminal isocyanate group.
[15]
The coating composition containing the polyurethane resin obtained by making the polycarbonate diol composition in any one of said [1]-[12], organic polyisocyanate, and a chain extender react.
[16]
An aqueous coating composition comprising water, polyurethane obtained by reacting the polycarbonate diol composition according to any one of [1] to [12] above, an organic polyisocyanate and a chain extender.
[17]
A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of the above [1] to [12] and an organic polyisocyanate.

  When the polycarbonate diol composition of the present invention is used as a constituent material of a paint, a smooth coating film can be obtained without impairing chemical resistance. Further, when the polycarbonate diol composition of the present invention is used as a raw material for polyurethane, it is possible to obtain a polyurethane having excellent oil resistance without impairing mechanical strength. Because of these characteristics, the polycarbonate diol composition of the present invention can be suitably used as a constituent material for paints and further as a raw material for polyurethane.

  Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

（式（Ａ）中、Ｒは、炭素数２〜１５の二価の脂肪族又は脂環族炭化水素を表す。）
下記式（Ｂ）で表されるカーボネート化合物を０．０５〜５重量％含む。

（式（Ｂ）中、ｌ及びｍは、２〜１５の整数を表し、ｌ≠ｍである。） <Polycarbonate diol composition>
The polycarbonate diol composition of this embodiment is
A polycarbonate diol containing a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and

(In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)
The carbonate compound represented by the following formula (B) is contained in an amount of 0.05 to 5% by weight.

(In formula (B), l and m represent an integer of 2 to 15, where l ≠ m.)

  The polycarbonate diol used in this embodiment has a repeating unit represented by the above formula (A) and a terminal hydroxyl group.

  In formula (A), R represents a C2-C15 bivalent aliphatic or alicyclic hydrocarbon, and can select 1 type (s) or 2 or more types in all the repeating units. In the formula (A), when R is a divalent aliphatic hydrocarbon having no side chain, the chemical resistance and mechanical strength of the polyurethane are preferably increased. Furthermore, in the formula (A), when R is one or more divalent aliphatic hydrocarbons selected from the following formula (D), the balance between chemical resistance and mechanical strength is good, This is preferable because a polyurethane having good moldability can be obtained.

（式（Ｄ）中、ｎは、４〜６の整数を表す。）

(In formula (D), n represents an integer of 4 to 6)

  When R is two kinds of divalent aliphatic hydrocarbons when n = 5 and divalent aliphatic hydrocarbons when n = 6 in the formula (D), polycarbonate diol even at a low temperature of −5 ° C. Since the composition becomes liquid, it is more preferable.

  In the polycarbonate diol, the ratio of the repeating unit represented by the formula (A) is preferably from 95 mol% to 100 mol%, more preferably from 97 mol% to 100 mol, from the viewpoint of heat resistance and hydrolysis resistance. % Or less, more preferably 99 mol% or more and 100 mol% or less.

  The polycarbonate diol composition of the present embodiment is preferably liquid at normal temperature. When the polycarbonate diol composition of the present embodiment is used as a constituent component of a paint, it is less likely to become clouded even when used in a transparent paint, and therefore, its use is rarely limited. In the present embodiment, the liquid state means that the polycarbonate diol composition heated to 80 ° C. is placed in a transparent sample bottle, is transparent when visually observed when cooled to room temperature, and flows slightly even when the sample bottle is tilted. A state that has sex.

  The polycarbonate diol composition of the present embodiment includes a carbonate compound represented by the above formula (B), that is, a cyclic compound having two carbonate bonds. The polycarbonate diol composition of the present embodiment can obtain a desired coating film by containing a predetermined amount of the carbonate compound having the structure. In the composition of the present embodiment, when the carbonate compound represented by the formula (B) is present in a predetermined amount together with the polycarbonate diol, each carbonate bond of the carbonate compound may be two carbonate bonds in the polycarbonate diol molecule or different from each other. It interacts with the carbonate bond of the polycarbonate diol molecule. As a result, the carbonate bond distance within the molecule or between the molecules increases, and the interaction within or between the polycarbonate diol molecules decreases. As a result, using the polycarbonate diol composition of the present embodiment, for example, when a coating film is obtained by spray coating, the sprayed coating liquid droplets are less likely to aggregate and easily adhere to the substrate. Smoothness is improved. Furthermore, since the carbonate compound directly acts on the carbonate bond of the polycarbonate diol, the effect is exhibited in a small amount and the bleed-out is less likely. In addition, since the carbonate compound used in this embodiment has methylene chains having different chain lengths, it has low crystallinity and is liquid at room temperature. Therefore, when the carbonate compound is used as a constituent material of a paint, the transparency of the coating film is not impaired. Moreover, since the carbonate compound has two carbonate bonds in the molecule, it generates two molecules of carbon dioxide per molecule when decomposed. Such a carbonate compound has a possibility of imparting flame retardancy to a coating film or polyurethane. Moreover, since the carbonate compound used for this embodiment has a methylene chain of different chain length, it has a distortion in the ring structure, and it can be expected to generate carbon dioxide before the coating film and polyurethane are decomposed.

  The carbonate compound used in the present embodiment is stable if the methylene chain between carbonate bonds is 2 or more, and the above effect can be obtained if the methylene chain between carbonate bonds is 15 or less. The carbonate compound is not particularly limited. For example, 1,3,6,8-tetraoxacycloundecane-2,7-dione, 1,3,7,9-tetraoxacyclotridecane-2,8- Dione, 1,3,8,10-tetraoxacyclopentadecane-2,9-dione, 1,3,9,11-tetraoxacycloheptadecane-2,10-dione, 1,3,10,12-tetra Oxacyclononadecane-2,11-dione, 1,3,11,13-tetraoxacycloheneicosane-2,12-dione, 1,3,12,14-tetraoxacyclotricosane-2,13- Dione, 1,3,13,15-tetraoxacyclopentacosane-2,14-dione, 1,3,14,16-tetraoxacycloheptacosane-2,15-dione, 3,15,17-tetraoxacyclononacosane-2,16-dione, 1,3,16,18-tetraoxacyclohentriacontane-2,16-dione, 1,3,17,19-tetraoxacyclo Carbonate compounds in which the difference between l and m in the above formula (B) is 1, such as tritriacontane-2,18-dione, 1,3,18,20-tetraoxacyclopentatricontane-2,19-dione; 1,3,6,8-tetraoxacyclododecane-2,7-dione, 1,3,7,9-tetraoxacyclotetradecane-2,8-dione, 1,3,8,10-tetraoxacyclohexadecane -2,9-dione, 1,3,9,11-tetraoxacyclooctadecane-2,10-dione, 1,3,10,12-tetraoxacycloicosane- , 11-dione, 1,3,11,13-tetraoxacyclodocosane-2,12-dione, 1,3,12,14-tetraoxacyclotetracosane-2,13-dione, 1,3,13 , 15-tetraoxacyclohexacosane-2,14-dione, 1,3,14,16-tetraoxacyclooctacosane-2,15-dione, 1,3,15,17-tetraoxacyclotriacontane-2 , 16-dione, 1,3,16,18-tetraoxacyclodotriacontane-2,17-dione, 1,3,17,19-tetraoxacyclotetratriacontane-2,18-dione and the like ( B) carbonate compounds in which the difference between l and m is 2; 1,3,6,8-tetraoxacyclotridecane-2,7-dione, 1,3,7,9-tetrao Xacyclopentadecane-2,8-dione, 1,3,8,10-tetraoxacycloheptadecane-2,9-dione, 1,3,9,11-tetraoxacyclononadecane-2,10-dione, 1,3,10,12-tetraoxacyclohenicosane-2,11-dione, 1,3,11,13-tetraoxacyclotricosane-2,12-dione, 1,3,12,14-tetra Oxacyclopentacosane-2,13-dione, 1,3,13,15-tetraoxacycloheptacosane-2,14-dione, 1,3,14,16-tetraoxacyclononacosane-2,15-dione 1,3,15,17-tetraoxacyclohentriacontane-2,16-dione, 1,3,16,18-tetraoxacyclotritriacontane-2,17-dio Carbonate compound difference between l and m in the formula (B) is 3 and the like. When the difference between 1 and m in the above formula (B) is 1, it is preferable because the distortion of the ring structure is small and the stability of the carbonate compound is high.

