JP6866037B2 - Polycarbonate diol composition - Google Patents

Description

The present invention relates to a polycarbonate diol composition.

Polycarbonate diol is known as a material having excellent hydrolysis resistance, light resistance, oxidation deterioration resistance, heat resistance and the like as a soft segment such as polyurethane and thermoplastic elastomer, for example. However, when the polycarbonate diol is used as a constituent material of a coating material, the flexibility of the coating film may be impaired because the interaction between the polycarbonate diol bonds is strong.

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 (see, for example, 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 (see, for example, Patent Document 2). Further, a polycarbonate diol composition containing 5-methyl-1,3-dioxane-2-one is disclosed (see, for example, Patent Document 3).

Special Table 2013-528652 Japanese Patent No. 5479844 Japanese Patent No. 5068159

However, when the cyclic carbonates described in Patent Documents 1 and 2 are used as constituent materials of paints, the mechanical strength of the coating film cannot be improved by adding a small amount, and bleeding out may occur when a large amount is added. Yes, there is room for improvement. Further, when the polycarbonate diol composition described in Patent Document 3 is used as a constituent material of a coating material, there is room for improvement in order to obtain a coating film having both mechanical strength and flexibility.
As described above, the conventional technique has not developed a polycarbonate diol capable of obtaining a coating film having mechanical strength and flexibility.

Therefore, an object of the present invention is to provide, for example, a polycarbonate diol composition capable of obtaining a coating film having mechanical strength and flexibility without impairing chemical resistance when used as a constituent material of a coating material. To do.

As a result of diligent research 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 achieved the present invention.

（式（Ａ）中、Ｒ¹は、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表す。）

（式（Ｃ）中、Ｒ²は、同一でも異なっていてもよく、（ＣＨ₂）₄又はＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₂を表し、ｍは、２〜８の整数を表す。）

［２］
前記式（Ｃ）で表されるカーボネート化合物が、下記式（Ｄ）で表されるカーボネート化合物である、［１］に記載のポリカーボネートジオール組成物。

（式（Ｄ）中、Ｒ²は、同一でも異なっていてもよく、（ＣＨ₂）₄又はＣＨ₂ＣＨ（ＣＨ₃）ＣＨ₂を表し、ｍは、３〜６の整数を表す。）
［３］
前記式（Ａ）で表される繰り返し単位の５〜９５モル％が下記式（Ｅ）で表される繰り返し単位である、［１］又は［２］に記載のポリカーボネートジオール組成物。

（式（Ｅ）中、ｎは、２〜１２の整数を表す。）
［４］
ＩＣＰにより測定した際の、チタン、イッテルビウム、及びジルコニウムの総含有量が０．０００１〜０．０２重量％である、［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リン元素の含有量が０．０００５〜０．０５重量％である、［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］
水分量が１〜５００ｐｐｍである、［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］
［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。
［８］
［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。
［９］
［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。
［１０］
［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、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。
［１１］
［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と、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。 That is, the configuration of the present invention is as follows.
[1]
A polycarbonate diol composition containing 0.05 to 5% by weight of a polycarbonate diol composed of a repeating unit represented by the following formula (A) and a terminal hydroxyl group and a carbonate compound represented by the following formula (C). ,
The polycarbonate diol composition, wherein 5 to 100 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (B).

(In the formula (A), R ¹ represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

(In the formula (C), R ² may be the same or different, and represents (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m represents an integer of 2 to 8.)

[2]
The polycarbonate diol composition according to [1], wherein the carbonate compound represented by the formula (C) is a carbonate compound represented by the following formula (D).

(In the formula (D), R ² may be the same or different, and represents (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m represents an integer of 3 to 6).
[3]
The polycarbonate diol composition according to [1] or [2], wherein 5 to 95 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (E).

(In formula (E), n represents an integer of 2 to 12.)
[4]
The polycarbonate diol composition according to any one of [1] to [3], wherein the total content of titanium, ytterbium, and zirconium as measured by ICP is 0.0001 to 0.02% by weight.
[5]
The polycarbonate diol composition according to any one of [1] to [4], wherein the content of the phosphorus element as measured by ICP is 0.0005 to 0.05% by weight.
[6]
The polycarbonate diol composition according to any one of [1] to [5], which has a water content of 1 to 500 ppm.
[7]
A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of [1] to [6] and an organic polyisocyanate.
[8]
A coating composition containing the polycarbonate diol composition according to any one of [1] to [6] and an organic polyisocyanate.
[9]
A coating composition containing a urethane prepolymer obtained by reacting the polycarbonate diol composition according to any one of [1] to [6] with an organic polyisocyanate, and the urethane prepolymer having a terminal isocyanate group.
[10]
A coating composition containing the polycarbonate diol composition according to any one of [1] to [6], an organic polyisocyanate, and a polyurethane resin obtained by reacting with a chain extender.
[11]
An aqueous coating composition containing the polycarbonate diol composition according to any one of [1] to [6] and polyurethane obtained by reacting an organic polyisocyanate with a chain extender.

When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, a coating film having mechanical strength and flexibility can be obtained. Since the polycarbonate diol composition of the present invention has these properties, it can be suitably used as a constituent material of a coating material and further as a raw material of polyurethane.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

<Polycarbonate diol composition>
The polycarbonate diol composition of the present embodiment contains 0.05 to 5 weight by weight of a polycarbonate diol composed of a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and a carbonate compound represented by the following formula (C). % Of a polycarbonate diol composition
5 to 100 mol% of the repeating unit represented by the formula (A) is the polycarbonate diol composition which is the repeating unit represented by the following formula (B).

(In the formula (A), R ¹ represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

(In formula (C), R ² may be the same or different, representing (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m representing an integer of 2-8.)

The polycarbonate diol used in the present embodiment comprises a repeating unit represented by the above formula (A) and a terminal hydroxyl group, and 5 to 100 mol% of the repeating unit represented by the formula (A) is represented by the above formula (B). It is a polycarbonate diol which is a repeating unit represented.
Since the polycarbonate diol in the present embodiment has the repeating unit represented by the formula (B), it has mechanical strength and flexibility, and further has chemical resistance such as sweat resistance, alkali resistance, and alcohol resistance. A coating film having the above is obtained. Since the repeating unit represented by the formula (B) can obtain even higher chemical resistance, it is preferably 20 to 100 mol%, preferably 40 to 100 mol% of the repeating unit represented by the formula (A). Is more preferable. Further, the repeating unit represented by the formula (B) may be 90 mol% or less of the repeating unit represented by the formula (A) because the viscosity of the obtained polycarbonate diol increases as the ratio increases. It is preferably 75 mol% or less, and more preferably 75 mol% or less.

For the repeating unit represented by the formula (A), in addition to the repeating unit represented by the formula (B), one or more repeating units represented by the following formula (F) shall be selected. Can be done.

(In the formula (F), R ³ represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms, except for the repeating unit represented by the formula (B).)

The repeating unit represented by the formula (F) is preferably the repeating unit represented by the following formula (E) from the viewpoint of enhancing the mechanical strength and flexibility of the coating film. Further, n in the formula (E) is preferably 4 to 6 from the viewpoint of further enhancing the mechanical strength and flexibility of the coating film.

(N in the formula (E) represents an integer of 2 to 12.)

The ratio of the repetition represented by the formula (E) in the repeating unit represented by the formula (A) is preferably 5 to 95 mol%. Further, the ratio of the repetition represented by the formula (E) in the repeating unit represented by the formula (A) is 10 to 80 mol% from the viewpoint of enhancing the mechanical strength and flexibility of the coating film. More preferably, it is 25 to 60 mol%.

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

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

(In the formula (G), R'represents an alkylene group, and in the unit of all repetitions, there may be two or more kinds of the alkylene group, and x represents an integer of two 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, and for example, polyoxyethylene glycol, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, and polyoxytetramethylene. An ether-based polyol such as glycol or 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 as the amount increases. Heat resistance and chemical resistance may decrease. Therefore, when the repeating unit represented by the formula (G) is introduced into the polycarbonate diol, the repeating unit represented by the formula (A) is represented by the formula (G) (the structure derived from ether). The repeating unit (having) 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 5000. When the number average molecular weight of the polycarbonate diol is 300 or more, the flexibility of the coating film can be obtained. When the number average molecular weight of the polycarbonate diol is 5000 or less, when it is used as a constituent material of a paint, the solid content concentration of the paint is not limited, and the moldability of the obtained polyurethane is not deteriorated, which is preferable. .. The number average molecular weight of the polycarbonate diol is more preferably 450 to 3000.
In this embodiment, the number average molecular weight of the polycarbonate diol can be measured by the method described in Examples described later.

The polycarbonate diol used in the present embodiment includes a polycarbonate diol in which the repeating unit represented by the formula (A) is composed of only the repeating unit represented by the formula (B), or the repeating unit represented by the formula (A). It is preferably a polycarbonate diol composed of a repeating unit represented by the formula (B) and a repeating unit represented by the formula (E).

The polycarbonate diol composition of the present embodiment contains a carbonate compound represented by the above formula (C).
Formula carbonate compound represented by (C), for example, when m in the formula (C) is 4, compounds all four of R ² is tetramethylene [(CH _{2) 4],} the R ² Three compounds are tetramethylene and one is 2-methyltrimethylene [CH ₂ CH (CH ₃ ) CH ₂ ^{], two} of R 2 are compounds of tetramethylene and two are 2-methyltrimethylene, R ² A mixture containing a compound in which one of the compounds is tetramethylene and three of which are 2-methyltrimethylene and a compound in which ^{all four of R 2} are 2-methyltrimethylene, and the proportion of each compound is not particularly limited. .. Further, the order of binding of tetramethylene and 2-methyltrimethylene is not particularly limited.

In the polycarbonate diol composition of the present embodiment, when a predetermined amount of the carbonate compound represented by the formula (C) is present together with the polycarbonate diol, each carbonate bond in the carbonate compound interacts with the carbonate bond of the plurality of polycarbonate diols. Has. Further, since the carbonate compound represented by the formula (C) has a large cyclic structure, when the polycarbonate diol composition of the present embodiment is used as a constituent material of a coating material, a tough and soft coating film can be obtained. ..

Since the carbonate compound represented by the formula (C) in the present embodiment has a high carbonate density, the effect obtained by the carbonate bond is enhanced, and the distance between the carbonate bonds in the carbonate compound is within an appropriate range. Since a strong interaction with the polycarbonate diol can be obtained, R ² in the carbonate compound of the present embodiment is tetramethylene or 2-methyltrimethylene.

It is preferable that at least one ^{of R 2} in the carbonate compound represented by the formula (C) is 2-methyltrimethylene.
That is, the polycarbonate diol composition of the present embodiment preferably contains a carbonate compound represented by the formula (C), in which at least one of ^{R 2 is 2-methyltrimethylene.}
Since ^{at least one of R 2} is 2-methyltrimethylene, the interaction between each carbonate bond in the carbonate compound and the carbonate bond of a plurality of polycarbonate diols becomes moderately strong, and further flexibility and tension are obtained. There is a tendency to obtain a coating film having excellent elongation.