  Further, when the carbonate compound used in the present embodiment is a carbonate compound represented by the following formula (C), that is, when the number of methylenes between the carbonate bonds is 4 to 6, the distance between the carbonate bonds and the carbonate The ratio of carbonate bonds in the compound is preferred.

（式（Ｃ）中、ｌ及びｍは、４〜６の整数を表し、ｌ≠ｍである。）

(In formula (C), l and m represent an integer of 4 to 6, where l ≠ m.)

  Furthermore, when the carbonate compound represented by the formula (B) is a carbonate compound represented by the following formula (E) or (F), the stability of the carbonate compound is high, the distance between the carbonate bonds and the carbonate in the carbonate compound. The bonding ratio is more preferable.

  The content of the carbonate compound contained in the polycarbonate diol composition of the present embodiment is 0.05 to 5% by weight. A smooth coating film is obtained when the content of the carbonate compound is 0.05% by weight or more, and a transparent coating film having chemical resistance is obtained when the content of the carbonate compound is 5% by weight or less. . The content of the carbonate compound is more preferably 0.07 to 4% by weight, and even more preferably 0.08 to 2% by weight. In the polycarbonate diol composition of the present embodiment, the content of the carbonate compound is small compared to the amount of general plasticizer added, so that the mechanical properties and chemical resistance are not deteriorated. The carbonate compound used in the present embodiment is also produced in the production of polycarbonate diol, but is preferably added to the polycarbonate diol so as to be the above-mentioned predetermined amount.

  The polycarbonate diol composition of the present embodiment can also contain a carbonate compound represented by the following formula (I), that is, a cyclic compound having a methylene chain of the same length and having two carbonate bonds. When the carbonate compound represented by the following formula (I) is present in a predetermined amount together with the polycarbonate diol, the polyurethane obtained using the polycarbonate diol composition of the present embodiment has a high flow start temperature and is less likely to block. The smoothness of the resin surface is increased. In addition, when the carbonate compound represented by the following formula (I) is present in a predetermined amount together with the polycarbonate diol, a smooth and tough coating film can be obtained when the polycarbonate diol composition of the present embodiment is used as a constituent material of the paint. it can. When r in the following formula (I) is 4 to 6, that is, when the number of methylenes between carbonate bonds is 4 to 6, the above effect is remarkable, which is preferable.

（式（Ｉ）中、ｒは、２〜１５の整数を表す。）

(In formula (I), r represents an integer of 2 to 15)

  The content of the carbonate compound represented by the formula (I) contained in the polycarbonate diol composition of the present embodiment is preferably 0.01 to 3% by weight. If the polycarbonate diol composition of the present embodiment has a content of the carbonate compound of 0.01% by weight or more, the flow start temperature of the polyurethane obtained using the polycarbonate diol composition of the present embodiment becomes high, and blocking. When the content of the carbonate compound is 3% by weight or less, a transparent coating film having chemical resistance can be obtained. The content of the carbonate compound is more preferably 0.01 to 0.5% by weight, and further preferably 0.01 to 0.05% by weight.

  In addition, in this embodiment, content of each carbonate compound can be calculated | required by the method described in the below-mentioned Example.

  The polycarbonate diol composition of the present embodiment can contain a carbonate multimer represented by the following formula (J), that is, a cyclic compound having 3 to 10 carbonate bonds.

（式（Ｊ）中、ｌは、２〜１５の整数を表し、ｐは、３〜１０の整数を表す。）

(In formula (J), l represents an integer of 2 to 15, and p represents an integer of 3 to 10).

  When the carbonate multimer is a carbonate compound represented by the following formula (H), that is, a cyclic compound having three carbonate bonds and two methylene chains having different lengths, the present embodiment including the cyclic compound The polycarbonate diol composition in the form is preferable because it can improve the moldability without lowering the strength of the polyurethane obtained, and can form a smoother coating film. Furthermore, when the carbonate multimer is a carbonate compound represented by the following formula (H) and i and k are represented by integers of 4 to 6, the effect is even greater.

（式（Ｈ）中、ｉ及びｋは、２〜１５の整数を表し、ｉ≠ｋである。）

(In formula (H), i and k represent an integer of 2 to 15, and i ≠ k.)

  The content of the carbonate multimer contained in the polycarbonate diol composition of the present embodiment is preferably 0.03 to 5% by weight.

  In the polycarbonate diol composition of the present embodiment, if the content of the carbonate multimer is 0.03% by weight or more, the resulting polyurethane has better moldability, and the content of the carbonate multimer is 5% by weight. If it is below, a tough and smooth coating film having good adhesion can be obtained. The carbonate multimer content is preferably 0.03 to 3% by weight, more preferably 0.03 to 0.5% by weight, and even more preferably 0.03 to 0.2% by weight. 0.03 to 0.1 weight is even more preferable.

  In addition, in this embodiment, fixed_quantity | quantitative_assay of content of each carbonate multimer can be performed with the determination method of the carbonate compound described in the below-mentioned Example.

  The polycarbonate diol composition of the present embodiment can also contain a cyclic ether compound represented by the following formula (K).

（式（Ｋ）中、ｑは３〜１５の整数を表す。）

(In formula (K), q represents an integer of 3 to 15)

  The cyclic ether compound is tetrahydrofuran (when q is 4 in formula (K)), tetrahydropyran (when q is 5 in formula (K)), or oxepane (when q is 6 in formula (K)). In this case, the polycarbonate diol composition containing the cyclic ether compound is preferable because the compatibility with the solvent is improved and a smoother coating film is obtained due to a synergistic effect with the effect of the carbonate compound represented by the formula (B).

  In the polycarbonate diol composition of the present embodiment, the content of the cyclic ether compound is preferably 0.01 to 50 ppm. When the content of the cyclic ether compound is 0.01 to 5 ppm, the cyclic ether compound is more preferable because it does not volatilize from the carbonate compound, and when the content is 0.01 to 0.5 ppm, it is more preferable.

  In the polycarbonate diol composition of the present embodiment, the content of at least one cyclic ether compound selected from the group consisting of tetrahydrofuran, tetrahydropyran and oxepane is preferably 0.01 to 50 ppm, preferably 0.01 to 5 ppm. It is more preferable that it is 0.01-0.5 ppm. In the polycarbonate diol composition of the present embodiment, the total content of tetrahydrofuran, tetrahydropyran and oxepane is preferably 0.01 to 50 ppm, more preferably 0.01 to 5 ppm, More preferably, it is -0.5 ppm.

  In addition, in this embodiment, content of a cyclic ether compound can be calculated | required by the method described in the below-mentioned Example.

  The polycarbonate diol used in the present embodiment can also include a structure represented by a repeating unit of the following formula (G) in the molecule for the purpose of imparting flexibility.

（式（Ｇ）中、Ｒ’はアルキレン基を表し、全繰り返しの単位において、該アルキレン基は２種以上あっても構わない。また、ｘは２以上の整数を表す。）

(In formula (G), R ′ represents an alkylene group, and in all repeating units, there may be two or more of the alkylene groups. X represents an integer of 2 or more.)

  The method for introducing the repeating unit of the above formula (G) into the molecule of the polycarbonate diol is not particularly limited. For example, polyoxyethylene glycol, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, polyoxytetramethylene glycol An ether-based polyol such as polyoxypropylene glycol may be added to the raw material diol, or an alkylene oxide such as ethylene oxide and / or propylene oxide may be added during the polymerization.