Further, since the carbonate compound in the present embodiment produces carbon dioxide by decomposing, there is a possibility that a flame-retardant effect can be imparted to the resin. The formula (C) is preferably the following formula (D) because the effects of the mechanical strength and flexibility of the carbonate compound appear more prominently, and m in the formula (D) is preferably 4. More preferred.

(In the formula (D), R ² may be the same or different, and represents (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m represents an integer of 3 to 6).

The total content of the carbonate compound represented by the formula (C) contained in the polycarbonate diol composition of the present embodiment is 0.05 to 5% by weight. When the content of the carbonate compound is 0.05% by weight or more, a flexible coating film is obtained, and when the content of the carbonate compound is 5% by weight or less, the carbonate compound does not bleed out and is tough. A coating film is obtained. The content of the carbonate compound is more preferably 0.07 to 4% by weight, and even more preferably 0.08 to 3% by weight.
In this embodiment, the content of each carbonate compound can be measured by the method described in Examples described later.
The method for adjusting the total content of the carbonate compound represented by the formula (C) contained in the polycarbonate diol composition of the present embodiment within the above range is not particularly limited, but is represented by, for example, a separately produced formula (C). Examples thereof include a method of adding the carbonate compound to be added to the polycarbonate diol so as to fall within the above range.

As the carbonate compound represented by the formula (C), for example, 1,4-butanediol and / or a polycarbonate obtained by using 2-methyl-1,3-propanediol as a diol raw material is used, and the pressure is reduced. It can be obtained by distillation purification from the distillate produced when heating at a high temperature of 190 to 210 ° C. below. The carbonate compound represented by the formula (C) is composed of 1,4-butanediol and / or 2-methyl-1,3-propanediol and a carbonate used for producing a polycarbonate diol described later as a diol. It is obtained by dissolving it in a solvent having a boiling point of 100 ° C. or higher to prepare a dilute solution, reacting it at 90 to 120 ° C., and then distilling and purifying it so that the total concentration of carbonate is 5 to 30% or less of the whole solution. Can be done.

When the water content of the polycarbonate diol composition of the present embodiment is 500 ppm or less, there is an effect of obtaining a smooth coating film without becoming cloudy due to foaming, and when it is 1 ppm or more, carbonate is easily contained in the polycarbonate diol. It is preferably 1 to 500 ppm because it has the effect of dispersing the compound. Further, since the above effect becomes more remarkable, the water content is more preferably 5 to 250 ppm, further preferably 10 to 150 ppm.
In this embodiment, the water content of the polycarbonate diol composition can be determined by the method described in Examples described later.

The method for producing the polycarbonate diol used in this embodiment is not particularly limited, and for example, it can be produced by various methods described in Schnell, Polymer Reviews, Vol. 9, pp. 9-20 (1994). ..

The polycarbonate diol used in this embodiment is not particularly limited, but is produced, for example, using a diol and a carbonate as raw materials.

In the production of the polycarbonate diol in the present embodiment, 2-methyl-1,3-propanediol can be preferably used as the diol. In addition to them, other diols can also be used. The diol used is not particularly limited, but for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, Diols without side chains such as 8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol; 2-methyl-1,8-octane Diol, 2-ethyl-1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, Diols with side chains such as 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 2-bis (4-bis) Hydroxycyclohexyl) -Cyclic diols such as propane can be mentioned. One type or two or more types of the diol may be used as a raw material for the polycarbonate diol.

Further, a compound having 3 or more hydroxyl groups in one molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc., is used as a raw material for the polycarbonate diol as long as the performance of the polycarbonate diol used in the present embodiment is not impaired. Can also be used as. If too many compounds having 3 or more hydroxyl groups in one molecule are used as a raw material for the polycarbonate diol, they will be crosslinked during the polymerization reaction of the polycarbonate and gelation will occur. Therefore, even when a compound having 3 or more hydroxyl groups in one molecule is used as a raw material for a polycarbonate diol, the compound is 0.1 to 5 with respect to the total number of moles of the diol used as a raw material for the polycarbonate diol. It is preferably mol%. This ratio is more preferably 0.1 to 1 mol%.

The carbonate used in the present embodiment is not particularly limited, and is, for example, a dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, or dibutyl carbonate; a diaryl carbonate such as diphenyl carbonate; ethylene carbonate, trimethylene carbonate, 1,2-. Examples thereof include alkylene carbonates such as propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate and 1,2-pentylene carbonate. Of 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 this embodiment, it is preferable to add a catalyst. The catalyst is not particularly limited, but for example, alkali metals such as lithium, sodium and potassium, alkali earth metals such as magnesium, calcium, strontium and barium, alcoholates, hydrides, oxids, amides, carbonates and hydroxides. Examples include substances, nitrogen-containing borates, and basic alkali metal salts and alkaline earth metal salts of organic acids. The catalyst is not particularly limited, but for example, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, and silver. , Indium, tin, antimony, tungsten, rhenium, osminium, iridium, platinum, gold, tallium, lead, bismuth, itterbium, metals, salts, alkoxides, organic compounds. One or more catalysts can be selected and used from them. When one or more catalysts are used from metals, salts, alkoxides and organic compounds of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead and itterbium, the polycarbonate diol is successfully polymerized and obtained. It is preferable because it has little effect on the urethane reaction using the polycarbonate diol. It is more preferable to use titanium, ytterbium, or zirconium as the catalyst.

The polycarbonate diol composition of the present embodiment may contain the above catalyst in an amount of 0.0001 to 0.02% by weight as the amount of metal elements measured using ICP. When the content of the catalyst is within the above range, the polycarbonate diol is polymerized well, 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.