  In the polycarbonate diol used in the present embodiment, the content of the repeating unit of the formula (G) in the molecule is not particularly limited as long as it does not affect the present invention, but the polyurethane obtained when the amount increases. Heat resistance and chemical resistance may be reduced. Therefore, when the repeating unit represented by the formula (G) is introduced into the polycarbonate diol, the repeating unit of the carbonate represented by the formula (A) is represented by the formula (G) (the structure derived from the ether). The repeating unit is preferably 0.05 to 5 mol%, more preferably 0.05 to 3 mol%.

  The number average molecular weight of the polycarbonate diol used in this embodiment is preferably 300 to 5,000. If the number average molecular weight of the polycarbonate diol is 300 or more, the flexibility of the coating film can be obtained. If the number average molecular weight of the polycarbonate diol is 5000 or less, when used as a constituent material of a paint, the solid content concentration of the paint is not limited, and the molding processability of the resulting polyurethane is not lowered, which is preferable. . The number average molecular weight of the polycarbonate diol is more preferably 450 to 3000.

  In addition, in this embodiment, the number average molecular weight of polycarbonate diol can be measured by the method as described in the below-mentioned Example.

  The polycarbonate diol used in this embodiment preferably has a terminal OH group ratio of 95.0 to 99.9%. If the terminal OH group ratio is 99.9% or less, a fine high molecular weight gel or the like is not generated, and the smoothness of the coating film surface is not lowered, and the terminal OH group ratio is 95.0% or more. If the coating film is cured, the coating film surface does not leave a slimy feeling, which is preferable. The terminal OH group ratio is more preferably 97.0 to 99.9%, further preferably 98.0 to 99.9%.

  In the present embodiment, the terminal OH group ratio is defined as follows. 70 g to 100 g of the polycarbonate diol was heated and stirred at a temperature of 160 ° C. to 200 ° C. under a pressure of 0.4 kPa or less to obtain a fraction corresponding to about 1 to 2% by weight of the polycarbonate diol, ie about 1 g ( An initial fraction of 0.7-2 g) is obtained. The obtained fraction is dissolved in about 100 g (95 to 105 g) of ethanol and recovered as a solution. The recovered solution is subjected to gas chromatography analysis (hereinafter also referred to as “GC analysis”), and the terminal OH group ratio calculated by the following formula (1) from the value of the peak area of the chromatograph obtained. For GC analysis, gas chromatography 6890 (manufactured by Hewlett-Packard USA) with DB-WAX (manufactured by J & W USA) 30 m and film thickness 0.25 μm was used as a column, and a flame ionization detector ( FID). The temperature rise profile of the column is a profile in which the temperature is raised from 60 ° C. to 250 ° C. at 10 ° C./min and then held at that temperature for 15 minutes. Identification of each peak in the GC analysis was performed using the following GC-MS apparatus. The GC apparatus uses 6890 (manufactured by Hewlett-Packard USA) with DB-WAX (manufactured by J & W USA) as a column. In the GC apparatus, the temperature is raised from an initial temperature of 40 ° C. to 220 ° C. at a heating rate of 10 ° C./min. The MS apparatus uses Auto-massSUN (manufactured by Japan JEOL). In the MS apparatus, measurement is performed with an ionization voltage of 70 eV, a scan range m / z = 10 to 500, and a photomultiplier gain of 450V.

Terminal OH group ratio (%) = B ÷ A × 100 (1)
A: Sum of peak areas of alcohols (excluding ethanol) containing diol B: Sum of peak areas of diol

  The terminal OH group ratio corresponds to the ratio of OH groups in all terminal groups of the polycarbonate diol. That is, as shown above, when the polycarbonate diol is heated to a temperature of 160 ° C. to 200 ° C. under a pressure of 0.4 kPa or less, the terminal portion of the polycarbonate diol is distilled as an alcohol (see the following formula (a)). ). Although it does not specifically limit as alcohol to distill, For example, the monoalcohol derived from the carbonate compound of raw materials, such as the diol used for the raw material, impurities contained in raw materials, such as cyclohexanediol and 1,5-hexanediol, and methanol And monoalcohols having unsaturated hydrocarbons produced by side reactions during polymerization.

（式（ａ）中、Ｘは−Ｒ²−ＯＨまたは−Ｒ²であり、Ｒ¹及びＲ²は炭化水素を表す。）

(In formula (a), X is —R ² —OH or —R ² , and R ¹ and R ² represent hydrocarbons.)

  The proportion of diol in all alcohols in this fraction is the proportion of terminal OH groups.

  In the polycarbonate diol composition of the present embodiment, the water content is preferably 1 to 500 ppm. It is preferable that the polycarbonate diol composition of the present embodiment has a water content of 500 ppm or less because a smooth coating film can be obtained without being clouded by the reaction between water and isocyanate. In addition, the polycarbonate diol composition of the present embodiment is preferable if the water content is 1 ppm or more because the carbonate compound can be easily dispersed in the polycarbonate diol. If the moisture content is 5 to 250 ppm, the effect becomes more remarkable, and if it is 10 to 150 ppm, it is more preferable.

  In this embodiment, the water content of the polycarbonate diol composition can be determined by the method described in the examples described later.

  As for the number of colors of the polycarbonate diol composition of this embodiment, 5-100 are preferable. If the number of colors is 100 or less, the polycarbonate diol composition of the present embodiment is preferable because the coating film is not colored. Moreover, the polycarbonate diol composition of this embodiment is preferable, if the number of colors is 5 or more, without restricting the production conditions of the polycarbonate diol. If the number of colors is 5 to 50, the effect becomes more remarkable, and if it is 5 to 30, it is more preferable.

  A method for obtaining a polycarbonate diol composition having a color number within the above range is not particularly limited, and examples thereof include a method of polymerizing at a temperature of 200 ° C. or lower, preferably 170 ° C. or lower.

  In the present embodiment, the number of colors of the polycarbonate diol composition can be determined by determining the number of colors of the polycarbonate diol composition described in Examples described later.

  The manufacturing method of the polycarbonate diol used for this embodiment is not specifically limited. The polycarbonate diol used in the present embodiment can be produced by various methods described in, for example, Schnell, Polymer Reviews Vol. 9, p9-20 (1994).

  Although the polycarbonate diol used for this embodiment is not specifically limited, For example, diol and a carbonate are manufactured from a raw material.

  The diol used in the present embodiment is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14- Diols having no side chain such as tetradecanediol and 1,15-pentadecanediol; 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4 Diols having side chains such as diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexane And cyclic diols such as dimethanol and 2-bis (4-hydroxycyclohexyl) -propane. One or two or more diols may be used as a raw material for polycarbonate diol. When one or two or more diols are used as a raw material for polycarbonate diol from a diol having no side chain, it is preferable because chemical resistance and mechanical strength of the coating film are increased. It is more preferable when two types of diols selected from the group consisting of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are used as raw materials for polycarbonate diol. More preferably, 1,5-pentanediol or 1,6-hexanediol is used as the diol raw material.

  In the production of the polycarbonate diol used in the present embodiment, when two or more kinds of diols are used as raw materials, the ratio of these raw materials is not particularly limited. It is preferable to set the ratio of the raw materials used so that the obtained polycarbonate diol is liquid at normal temperature. When using 2 types of diol as a raw material, it is preferable to set up preparation amount by molar ratio between 20/80-80/20. If it is this range, the polycarbonate diol obtained will be in a liquid state. 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is more preferable because it becomes liquid even at 0 ° C. or less.

  Further, a compound having 3 or more hydroxyl groups per molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc., is a raw material for polycarbonate diol within a range that does not impair the performance of the polycarbonate diol used in the present embodiment. Can also be used. If a compound having three or more hydroxyl groups in one molecule is used as a raw material for polycarbonate diol, gelation occurs due to crosslinking during the polymerization reaction of the polycarbonate. Therefore, even when a compound having three or more hydroxyl groups in one molecule is used as a raw material for polycarbonate diol, the compound is used in an amount of 0.1 to 5 with respect to the total number of moles of diol used as a raw material for polycarbonate diol. It is preferable to make it mol%. This ratio is more preferably 0.1 to 1 mol%.