The polycarbonate diol composition of the present embodiment preferably has a total content of titanium, ytterbium and zirconium of 0.0001 to 0.02% by weight, preferably 0.0005 to 0.01% by weight, as measured by ICP. More preferably.
In this embodiment, the content of the metal element in the polycarbonate diol composition can be measured by the method described in Examples described later.

When the polycarbonate diol used in the present embodiment is used as a raw material for polyurethane, for example, it is preferable to treat the catalyst used in the production of the polycarbonate diol with a phosphorus compound. The phosphorus compound is not particularly limited, and is, for example, a phosphorous acid triester such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, cresil diphenyl phosphate; methyl acid. 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, oleyl acid phosphate, tetracosyl acid. Acidic phosphates such as phosphate, ethylene glucol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate; triphenyl phosphate, trisnonylphenyl Phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, diphenylmono (2-ethylhexyl) ) Phosphite, diphenylmonodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethylhydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilaurylhydrogen phosphite, diorail hydrogen phosphite, diphenyl Hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis (decyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) ) Phosphorous acid esters such as phosphite; further, phosphorous acid, phosphorous acid, hypophosphite and the like can be mentioned.

The amount of the phosphorus compound contained in the polycarbonate diol composition of the present embodiment is preferably 0.0005 to 0.05% by weight as the content of the phosphorus element when measured using ICP. When the polycarbonate diol composition of the present embodiment has a phosphorus compound in the above range, for example, when it is used as a raw material for polyurethane, the catalyst used in the production of the polycarbonate diol has almost no effect on the reaction for producing the polyurethane. In addition, the phosphorus compound has little effect on the polyurethane production reaction and the physical properties of the reaction product. Furthermore, when a transesterification reaction catalyst is present in the polycarbonate diol, the decomposition of the carbonate compound present in the polycarbonate diol composition is suppressed. In the polycarbonate diol composition of the present embodiment, the content of the phosphorus element as measured by ICP is more preferably 0.0005 to 0.03% by weight.

Specific examples of the method for producing the polycarbonate diol used in this embodiment are shown below. The production of the polycarbonate diol used in the present embodiment is not particularly limited, but can be carried out in two steps, for example. The diol and carbonate are mixed in a molar ratio (diol: carbonate), for example, at a ratio of 20: 1 to 1:10, preferably at a ratio of 10: 1 to 1: 2, and 100 to 100 under normal pressure or reduced pressure. The first stage reaction is carried out at 250 ° C. When dimethyl carbonate is used as the carbonate, the methanol produced 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 ethanol produced 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 ethylene glycol produced 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 of the first stage is heated at 160 to 250 ° C. under reduced pressure to remove unreacted diols and carbonates, and condensate a low molecular weight polycarbonate diol. , A reaction to obtain a polycarbonate diol having a predetermined molecular weight. The first-stage reaction is started at a temperature of 100 to 150 ° C., the reaction is carried out at the reaction start temperature for 5 hours or more, and then the temperature is raised at a rate of 15 ° C. or less per hour, and the second-stage reaction is carried out. The amount of the carbonate compound produced in the reaction can be suppressed to a low level by performing the operation at a temperature of 120 to 170 ° C. and a pressure of 15 kPa or less, and a predetermined amount of the carbonate compound is added to the obtained polycarbonate diol. This is more preferable because the amount of the carbonate compound contained in the polycarbonate diol can be controlled.

<Use>
The polycarbonate diol composition used in this embodiment can be used as a constituent material for paints and adhesives, as a raw material for polyurethanes and thermoplastic elastomers, and as a modifier for polyesters and polyimides. In particular, when the polycarbonate diol composition of the present embodiment is used as a constituent material of a coating material, a coating film having both mechanical strength and flexibility can be obtained. Further, when the polycarbonate diol composition of the present embodiment is used as a raw material for polyurethane or thermoplastic elastomer, it is possible to obtain polyurethane or thermoplastic elastomer tough, having chemical resistance and excellent moldability.

The thermoplastic polyurethane of the present embodiment can be obtained by using the above-mentioned polycarbonate diol and organic polyisocyanate.
In addition, the coating composition of the present embodiment contains the above-mentioned polycarbonate diol composition and organic polyisocyanate.
Further, the coating composition of the present embodiment contains a urethane prepolymer obtained by reacting the above-mentioned polycarbonate diol composition with an organic polyisocyanate, and it is preferable that the urethane prepolymer has an isocyanate terminal group.
Furthermore, the coating composition of the present embodiment more preferably contains the above-mentioned polycarbonate diol composition, organic polyisocyanate and polyurethane resin obtained by reacting with a chain extender, and the above-mentioned polycarbonate diol composition and organic poly A water-based coating composition containing a polyurethane obtained by reacting an isocyanate and a chain extender is more preferable.

The organic polyisocyanate used is not particularly limited, but is, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and a mixture thereof (TDI), crude TDI, diphenylmethane-4,4'-diisocyanate ( MDI), crude MDI, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenylenediocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylenedi isocyanate and the like. Aromatic diisocyanates, known aliphatic diisocyanates such as 4,4'-methylenebiscyclohexyldiisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexanediisocyanate (hydrogenated XDI), and these. Examples thereof include isocyanurate-modified products, carbodiimide-modified products, and biuret-modified products of isocyanates. These organic polyisocyanates may be used alone or in combination of two or more. Further, these organic polyisocyanates may be used by masking the isocyanate group 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. The chain extender is not particularly limited, and for example, a chain extender commonly used in the polyurethane industry, that is, water, a low molecular weight polyol, a polyamine, or the like can be used. Examples of the chain extender are not particularly limited, but for example, 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-weight polyols, ethylenediamine, Examples thereof include polyamines such as hexamethylenediamine, isophoronediamine, xylylenediamine, diphenyldiamine and diaminodiphenylmethane. These chain extenders may be used alone or in combination of two or more.