  In the production of the polycarbonate diol used in the present embodiment, the raw material carbonate is not particularly limited. For example, dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonate such as diphenyl carbonate; ethylene carbonate, Examples include alkylene carbonates such as trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Among these, one or more carbonates can be used as a raw material for the polycarbonate diol. From the viewpoint of easy availability and easy setting of conditions for the polymerization reaction, it is preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, or ethylene carbonate.

  In the production of the polycarbonate diol used in the present embodiment, it is preferable to add a catalyst. Examples of the catalyst include, but are not limited to, alkali metals such as lithium, sodium, and potassium, alkaline earth metal alcoholates such as magnesium, calcium, strontium, and barium, hydrides, oxides, amides, carbonates, hydroxides, and the like. Products, nitrogen-containing borates, and basic alkali metal salts and alkaline earth metal salts of organic acids. Further, the catalyst is not particularly limited. For example, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver , Indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, ytterbium, metals, salts, alkoxides, and organic compounds. One or more catalysts can be selected and used from them. When one or more catalysts are used from sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead, ytterbium metal, salt, alkoxide, organic compound, the polymerization of polycarbonate diol is successfully performed and obtained. This is preferable because it has little influence on the urethane reaction using polycarbonate diol. More preferably, titanium, ytterbium, tin, or zirconium is used as the catalyst.

  The polycarbonate diol composition of the present embodiment may contain 0.0001 to 0.02% by weight of the above catalyst as the amount of metal element measured using ICP. When the content of the catalyst is within the above range, the polymerization of the polycarbonate diol is carried out satisfactorily, and the influence on the urethane reaction using the obtained polycarbonate diol composition is small. The content of the catalyst is more preferably 0.0005 to 0.01% by weight.

  In the polycarbonate diol composition of the present embodiment, the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin and zirconium when measured by ICP is 0.0001 to 0.02% by weight. It is preferable that it is 0.0005 to 0.01 weight%. The polycarbonate diol composition of the present embodiment preferably has a total content of titanium, ytterbium, tin and zirconium of 0.0001 to 0.02% by weight as measured by ICP. More preferably, it is -0.01 weight%.

  In addition, in this embodiment, content of the metal element in a polycarbonate diol composition can be measured by the method as described in the below-mentioned Example.

  For example, when the polycarbonate diol used in the present embodiment is used as a raw material for polyurethane, it is preferable to treat the catalyst used in the production of the polycarbonate diol with a phosphorus compound. Although it does not specifically limit as a phosphorus compound, For example, phosphoric acid triesters, such as a trimethyl phosphate, a triethyl phosphate, a tributyl phosphate, a di-2-ethylhexyl phosphate, a triphenyl phosphate, a tricresyl phosphate, a cresyl diphenyl phosphate; Phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleic acid tetraphosphate, Ruacid phosphate, ethylene glycol Acid phosphates such as phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate; triphenyl phosphite, trisnonylphenyl phosphate, tricresyl Phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl mono Decyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis (2 Ethyl hexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis (decyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl penta Phosphites such as erythritol diphosphite and tris (2,4-di-tert-butylphenyl) phosphite; and phosphoric acid, phosphorous acid, hypophosphorous acid and the like.

  The amount of the phosphorus compound contained in the polycarbonate diol composition used in the present embodiment is preferably 0.0001 to 0.02% by weight as the phosphorus element content when measured using ICP. In the polycarbonate diol composition of the present embodiment, if the amount of the phosphorus compound is within the above range, for example, when used as a polyurethane raw material, the polyurethane diol reaction hardly affects the catalyst used in the production of the polycarbonate diol. In addition, the phosphorus compound hardly affects the production reaction of polyurethane and the physical properties of the reaction product. Furthermore, when a transesterification catalyst is present in the polycarbonate diol, decomposition of the carbonate compound present in the polycarbonate diol composition can be suppressed. In the polycarbonate diol composition of the present embodiment, the content of phosphorus element as measured by ICP is more preferably 0.0005 to 0.01% by weight.

  The specific example of the manufacturing method of the polycarbonate diol used for this embodiment is shown below. The production of the polycarbonate diol used in the present embodiment is not particularly limited, but can be performed, for example, in two stages. Diol and carbonate are mixed in a molar ratio (diol: carbonate), for example, in a ratio of 20: 1 to 1:10, preferably in a ratio of 10: 1 to 1: 2, and 100 to 100 at normal pressure or reduced pressure. The first stage reaction is performed at 250 ° C. When dimethyl carbonate is used as the carbonate, the resulting methanol can be removed as a mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate diol. When diethyl carbonate is used as the carbonate, the generated ethanol can be removed as a mixture with diethyl carbonate to obtain a low molecular weight polycarbonate diol. When ethylene carbonate is used as the carbonate, the resulting ethylene glycol can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate diol. Next, in the second stage reaction, the reaction product in the first stage is heated at 160 to 250 ° C. under reduced pressure to remove unreacted diol and carbonate and to condense low molecular weight polycarbonate diol. The reaction for obtaining a polycarbonate diol having a predetermined molecular weight. The first stage reaction is started at a temperature of 100 to 150 ° C., reacted at the reaction start temperature for 5 hours or more, and then heated at a rate of 15 ° C. or less per hour, and the second stage reaction is performed. By performing the reaction at a temperature of 120 to 170 ° C. under a pressure of 15 kPa or less, the amount of the carbonate compound produced by the reaction can be kept low, and a predetermined amount of the carbonate compound is added to the obtained polycarbonate diol. Thus, the amount of the carbonate compound contained in the polycarbonate diol can be controlled, which is more preferable. Further, the terminal OH group ratio of the polycarbonate diol used in the present embodiment is the production conditions such as impurities in the raw material, temperature and time, and when dialkyl carbonate and / or diaryl carbonate is used as the raw material carbonate, It can be adjusted by selecting one method or appropriately combining the conditions such as the charging ratio of diol and carbonate. When dialkyl carbonate and / or diaryl carbonate is used as the carbonate as the raw material, the reaction is carried out by adding the diol and carbonate as the raw material in a stoichiometric amount or a ratio close to it in accordance with the molecular weight of the target polycarbonate diol. As a result, an alkyl group or an aryl group derived from carbonate often remains at the end of the polycarbonate diol. Therefore, by setting the amount of diol with respect to carbonate, for example, 1.01 to 1.10 times the stoichiometric amount, polycarbonate diol has fewer terminal alkyl groups and terminal aryl groups, and more terminal hydroxyl groups. Can do. Furthermore, due to a side reaction, the end of the polycarbonate diol becomes a vinyl group, or, for example, when dimethyl carbonate is used as the carbonate, it becomes a methyl ester or methyl ether. In general, the side reaction is more likely to occur as the reaction temperature is higher and the reaction time is longer.

<Application>
The polycarbonate diol composition of the present embodiment can be used as a constituent material for paints and adhesives, as a raw material for polyurethane and thermoplastic elastomer, and for applications such as polyester and polyimide modifiers. In particular, when the polycarbonate diol composition of the present embodiment is used as a constituent material of a paint, a coating film having a smooth surface and a good balance of performance such as strength and chemical resistance can be obtained. In addition, when the polycarbonate diol composition of the present embodiment is used as a raw material for polyurethane or thermoplastic elastomer, a polyurethane or thermoplastic elastomer having a smooth surface, toughness and excellent chemical resistance can be obtained.

  The thermoplastic polyurethane of this embodiment can be obtained using the above-mentioned polycarbonate diol composition and organic polyisocyanate.

  Moreover, the coating composition of this embodiment contains the above-mentioned polycarbonate diol composition and organic polyisocyanate.

  Furthermore, it is preferable that the coating composition of this embodiment contains the urethane prepolymer obtained by making the above-mentioned polycarbonate diol composition and organic polyisocyanate react, and this urethane prepolymer has an isocyanate terminal group.