The 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-mentioned polycarbonate diol composition with an organic polyisocyanate under atmospheric pressure at room temperature to 200 ° C. 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 the present embodiment, for example, US Pat. No. 5,070,173 can be referred to.

In the polyurethaneization 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, a silicone oil, a foaming agent, a flame retardant and the like may be added.

As a method for producing the coating composition (paint) of the present embodiment, a production method known in the industry is used. For example, a two-component solvent-based coating composition in which a coating main agent obtained from the above-mentioned polycarbonate diol composition and a curing agent composed of an organic polyisocyanate are mixed immediately before coating; the above-mentioned polycarbonate diol composition and an organic polyisocyanate are mixed. A one-component solvent-based coating composition composed of a urethane prepolymer having an isocyanate terminal group obtained by reaction; a one-component consisting of a polyurethane resin obtained by reacting the above-mentioned polycarbonate diol composition, organic polyisocyanate and chain extender. A type solvent-based coating composition; or a one-component water-based coating composition can be produced.

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 mold release agent, and a fluidity adjustment according to various uses. Agents, plasticizers, antioxidants, UV absorbers, light stabilizers, defoamers, leveling agents, colorants, solvents and the like can be added.

The solvent of the coating composition (paint) of the present embodiment is not particularly limited, but for example, dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methylethylketone, methylisobutylketone, dioxane, cyclohexanone, benzene, etc. Examples thereof include toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol, n-butanol, water and the like. These solvents may be used alone or in admixture of a plurality of types.

Next, the present invention will be described with reference to Examples and Comparative Examples.
The following examples are described for the purpose of exemplifying the present invention, and do not limit the scope of the present invention in any way.
The physical property values and terms shown in the following Examples and Comparative Examples are as shown below.

1. 1. Quantification of carbonate compounds The quantification of carbonate compounds was performed 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, the carbonate compound in the sample was quantified using a calibration curve prepared in advance using 1,3,10,12-tetraoxacyclooctadecane-2,11-dione. It was. As the LC apparatus, SIMADZU Nexus X2 (manufactured by Shimadzu Corporation) equipped with Waters ACQUITY UPLC HHS C18 (manufactured by Waters) was used as a column. In the LC apparatus, the flow rate was set to 0.2 ml / min, and measurement was performed by applying a gradient from methanol: water = 30:70 to methanol: water = 100: 0. As the MS apparatus, BRUKER amaZon SL (manufactured by BRUKER) was used. In the MS apparatus, the measurement was carried out at ionization: APCl + and scan range: m / z 70 to 1200.

2. Determination of Polycarbonate Diol Composition The composition of the polycarbonate diol was determined as follows. First, 1 g of a sample was measured in 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 and stirred in an oil bath at 100 ° C. for 1 hour. After cooling the mixture to room temperature, 1 to 2 drops of phenolphthalein was added to the mixture as an indicator and neutralized with hydrochloric acid. Then, 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). For GC analysis, a gas chromatography GC2014 (manufactured by Shimadzu Corporation) with a column of DB-WAX (manufactured by J & W, USA) 30 m and a film thickness of 0.25 μm was used, and diethylene glycol diethyl ester was used as an internal standard, and a detector was used. This was performed using a hydrogen flame ionization detector (FID). The temperature rise profile of the column was a profile in which the temperature was maintained at 60 ° C. for 5 minutes and then raised to 250 ° C. at 10 ° C./min.
The composition of the polycarbonate diol was determined based on the area value of the diol obtained by GC analysis.

3. 3. Determining the Number Average Molecular Weight of Polycarbonate Diol The number average molecular weight of polycarbonate diol is the hydroxyl value (OH value) by the "neutralization titration method (JIS K0070-1992)" in which anhydrous acetic acid and pyridine are titrated with an ethanol solution of potassium hydroxide. ) Was determined and calculated using the following equation (4).

Number average molecular weight = 2 / (OH value x 10 ^-3 / 56.1) (4)

4. Analysis of Inductively Coupled Plasma (ICP) of Containing Elements Each element contained in the polycarbonate diol composition was analyzed as follows. First, the sample was weighed in a Teflon (registered trademark) decomposition container, high-purity nitric acid (manufactured by Kanto Chemical Co., Inc.) 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 liquid 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 an inductively coupled plasma analyzer (iCAP6300 Duo manufactured by Thermo Fisher Scientific Co., Ltd.).

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

6. Evaluation of Coating Film (1) With respect to the coating film obtained from the sweat-resistant polycarbonate diol composition, the appearance of the coating film after being immersed in oleic acid at 23 ± 2 ° C. for 24 hours was visually evaluated. The degree and amount of defects were represented by grades 0 to 5 according to JIS K5600-8-1, and the sweat resistance of the coating film was defined.

(2) Alkali resistance of coating film With respect to the coating film obtained from the polycarbonate diol composition, the appearance of the coating film after being immersed in a 0.1 mol / L NaOH aqueous solution at 23 ± 2 ° C. for 24 hours was visually evaluated. The degree and amount of defects were represented by grades 0 to 5 according to JIS K5600-8-1, and the coating film was made alkaline resistant.

(3) Alcohol Resistance of Coating Film With respect to the coating film obtained from the polycarbonate diol composition, the appearance of the coating film after being immersed in a 50% ethanol aqueous solution at 23 ± 2 ° C. for 4 hours was visually evaluated. The degree and amount of defects were represented by grades 0 to 5 according to JIS K5600-8-1, and the coating film was made ethanol resistant.

(4) Flexibility The coating film obtained from the polycarbonate diol composition has an amplitude angle of 3 ° or less according to ISO 1522 using a pen drum hardness tester (manufactured by BYK-Gardner) equipped with a König pen drum. The number of runouts was measured.

(5) Abrasion resistance With respect to the coating film obtained from the polycarbonate diol composition, according to the method of JIS K5600-5-8, the Taber type abrasion tester No. Using 410 (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the weight change before the wear test and the weight change of the coating film plate after the wear test (500 rotations) were measured.

(6) Breaking strength and breaking elongation With respect to the coating film obtained from the polycarbonate diol composition, a measurement sample was cut out in a strip shape having a width of 10 mm, a length of 50 mm and a thickness of 0.05 mm, and the tensile strength was determined according to JIS K6251. Breaking strength) and tensile elongation (breaking elongation) were measured. The tensile strength (breaking strength) means the mechanical strength.

7. Carbonate compound represented by the formula (C) The carbonate compound represented by the formula (C) added in Examples 1 to 18 and Comparative Examples 1, 2, 4 and 5 below is a mixture. For example, the carbonate compound having m of 4 in the formula (C) is a compound in which all four are tetramethylene and three are tetramethylene and one is 2-methyltrimethylene ^{for R 2 in the formula (C).} Of some compounds, two of which are tetramethylene and two of which are 2-methyltrimethylene, one of which is tetramethylene and three of which are 2-methyltrimethylene, and four of which are all 2-methyltrimethylene. It is a mixture. The order of tetramethylene and 2-methyltrimethylene in the compound in which the above two are tetramethylene and two are 2-methyltrimethylene is not particularly limited. Further, the carbonate compound represented by the formula (C) added in Examples 19 and 20 is a compound having m in the formula of 4 and all four of ^{R 2 being tetramethylene.}
The carbonate compound represented by the formula (C) added in Examples 1 to 18 and Comparative Examples 1, 2, 4, and 5 contains 1,4-butanediol and 2-methyl-1,3-propanediol. Using the polycarbonate obtained by using it as a diol raw material, a distillate produced when heated at a high temperature of 190 to 200 ° C. under a reduced pressure of 0.1 to 0.5 kPa was obtained by distillation purification. Further, as the carbonate compound represented by the formula (C) added in Examples 19 and 20, polycarbonate obtained by using 1,4-butanediol as a diol raw material was used, and 0.1 to 0.5 kPa was used. The distillate produced when heated at a high temperature of 190 to 200 ° C. under reduced pressure was obtained by distillation purification.

[Example 1]
800 g (9.1 mol) of ethylene carbonate, 400 g (4.4 mol) of 2-methyl-1,3-propanediol in a 2 L glass flask equipped with a rectification column filled with a regular filling and a stirrer. 415 g (4.6 mol) of 1,4-butanediol was charged. 0.24 g of titanium tetraisopropoxide was further added to the flask as a catalyst, and the reaction was carried out at a temperature of 140 ° C. and a pressure of 1.0 to 1.5 kPa for 15 hours while distilling off a mixture of ethylene glycol and ethylene carbonate to be produced. .. Then, the rectification column filled with the regular packing was replaced with a simple distillation apparatus, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 12 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. .. Then, 0.69 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 2.0 g of a carbonate compound having m of 4 in the formula (C) and 2.0 g of a carbonate compound having m of 5 in the formula (C) were added, and the mixture was added at 100 ° C. for 5 hours. Stirring gave a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-1. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Examples 2 to 8]
A polycarbonate diol composition was obtained by adding a mixture of carbonate compounds in the amounts shown in Table 1 to 400 g of the polycarbonate diol obtained in Example 1 and stirring at 100 ° C. for 5 hours. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-2 to 8 respectively. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Comparative Examples 1-2]
A polycarbonate diol composition was obtained by adding a mixture of carbonate compounds in the amounts shown in Table 1 to 400 g of the polycarbonate diol obtained in Example 1 and stirring at 100 ° C. for 5 hours. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-31 to 32, respectively.

[Comparative Example 3]
To 400 g of the polycarbonate diol obtained in Example 1, 6 g of 5-methyl-1,3-dioxane-2-one was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The obtained polycarbonate diol composition was analyzed. The content of 5-methyl-1,3-dioxane-2-one was 1.5% by weight, and other results are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-33.

[Example 9]
Using the apparatus used in Example 1, 800 g (9.1 mol) of ethylene carbonate and 815 g (9.1 mol) of 2-methyl-1,3-propanediol were charged. 0.24 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out by the method of Example 1. Then, 0.68 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-9. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) is as shown in Table 2.

[Comparative Example 4]
730 g (8.3 mol) of ethylene carbonate, 35 g (0.4 mol) of 2-methyl-1,3-propanediol in a 2 L glass flask equipped with a rectification column filled with a regular filling and a stirrer. 420 g (4.0 mol) of 1,5-pentanediol and 470 g (4.0 mol) of 1,6-hexanediol were charged. 0.25 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out at a temperature of 140 ° C. and a pressure of 1.0 to 1.5 kPa for 15 hours while distilling off a mixture of ethylene glycol and ethylene carbonate to be produced. Then, the rectification column filled with the regular packing was replaced with a simple distillation apparatus, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 12 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. .. Then, 0.70 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-34.