  Furthermore, the coating composition of the present embodiment more preferably includes a polyurethane resin obtained by reacting the above polycarbonate diol composition, organic polyisocyanate and chain extender. It is more preferable that the aqueous coating composition contains a polyurethane obtained by reacting an isocyanate and a chain extender.

  Although it does not specifically limit as organic polyisocyanate used, For example, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, and its mixture (TDI), crude TDI, diphenylmethane-4,4'-diisocyanate (MDI), crude MDI, naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, etc. Known aromatic diisocyanates, 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate Examples include known aliphatic diisocyanates such as (hydrogenated XDI), isocyanurate-modified products, carbodiimidization-modified products, and biuret-modified products of these isocyanates. These organic polyisocyanates may be used alone or in combination of two or more. These organic polyisocyanates may be used by masking isocyanate groups with a blocking agent.

  Further, in the reaction between the polycarbonate diol composition and the organic polyisocyanate, a chain extender can be used as a copolymerization component if desired. Although it does not specifically limit as a chain extender, For example, the usual chain extender in the polyurethane industry, ie, water, a low molecular polyol, a polyamine, etc. can be used. Examples of chain extenders include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1 , 10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane and other low molecular polyols, ethylenediamine, Examples include polyamines such as hexamethylenediamine, isophoronediamine, xylylenediamine, diphenyldiamine, and diaminodiphenylmethane. These chain extenders may be used alone or in combination of two or more.

  As a method for producing the coating composition (paint) of this embodiment, a production method known in the industry is used. For example, a two-component solvent-based coating composition in which a coating material obtained from the above polycarbonate diol composition and a curing agent composed of an organic polyisocyanate are mixed immediately before coating; the above polycarbonate diol composition and an organic polyisocyanate. 1-component solvent-based coating composition comprising a urethane prepolymer having isocyanate end groups obtained by reaction; 1-component comprising a polyurethane resin obtained by reacting the above polycarbonate diol composition, organic polyisocyanate and chain extender Type solvent-based coating compositions; or one-part water-based coating compositions.

  The coating composition (paint) of the present embodiment includes, for example, a curing accelerator (catalyst), a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a release agent, and a fluidity adjustment according to various applications. Agents, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, colorants, solvents and the like can be added.

  Although it does not specifically limit as a solvent of the coating composition (paint) of this embodiment, For example, dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, Examples include toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol, n-butanol, and water. These solvents can be used alone or in combination.

  A method for producing the thermoplastic polyurethane of the present embodiment is not particularly limited, and a polyurethane reaction technique known in the polyurethane industry is used. For example, a thermoplastic polyurethane can be produced by reacting the above-described polycarbonate diol composition with an organic polyisocyanate at room temperature to 200 ° C. under atmospheric pressure. When a chain extender is used, it may be added from the beginning of the reaction or may be added from the middle of the reaction. For the method for producing the thermoplastic polyurethane of this embodiment, reference can be made, for example, to US Pat. No. 5,070,173.

  In the polyurethane reaction, a known polymerization catalyst or solvent may be used. The polymerization catalyst used is not particularly limited, and examples thereof include dibutyltin dilaurate.

  It is preferable to add a stabilizer such as a heat stabilizer (for example, an antioxidant) or a light stabilizer to the thermoplastic polyurethane of the present embodiment. Further, a plasticizer, an inorganic filler, a lubricant, a colorant, silicon oil, a foaming agent, a flame retardant, and the like may be added.

  Next, the present invention will be described with reference to examples and comparative examples.

  The following examples are given to illustrate the present invention and are not intended to limit the scope of the invention in any way.

  The physical property values shown in the following examples and comparative examples were measured by the following methods.

1. Quantification of carbonate compound The carbonate compound was quantified as follows. First, the sample was dissolved in acetonitrile to make a 1% solution. The solution was analyzed using a liquid chromatograph mass spectrometer (LC / MS). Based on the area value obtained by the analysis, each carbonate compound in the sample was quantified using a calibration curve prepared in advance. The LC apparatus used was a Waters 2690 (Waters) equipped with a Waters Symmetry C8 (Waters) as a column. In the LC apparatus, the flow rate was 0.5 ml / min, and the measurement was performed with a gradient from acetonitrile: water = 30: 70 to acetonitrile: water = 100: 0 over 15 minutes. As the MS apparatus, Waters ZMD (manufactured by Waters) was used. In the MS apparatus, measurement was performed with ionization: APCl + and a photomultiplier voltage of 650V.

2. Determination of the composition of the polycarbonate diol The composition of the polycarbonate diol was determined as follows. First, 1 g of a sample was weighed into a 100 ml eggplant flask, and 30 g of ethanol and 4 g of potassium hydroxide were added to obtain a mixture. The resulting mixture was heated in a 100 ° C. oil bath for 1 hour. After cooling the mixture to room temperature, 1-2 drops of phenolphthalein as an indicator was added to the mixture and neutralized with hydrochloric acid. Thereafter, the mixture was cooled in a refrigerator for 3 hours, the precipitated salt was removed by filtration, and the filtrate was analyzed by gas chromatography (GC). The GC analysis uses a gas chromatography GC14B (manufactured by Shimadzu Corporation) with a DB-WAX (manufactured by J & W, USA) 30 m and a film thickness of 0.25 μm as a column, and diethylene glycol diethyl ester as an internal standard. A flame ionization detector (FID) was used. The temperature rising profile of the column was a profile in which the temperature was raised to 250 ° C. at 10 ° C./min after holding at 60 ° C. for 5 minutes.
The composition of polycarbonate diol was determined based on the area value of diol obtained by GC analysis.

3. Determination of the number average molecular weight of the polycarbonate diol The number average molecular weight of the polycarbonate diol is determined by the “neutralization titration method (JIS K0070-1992)”, in which acetic anhydride and pyridine are used and titrated with an ethanol solution of potassium hydroxide. ) Was determined and calculated using the following formula (2).

Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.1) (2)

4). Confirmation of properties of polycarbonate diol composition The polycarbonate diol composition heated to 80 ° C was placed in a transparent sample bottle, and the state cooled to room temperature was visually observed. The case where it is transparent and has a slight fluidity when the sample bottle is tilted is defined as liquid, and the case where it is opaque or the state does not change even when the sample bottle is tilted and both cases are represented as solid.

5. Determination of terminal OH group ratio The terminal OH group ratio in the polycarbonate diol was determined as follows. First, 70 to 100 g of polycarbonate diol was weighed in a 300 ml eggplant flask. Using a rotary evaporator connected to a trap ball for collecting fractions, the polycarbonate diol in the eggplant flask was heated and stirred at a temperature of about 180 ° C. under a pressure of 0.4 kPa or less, and the polycarbonate diol was added to the trap ball. A fraction corresponding to about 1 to 2% by weight, that is, about 1 g (0.7 to 2 g) of an initial fraction was obtained. The obtained fraction was dissolved in about 100 g (95 to 105 g) of ethanol and recovered as a solution. The recovered solution was subjected to gas chromatography analysis (hereinafter also referred to as “GC analysis”), and the terminal OH group ratio in the polycarbonate diol was calculated from the value of the peak area of the chromatograph obtained by the following formula (1). For GC analysis, gas chromatography 6890 (manufactured by Hewlett-Packard USA) with DB-WAX (manufactured by J & W USA) 30 m and film thickness 0.25 μm was used as a column, and a flame ionization detector ( FID). The temperature rising profile of the column was a profile that was raised from 60 ° C. to 250 ° C. at 10 ° C./min and then held at that temperature for 15 minutes. Identification of each peak in the GC analysis was performed using the following GC-MS apparatus. The GC device used was 6890 (manufactured by Hewlett-Packard, USA) with DB-WAX (manufactured by J & W, USA) as a column. In the GC apparatus, the temperature was raised from an initial temperature of 40 ° C. to 220 ° C. at a heating rate of 10 ° C./min. As the MS apparatus, Auto-massSUN (manufactured by JEOL, Japan) was used. In the MS apparatus, the measurement was performed with an ionization voltage of 70 eV, a scan range of m / z = 10 to 500, and a photomultiplier gain of 450V.