[Comparative Example 5]
710 g (8.1 mol) of ethylene carbonate, 30 g (0.3 mol) of 2-methyl-1,3-propanediol in a 2 L glass flask equipped with a rectification column filled with a regular filling and a stirrer. 700 g (7.8 mol) of 1,4-butanediol was charged. 0.22 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out at a temperature of 140 ° C. and a pressure of 1.0 to 1.5 kPa for 15 hours while distilling off a mixture of ethylene glycol and ethylene carbonate to be produced. Then, the rectification column filled with the regular packing was replaced with a simple distillation apparatus, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 12 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. .. Then, 0.61 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-35.

[Example 10]
In Example 1, except that ethylene carbonate was 790 g (9.0 mol), 2-methyl-1,3-propanediol was 145 g (1.6 mol), and 1,4-butanediol was 670 g (7.4 mol). Polymerization was carried out under the conditions of Example 1 using the equipment used to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-10. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 11]
Used in Example 1 except that ethylene carbonate was 790 g (9.0 mol), 2-methyl-1,3-propanediol was 300 g (3.3 mol), and 1,4-butanediol was 510 g (5.7 mol). Polymerization was carried out under the conditions of Example 1 to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-11. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 12]
Using the apparatus used in the apparatus of Example 1, 790 g (9.0 mol) of ethylene carbonate, 575 g (6.4 mol) of 2-methyl-1,3-propanediol, and 235 g (6.4 mol) of 1,4-butanediol were used. 2.6 mol) Prepared. 0.24 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out at a temperature of 140 ° C. and a pressure of 1.0 to 1.5 kPa for 15 hours while distilling off a mixture of ethylene glycol and ethylene carbonate to be produced. Then, the rectification column filled with the regular packing was replaced with a simple distillation apparatus, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 4 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. .. Then, 0.68 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-12. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 13]
The reaction was carried out under the conditions of Example 12, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 8 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. Then, 0.68 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-13. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 14]
The reaction was carried out under the conditions of Example 13, and the reaction was carried out at a temperature of 140 to 150 ° C. for another 10 hours while reducing the pressure to 0.5 kPa and distilling off the diol and ethylene carbonate. Then, 0.68 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 3.6 g of a carbonate compound having m of 4 in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-15. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 15]
Using the apparatus used in Example 1, 800 g (9.1 mol) of ethylene carbonate, 500 g (5.6 mol) of 2-methyl-1,3-propanediol, and 380 g (3.) of 1,5-pentanediol. 7 mol) Prepared. 0.25 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out by the method of Example 1. Then, 0.71 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 2.0 g of a carbonate compound having m of 4 in the formula (C) and 2.0 g of a carbonate compound having m of 5 in the formula (C) were added, and 5 at 100 ° C. Stirring for hours gave a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-15. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 16]
Using the apparatus used in Example 1, 790 g (9.0 mol) of ethylene carbonate, 385 g (4.3 mol) of 2-methyl-1,3-propanediol, and 560 g (4.) of 1,6-hexanediol. 8 mol) Prepared. 0.26 g of titanium tetraisopropoxide was added as a catalyst, and the reaction was carried out by the method of Example 1. Then, 0.74 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 2.0 g of a carbonate compound having m of 4 in the formula (C) and 2.0 g of a carbonate compound having m of 5 in the formula (C) were added, and 5 at 100 ° C. Stirring for hours gave a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-16. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 17]
Using the apparatus used in Example 1, 650 g (7.2 mol) of dimethyl carbonate, 330 g (3.7 mol) of 2-methyl-1,3-propanediol, and 710 g (4.) of 1,0-decanediol. 8 mol) Prepared. 0.25 g of titanium tetraisopropoxide was added as a catalyst, the mixture was stirred at normal pressure, and the temperature was raised to 65 to 140 ° C., and the mixture of methanol and dimethyl carbonate to be produced was distilled off to carry out a reaction for 20 hours. Then, the pressure was reduced to 17 kPa, and the reaction was carried out at 140 to 150 ° C. for another 12 hours while distilling off a mixture of methanol and dimethyl carbonate. Then, 0.72 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 2.0 g of a carbonate compound having m of 4 in the formula (C) and 2.0 g of a carbonate compound having m of 5 in the formula (C) were added, and 5 at 100 ° C. Stirring for hours gave a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-17. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 18]
Using the apparatus used in Example 1, 850 g (7.2 mol) of diethyl carbonate, 330 g (3.7 mol) of 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol were added. 480 g (4.1 mol) was charged. 0.25 g of titanium tetraisopropoxide was added as a catalyst, the mixture was stirred at normal pressure, and the temperature was raised to 80 to 140 ° C., and the mixture of ethanol and diethyl carbonate to be produced was distilled off to carry out a reaction for 20 hours. Then, the pressure was reduced to 17 kPa, and the reaction was carried out at 140 to 150 ° C. for another 12 hours while distilling off a mixture of ethanol and diethyl carbonate. Then, 0.71 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ° C. for 5 hours to obtain a polycarbonate diol. To 400 g of the obtained polycarbonate diol, 2.0 g of a carbonate compound having m of 4 and 2.0 g of a carbonate compound having m of 5 in the formula (C) were added, and the mixture was stirred at 100 ° C. for 5 hours. A polycarbonate diol composition was obtained. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-18. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 19]
To 400 g of the polycarbonate diol obtained in Example 1, ^{8.8 g of a carbonate compound having m of 4 and R 2} of all tetramethylene in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain the polycarbonate diol. The composition was obtained. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-19. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Example 20]
To 400 g of the polycarbonate diol obtained in Example 1, ^{17.2 g of a carbonate compound having m of 4 and R 2} of all tetramethylene in the formula (C) was added, and the mixture was stirred at 100 ° C. for 5 hours to obtain the polycarbonate diol. The composition was obtained. The results of analysis of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-20. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the formula (B) when the repeating unit represented by the formula (A) is 100 mol%. The ratio (mol%) of the repeating unit represented by) and the repeating unit represented by the formula (E) is as shown in Table 2.

[Application Example 1]
40 g of polycarbonate diol composition PC-1, 0.75 g of BYK-331 (manufactured by BYK Chemical) as a leveling agent, and 2% by weight dissolved in thinner (xylene / butyl acetate = 70/30 (weight ratio)). 1.25 g of the dibutyltin dilaurate solution and 40 g of thinner were mixed and stirred to obtain a paint base material. An organic polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., isocyanate (NCO) content: 23.1%) was added to the obtained paint main agent as a curing agent in an amount of 7.7 g to prepare a coating liquid. The coating liquid was applied onto a coating plate, thinner was blown off at room temperature for 2 hours, and then heat-cured at 75 ° C. for 2 hours to obtain a coating film. The coating film was left at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 1 week, and then the physical properties were evaluated. The evaluation results are shown in Table 3. As the coating plate, a polypropylene resin plate was used for measuring the breaking strength and elongation of the coating film, a glass plate was used for the flexibility test, and an acrylonitrile-butadiene-styrene (ABS) resin plate was used for other resistance tests. ..

[Application Examples 2-11, 13, 15-20]
A coating film was obtained in the same manner as in Application Example 1 except that PC-2 to 11, 13, and 15 to 20 were used as the polycarbonate diol composition. Physical characteristics were evaluated using the coating film. The evaluation results are shown in Table 3.

[Application Example 12]
Dissolve 13 g of polycarbonate diol composition PC-12, 0.30 g of BYK-331 (manufactured by BYK Chemical) as a leveling agent, and 2% by weight in thinner (xylene / butyl acetate = 70/30 (weight ratio)). A coating film was obtained in the same manner as in Application Example 1 except that the amount of the dibutyltin dilaurate solution was 0.40 g and the amount of thinner was 20 g. Physical characteristics were evaluated using the coating film. The evaluation results are shown in Table 3.

[Application Example 14]
Dissolve 60 g of polycarbonate diol composition PC-14, 1.0 g of BYK-331 (manufactured by BYK Chemical) as a leveling agent, and 2% by weight in thinner (xylene / butyl acetate = 70/30 (weight ratio)). A coating film was obtained in the same manner as in Application Example 1 except that the amount of the dibutyltin dilaurate solution was 1.75 g and the amount of thinner was 60 g. Physical characteristics were evaluated using the coating film. The evaluation results are shown in Table 3.

[Comparative Application Examples 1 to 5]
A coating film was obtained in the same manner as in Application Example 1 except that PC-31-35 was used as the polycarbonate diol composition. Physical characteristics were evaluated using the coating film. The evaluation results are shown in Table 3.

[Application 21]
800 g of PC-1 obtained in Example 1 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 a terminal isocyanate (NCO) group. Obtained urethane prepolymer to have. To the urethane prepolymer, 107 g of 1,4-butanediol as a chain extender and 0.05 g of dibutyltin dilaurylate as a catalyst are added to a universal extruder for a laboratory with a built-in kneader (LABO manufactured by Kasamatsu Chemical Research Institute, Japan). The reaction was carried out at 140 ° C. for 60 minutes using a universal extruder KR-35) to obtain a thermoplastic polyurethane. Then, the obtained thermoplastic polyurethane was pelletized by an extruder.

When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, it is possible to obtain a coating film having mechanical strength and flexibility. Since the polycarbonate diol composition of the present invention has these properties, it can be suitably used as a constituent material of a coating material and further as a raw material of polyurethane.

Claims (11)

A polycarbonate diol composition containing 0.05 to 5% by weight of a polycarbonate diol composed of a repeating unit represented by the following formula (A) and a terminal hydroxyl group and a carbonate compound represented by the following formula (C). ,
The polycarbonate diol composition, wherein 5 to 100 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (B).

(In the formula (A), R ¹ represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

(In the formula (C), R ² may be the same or different, and represents (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m represents an integer of 2 to 8.)

The polycarbonate diol composition according to claim 1, wherein the carbonate compound represented by the formula (C) is a carbonate compound represented by the following formula (D).

(In the formula (D), R ² may be the same or different, and represents (CH ₂ ) ₄ or CH ₂ CH (CH ₃ ) CH ₂ , and m represents an integer of 3 to 6). The polycarbonate diol composition according to claim 1 or 2, wherein 5 to 95 mol% of the repeating unit represented by the formula (A) is the repeating unit represented by the following formula (E).

(In formula (E), n represents an integer of 2 to 12.) The polycarbonate diol composition according to any one of claims 1 to 3, wherein the total content of titanium, ytterbium, and zirconium as measured by ICP is 0.0001 to 0.02% by weight. The polycarbonate diol composition according to any one of claims 1 to 4, wherein the content of the phosphorus element as measured by ICP is 0.0005 to 0.05% by weight. The polycarbonate diol composition according to any one of claims 1 to 5, which has a water content of 1 to 500 ppm. A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of claims 1 to 6 and an organic polyisocyanate. A coating composition containing the polycarbonate diol composition according to any one of claims 1 to 6 and an organic polyisocyanate. A coating composition containing a urethane prepolymer obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 6 with an organic polyisocyanate, wherein the urethane prepolymer has a terminal isocyanate group. A coating composition containing the polycarbonate diol composition according to any one of claims 1 to 6, a polyurethane resin obtained by reacting an organic polyisocyanate with a chain extender. An aqueous coating composition containing the polycarbonate diol composition according to any one of claims 1 to 6, a polyurethane obtained by reacting an organic polyisocyanate with a chain extender.