Terminal OH group ratio (%) = B ÷ A × 100 (1)
A: Sum of peak areas of alcohols (excluding ethanol) containing diol B: Sum of peak areas of diol

6). Analysis of contained elements by dielectric coupled plasma (ICP) Each element contained in the polycarbonate diol composition was analyzed as follows. First, a sample was weighed in a Teflon (registered trademark) decomposition vessel, and high-purity nitric acid (manufactured by Kanto Chemical) was added, and the sample was decomposed using a microwave decomposition apparatus (ETHOS TC, manufactured by Milestone General). The sample was completely decomposed, and the obtained decomposition solution became colorless and transparent. Pure water was added to the decomposition solution to prepare a test solution. The obtained test solution was quantified based on the standard solution of each element using a dielectric coupled plasma analyzer (Thermo Fisher Scientific, iCAP6300 Duo).

7). Smoothness of coating film About the coating film obtained from a polycarbonate diol composition, the amplitude (micrometer) of the unevenness | corrugation of the surface was calculated | required using the laser microscope (the Olympus make, OLS4100). The smoothness was expressed as a ratio with the amplitude of the coating film obtained in Comparative Application Example 2 as 1.

8). Acid Resistance of Coating Film About the coating film obtained from the polycarbonate diol composition, the appearance of the coating film after immersion in a 0.1 mol / L H ₂ SO ₄ aqueous solution at room temperature for 24 hours was visually evaluated. In accordance with JIS K5600-8-1, the degree and amount of defects were represented by grades 0 to 5, and the acid resistance of the coating film was defined.

9. Alkali resistance of coating film About the coating film obtained from the polycarbonate diol composition, the coating film appearance after being immersed in a 0.1 mol / L NaOH aqueous solution at room temperature for 24 hours was visually evaluated. According to JISK5600-8-1, the degree and amount of defects were represented by grades 0 to 5, and the coating film was alkali resistance.

10. Ethanol resistance of the coating film About the coating film obtained from the polycarbonate diol composition, the appearance of the coating film after being immersed in a 50% aqueous EtOH solution at room temperature for 4 hours was visually evaluated. According to JISK5600-8-1, the degree and amount of defects were represented by grades 0 to 5, and the coating film was ethanol resistant.

11. Transparency of coating film A coating film obtained from the polycarbonate diol composition was immersed in distilled water at 90 ° C for 1 week. Thereafter, moisture was wiped from the coating film, and the coating film was cured for 3 days in a thermostatic chamber at 23 ° C. and 50% RH. According to JIS K 7105, the total light transmittance of the coating film before and after immersion was determined, and the transparency of the coating film was determined from the following formula (3).

Transparency = F / E x 100 (3)
E: Total light transmittance (%) of the coating film before immersion
F: Total light transmittance (%) of the coated film after immersion

12 Coating Film Adhesion Using a coating film obtained from a polycarbonate diol composition, coating film adhesion was evaluated according to JIS K5600-5-6 (cross-cut method) according to a 6-step classification of 0-5.

13. Mechanical Properties of Polyurethane Film A polyurethane film obtained from a polycarbonate diol composition was cut into 10 mm × 80 mm strips and cured in a temperature-controlled room at 23 ° C. and 50% RH for 3 days. Using the Tensilon tensile tester (produced by ORIENTEC, RTC-1250A), the test specimen thus obtained was measured at a breaking distance (unit: MPa) and a breaking elongation (unit:%) at a chuck distance of 50 mm and a tensile speed of 100 mm / min. Was measured.

14 Oil Resistance of Polyurethane Film A polyurethane film obtained from a polycarbonate diol composition was cut into a 10 mm × 80 mm strip shape to obtain a test specimen. 0.1 g of oleic acid was made to adhere to the obtained test body, it was left to stand at 20 degreeC for 4 hours, and the external appearance of the test body was evaluated visually. According to JISK5600-8-1, the degree and amount of defects were represented by grades 0 to 5 and defined as oil resistance.

15. Measurement of water content in polycarbonate diol composition The water content in the polycarbonate diol composition was measured by a volumetric analysis method according to JIS K0068 using a water measuring device (KF-100 type, manufactured by Mitsubishi Chemical Analytech).

16. Determination of cyclic ether compound in polycarbonate diol composition The amount of cyclic ether compound in the polycarbonate diol composition was determined as follows. 2 g of sample was precisely weighed and placed in a 20 ml vial and sealed. The vial was heated at 100 ° C. for 3 hours, and 1 ml of the gas phase was collected with a gas tight syringe heated to 100 ° C. and measured by GC / MS. The GC apparatus used 7890A (manufactured by Agilent), and the column used was Equity-1 (manufactured by Sigma-Aldrich) 30 m and a film thickness of 0.25 μm. The temperature rise profile was a temperature rise profile in which after holding at 40 ° C. for 7 minutes, the temperature was raised to 280 ° C. at 10 ° C./min and held at that temperature for 5 minutes. As the MS apparatus, Jms-Q1000GC (manufactured by JEOL Ltd.) was used, and measurement was performed with an ionization voltage of 70 eV, a scan range m / z = 10 to 500, and a photomultiplier gain of 1300 V. Quantification was performed by preparing a calibration curve with 1-butanol.

Amount of cyclic ether compound (ppm) = G / H × 1000 (4)
G: Sum of cyclic ether compounds (mg)
H: Sample amount (g)

17. Determination of the number of colors of the polycarbonate diol composition The color number of the polycarbonate diol composition was determined according to JIS K0071-1 using a colorimetric tube.

18. Flow characteristics of thermoplastic polyurethane With respect to thermoplastic polyurethane, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho) was used and the rate of temperature increase: 3 ° C./min, die: 1 mmφ × 10 mmL, load: 5. By measuring under the condition of 5 MPa, a temperature [° C.]-Viscosity [dPa · s] curve was obtained. Based on the flow start temperature [° C.] and the ratio of the viscosity at the flow start temperature + 10 ° C. to the viscosity at the flow start temperature (see the following formula (5)), the flow characteristics of the thermoplastic polyurethane were evaluated. It was evaluated that as the flow start temperature was higher and the viscosity ratio was smaller, blocking was less likely to occur and the moldability was more excellent.

  Viscosity ratio = (flow start temperature + viscosity at 10 ° C.) / (Viscosity at flow start temperature)

[Example 1]
640 g (7.3 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, 1,6- 410 g (3.5 mol) of hexanediol was charged. As a catalyst, 0.35 g of titanium tetraisopropoxide was further added to the flask, and the reaction was started by stirring and heating the mixture in the flask at normal pressure. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 15 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 15 hours, and the reaction was carried out while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out at 164 ° C. for 15 hours while distilling off the mixture of diol and ethylene carbonate. Thereafter, 0.39 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 2 g of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) In addition, a polycarbonate diol composition was obtained by stirring at 100 ° C. for 5 hours. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-1. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 2]
Except that the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound when l = 5 and m = 6 in formula (B)) was 0.5 g Obtained a polycarbonate diol composition in the same manner as in Example 1. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-2. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 3]
Except that the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) was 11 g, A polycarbonate diol composition was obtained in the same manner as in Example 1. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-3. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 4]
Except that the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) was 20.5 g Obtained a polycarbonate diol composition in the same manner as in Example 1. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-4. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 1]
Except that the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) was 26 g, A polycarbonate diol composition was obtained in the same manner as in Example 1. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-21. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 5]
550 g (6.1 mol) of dimethyl carbonate, 400 g (3.9 mol) of 1,5-pentanediol, 1,6- 460 g (3.9 mol) of hexanediol was charged. As a catalyst, 0.50 g of titanium tetraisopropoxide was further added to the flask, and the reaction was started by stirring and heating the mixture in the flask at normal pressure. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 20 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 15 hours, and the reaction was carried out while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the pressure in the flask was reduced to 11 kPa, and the reaction was further carried out at 165 ° C. for 20 hours while distilling off the diol and dimethyl carbonate. Thereafter, 0.55 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. 500 g of the obtained polycarbonate diol was mixed with 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)). 0.5 g was added and stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-5. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1. Further, PC-5 had a water content of 41 ppm, a tetrahydropyran content of 0.9 ppm, and an oxepane content of 0.04 ppm. The number of colors of PC-5 was 10.

[Comparative Example 2]
Except for the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in formula (B)) of 0.1 g Obtained a polycarbonate diol composition in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-22. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 6]
Other than the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in formula (B)) being 0.25 g Obtained a polycarbonate diol composition in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-6. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 7]
Except for the addition amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in formula (B)) being 0.3 g Obtained a polycarbonate diol composition in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-7. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 3]
Except for adding 9.5 g of 1,3,10,12-tetraoxacyclooctadecane-2,11-dione (carbonate compound in the case of l = 6 and m = 6 in the formula (B)) as the carbonate compound. A polycarbonate diol composition was obtained in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-23. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 8]
0.5 g of 1,3,11,13-tetraoxacyclohenicosane-2,12-dione (a carbonate compound in the case of l = 7 and m = 8 in the formula (B)) was added as a carbonate compound. Except for the above, a polycarbonate diol composition was obtained in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-8. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 9]
Except for adding 0.5 g of 1,3,6,8-tetraoxacycloundecane-2,7-dione (carbonate compound in the case of l = 2, m = 3 in the formula (B)) as the carbonate compound A polycarbonate diol composition was obtained in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-9. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 4]
0.5 g of 1,3,19,21-tetraoxacycloheptatritan-2,20-dione (a carbonate compound in the case of l = 15 and m = 16 in the formula (B)) was added as a carbonate compound. Except for the above, a polycarbonate diol composition was obtained in the same manner as in Example 5. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-24. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 10]
820 g (7.0 mol) of diethyl carbonate, 350 g (3.4 mol) of 1,5-pentanediol and 1,6-pentanediol were added to a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer. 420 g (3.6 mol) of hexanediol was charged. As a catalyst, 0.30 g of titanium tetraisopropoxide was further added to the flask, and the mixture in the flask was stirred and heated at normal pressure to initiate the reaction. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 20 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 15 hours, and the reaction was carried out while distilling off the resulting mixture of ethanol and diethyl carbonate. Thereafter, the pressure in the flask was reduced to 13 kPa, and the reaction was further performed at 160 ° C. for 25 hours while distilling off the diol and diethyl carbonate. Thereafter, 0.33 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 2 g of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) In addition, a polycarbonate diol composition was obtained by stirring at 100 ° C. for 5 hours. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-10. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 11]
A polycarbonate diol was obtained by carrying out the reaction under the same conditions as in Example 10 except that the addition amount of diethyl carbonate was changed to 860 g (7.3 mol). To 500 g of the obtained polycarbonate diol, 2 g of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) In addition, a polycarbonate diol composition was obtained by stirring at 100 ° C. for 5 hours. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-11. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 12]
670 g (7.6 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, 3-methyl-into a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer 450 g (3.8 mol) of 1,5-pentanediol was charged. Further, 0.10 g of titanium tetraisopropoxide was added as a catalyst to the flask, and the reaction was started by stirring and heating the mixture in the flask at normal pressure. The reaction start temperature was 140 ° C., and the reaction was performed at this temperature for 18 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 15 hours, and the reaction was carried out while distilling off a mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out at 165 ° C. for 15 hours while distilling off the mixture of diol and ethylene carbonate. Thereafter, 0.11 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 2 g of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) In addition, a polycarbonate diol composition was obtained by stirring at 100 ° C. for 5 hours. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-12. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 13]
450 g (5.0 mol) of dimethyl carbonate and 1000 g (6.2 mol) of 1,9-nonanediol were charged into a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer. As a catalyst, 0.90 g of titanium tetraisopropoxide was further added to the flask, and the mixture in the flask was stirred and heated at normal pressure to initiate the reaction. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 15 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 13 hours, and the reaction was carried out while distilling off the resulting mixture of methanol and dimethyl carbonate. Thereafter, the pressure in the flask was reduced to 13 kPa, and the reaction was further carried out at 162 ° C. for 18 hours while distilling off the diol and dimethyl carbonate. Thereafter, 1.0 g of mono-2-ethylhexyl phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,8,10-tetraoxacyclopentadecane-2,9-dione (a carbonate compound in the case of l = 4 and m = 5 in the formula (B)) is added. 5 g was added and stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-13. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 14]
650 g (7.4 mol) of ethylene carbonate, 410 g (4.6 mol) of 1,4-butanediol, and 1,5-butanediol were placed in a 2 L glass flask equipped with a rectification column packed with a regular packing and a stirrer. Pentanediol (300 g, 2.9 mol) was charged. As a catalyst, 0.6 g of titanium tetraisopropoxide was further added to the flask, and the reaction was started by stirring and heating the mixture in the flask at normal pressure. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 15 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 15 hours, and the reaction was carried out while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out at 166 ° C. for 15 hours while distilling off the mixture of diol and ethylene carbonate. Thereafter, 0.67 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1.52 g of 1,3,8,10-tetraoxacyclopentadecane-2,9-dione (a carbonate compound in the case of l = 4 and m = 5 in the formula (B)) In addition, a polycarbonate diol composition was obtained by stirring at 100 ° C. for 5 hours. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-14. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Example 15]
630 g (7.2 mol) of ethylene carbonate, 140 g (1.6 mol) of 1,4-butanediol, 1,6- 670 g (6.7 mol) of hexanediol was charged. To the flask, 0.3 g of 2-ethylhexyl acid phosphate was further added as a catalyst, and the mixture in the flask was stirred and heated at normal pressure to initiate the reaction. The reaction start temperature was 140 ° C., and the reaction was carried out at that temperature for 15 hours. Thereafter, the reaction temperature was gradually raised to 160 ° C. over 13 hours, and the reaction was carried out while distilling off the mixture of ethylene glycol and ethylene carbonate produced. Thereafter, the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out at 164 ° C. for 15 hours while distilling off the mixture of diol and ethylene carbonate. Thereafter, 0.33 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in formula (B)) was added 2 0.0 g was added and stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-15. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 5]
A polycarbonate diol composition was obtained in the same manner as in Example 5 except that 0.5 g of 5-methyl-1,3-dioxan-2-one was added instead of the carbonate compound represented by the formula (B). . Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-25. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 6]
640 g (7.3 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, 1,6- 410 g (3.5 mol) of hexanediol was charged. To the flask, 0.50 g of titanium tetraisopropoxide was added as a catalyst, and the mixture in the flask was stirred and heated at normal pressure to initiate the reaction. The reaction start temperature was 135 ° C., and the reaction was carried out at this temperature for 22 hours. Thereafter, the reaction temperature was gradually raised to 155 ° C. over 20 hours, and the reaction was carried out while distilling off the mixture of ethylene glycol and ethylene carbonate produced. Thereafter, the pressure in the flask was reduced to 7 kPa, and the reaction was further carried out at 158 ° C. for 25 hours while distilling off the mixture of diol and ethylene carbonate. Thereafter, 0.55 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C. for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) was changed to 0. 0.1 g was added and stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-26.

[Example 16]
Except that the amount of 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) was 1.5 g. A polycarbonate diol composition was obtained in the same manner as in Comparative Example 6. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-16. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Comparative Example 7]
In accordance with 1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in formula (B)), 1,3,9, 13,17,19-hexaoxacyclopentacosane-2,10,18-trione (a carbonate compound in the case of i = 5 and k = 6 in the formula (H)) 13 g, 1,3,9,11 , 18,20-hexaoxacyclohexacosane-2,10,19-trione (a carbonate compound in the case of i = 6 and k = 5 in formula (H)) except that 13.5 g was added. 6 to obtain a polycarbonate diol composition. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-27.

[Example 17]
1,3,9,11-tetraoxacycloheptadecane-2,10-dione (a carbonate compound in the case of l = 5 and m = 6 in the formula (B)) , 10,12-tetraoxacyclooctadecane-2,11-dione (carbonate compound in the case of r = 6 in formula (I)) was added in the same manner as in Example 5 except that 0.4 g was added. A diol composition was obtained. Table 1 shows the result of analyzing the obtained polycarbonate diol composition. This polycarbonate diol composition is abbreviated as PC-17. The obtained polycarbonate diol had a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the R and ratio of each repeating unit were as shown in Table 1.

[Application Example 1]
Polycarbonate diol composition PC-1 40 g, leveling agent BYK-331 (manufactured by BYK Chemical) 0.75 g, dissolved in thinner (xylene / butyl acetate = 70/30 (weight ratio)) to 2 wt% 1.25 g of the dibutyltin dilaurate solution and 40 g of thinner were mixed and stirred to obtain a paint base. 7.5 g of organic polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals, isocyanate (NCO) content: 23.1%) as a curing agent was added to the obtained coating material base to prepare a coating solution. The coating solution was spray-coated on an acrylonitrile-butadiene-styrene (ABS) resin plate, the thinner was blown off at room temperature for 2 hours, and then heat-cured at 80 ° C. for 2 hours to obtain a coating film. The physical properties were evaluated using the coating film. The evaluation results are shown in Table 2.

[Application Examples 2 to 17]
A coating film was obtained in the same manner as in Application Example 1 except that PC-2 to 17 were used as the polycarbonate diol composition. The physical properties were evaluated using the coating film. The evaluation results are shown in Table 2.

[Comparative Application Examples 1 to 7]
A coating film was obtained in the same manner as in Application Example 1, except that PC-21 to 27 were used as the polycarbonate diol composition. The physical properties were evaluated using the coating film. The evaluation results are shown in Table 2.

[Application Example 18]
In a reactor equipped with a stirrer, a thermometer and a condenser, 200 g of PC-1 obtained in Example 1, 34 g of hexamethylene diisocyanate and 0.02 g of dibutyltin dilaurate as a catalyst were charged and reacted at 70 ° C. for 5 hours. A urethane prepolymer having a terminal isocyanate (NCO) group was obtained. A solution was obtained by adding 600 g of dimethylformamide as a solvent to the urethane prepolymer. Thereafter, 17 g of isophoronediamine as a chain extender was added to the obtained solution and stirred at 35 ° C. for 1 hour to obtain a polyurethane resin solution. The obtained polyurethane resin solution was cast on a glass plate, allowed to stand at room temperature for 30 minutes to evaporate the solvent, and then placed in a dryer at 100 ° C. for 2 hours to dry to obtain a polyurethane film. The physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 3.

[Application Examples 19 to 34]
A polyurethane film was obtained in the same manner as in Application Example 16 except that PC-2 to 17 were used as the polycarbonate diol composition. The physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 3.

[Comparative Application Examples 8 to 14]
A polyurethane film was obtained in the same manner as in Application Example 16 except that PC-21 to 27 were used as the polycarbonate diol composition. The physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 3.

[Application Example 35]
800 g of PC-5 obtained in Example 5 and 255 g of hexamethylene diisocyanate were charged into a reactor equipped with a stirrer, a thermometer and a cooling tube, and reacted at 100 ° C. for 4 hours to obtain terminal isocyanate (NCO) groups. A urethane prepolymer was obtained. The prepolymer was added with 107 g of 1,4-butanediol as a chain extender and 0.05 g of dibutyltin dilaurate as a catalyst, and a universal extruder for kneader (for LABO manufactured by Kasamatsu Chemical Research Laboratory, Japan) Using a universal extruder KR-35 type), a reaction was carried out at 140 ° C. for 60 minutes to obtain a thermoplastic polyurethane. Then, the obtained thermoplastic polyurethane was made into pellets with an extruder. When the flow characteristics of the obtained thermoplastic polyurethane were evaluated, the flow initiation temperature was 168 ° C. and the viscosity ratio was 0.046.

[Application Example 36]
A thermoplastic polyurethane was obtained in the same manner as in Application Example 35 except that PC-17 was used instead of PC-5 as the polycarbonate diol composition. When the flow characteristics of the obtained thermoplastic polyurethane were evaluated, the flow initiation temperature was 172 ° C. and the viscosity ratio was 0.033.

  When the polycarbonate diol composition of the present invention is used as a constituent material of a paint, a smooth coating film can be obtained without impairing chemical resistance. Further, when the polycarbonate diol composition of the present invention is used as a raw material for polyurethane, it is possible to obtain a polyurethane having excellent oil resistance without impairing mechanical strength. Because of these characteristics, the polycarbonate diol composition of the present invention can be suitably used as a constituent material for paints and further as a raw material for polyurethane.

Claims (17)

A polycarbonate diol containing a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and

(In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms.)
A polycarbonate diol composition comprising 0.05 to 5% by weight of a carbonate compound represented by the following formula (B).

(In formula (B), l and m represent an integer of 2 to 15, where l ≠ m.) The polycarbonate diol composition according to claim 1, wherein the carbonate compound represented by the formula (B) is a carbonate compound represented by the following formula (C).

(In formula (C), l and m represent an integer of 4 to 6, where l ≠ m.)   The polycarbonate diol composition according to claim 1 or 2, wherein the terminal OH group ratio in the polycarbonate diol is 95.0 to 99.9%.   The content of at least one metal element selected from the group consisting of titanium, ytterbium, tin and zirconium when measured by ICP is 0.0001 to 0.02% by weight. The polycarbonate diol composition according to one item.   The polycarbonate diol composition according to any one of claims 1 to 4, wherein the total content of titanium, ytterbium, tin and zirconium as measured by ICP is 0.0001 to 0.02 wt%.   The polycarbonate diol composition according to any one of claims 1 to 5, wherein the phosphorus element content as measured by ICP is 0.0001 to 0.02 wt%. The polycarbonate diol composition according to any one of claims 1 to 6, comprising 0.03 to 5% by weight of a carbonate compound represented by the following formula (H).

(In formula (H), i and k represent an integer of 2 to 15, and i ≠ k.)   The polycarbonate diol composition according to any one of claims 1 to 7, wherein the content of at least one cyclic ether compound selected from the group consisting of tetrahydrofuran, tetrahydropyran, and oxepane is 0.01 to 50 ppm.   The polycarbonate diol composition according to any one of claims 1 to 8, wherein the total content of tetrahydrofuran, tetrahydropyran and oxepane is 0.01 to 50 ppm. The polycarbonate diol composition according to any one of claims 1 to 9, comprising 0.01 to 3% by weight of a carbonate compound represented by the following formula (I).

(In formula (I), r represents an integer of 2 to 15)   The polycarbonate diol composition according to any one of claims 1 to 10, wherein the water content is 1 to 500 ppm.   The polycarbonate diol composition according to any one of claims 1 to 11, wherein the number of colors is 5 to 100.   A coating composition comprising the polycarbonate diol composition according to any one of claims 1 to 12 and an organic polyisocyanate.   A coating composition comprising a urethane prepolymer obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 12 with an organic polyisocyanate, wherein the urethane prepolymer has a terminal isocyanate group.   A coating composition comprising a polyurethane resin obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 12, an organic polyisocyanate, and a chain extender.   An aqueous coating composition comprising polyurethane obtained by reacting water, the polycarbonate diol composition according to any one of claims 1 to 12, an organic polyisocyanate, and a chain extender.   A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of claims 1 to 12 and an organic polyisocyanate.