JP2018178000A - Polycarbonate diol composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol composition good in handleability because it has visibility and fluidity, and capable of providing a resin (e.g. polyurethane resin) or a coated film excellent in transparency when used as a raw material or a coating component of the resin (e.g. polyurethane resin).SOLUTION: There is provided a polycarbonate diol composition containing one or more kind of repeating unit represented by the formula (A), and a terminal hydroxyl group, and satisfying following properties (1) to (3). R is a bivalent hydrocarbon group. (1) it has fluidity at 20°C. (2) turbidity at 20°C is 5 to 100 NTU. (3) turbidity at 40°C is less than 5 NTU.SELECTED DRAWING: None

Description

  The present invention relates to polycarbonate diol compositions.

  For example, when polycarbonate diol is used as a soft segment of resin such as polyurethane or thermoplastic elastomer, it is known that a material having excellent hydrolysis resistance, light resistance, oxidation deterioration resistance, heat resistance and the like can be obtained. There is. However, polycarbonate diol mainly composed of 1,6-hexanediol has high crystallinity, so it exists in a solid state at room temperature. For this reason, when using the said polycarbonate diol as a coating material component, when manufacturing resin (for example, polyurethane resin) by superposition | polymerization, there existed a problem of handling being disturbed, for example, a large amount of solvent is needed.

  In order to solve such a problem, it has been proposed to lower the crystallinity of polycarbonate diol by using two or more diols as raw materials. For example, copolycarbonate diols in which the diol component is composed of 1,6-hexanediol and 1,4-cyclohexanedimethanol and is liquid at normal temperature have been proposed (see, for example, Patent Document 1). Moreover, the copolycarbonate diol obtained using 3-methyl 1, 5- pentanediol as a main glycol raw material is proposed (for example, refer patent document 2). Furthermore, copolycarbonate diols composed of repeating units derived from 1,6-hexanediol and 1,5-pentanediol have been proposed (see, for example, Patent Documents 3 and 4).

JP, 2011-84751, A WO 2007/108198 pamphlet Unexamined-Japanese-Patent No. 2-289616 WO 2009/63768 pamphlet

  However, the polycarbonate diols described in Patent Documents 1 to 4 have a problem that it is difficult to confirm their presence in a container or a reactor because they are colorless and transparent at normal temperature, and in the prior art, the fluidity and the visibility A polycarbonate diol having good handleability by having it has not been developed.

  Therefore, the present invention is excellent in handleability by having visibility and flowability, and when used as a raw material of a resin (for example, a polyurethane resin) or a paint component, a resin having excellent transparency (for example, a polyurethane resin) It is an object of the present invention to provide a polycarbonate diol composition capable of obtaining a coating film.

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, this inventor discovers that the polycarbonate diol composition which satisfy | fills a predetermined | prescribed characteristic can achieve the said subject, and came to complete this invention.

That is, the present invention is as follows.
[1]
The polycarbonate diol composition which contains the polycarbonate diol which has 1 or more types of repeating units represented by following formula (A), and a terminal hydroxyl group, and satisfy | fills the following characteristics (1)-(3).
(In formula (A), R shows a bivalent hydrocarbon group.)

(1) Has fluidity at 20 ° C (2) The turbidity at 20 ° C is 5 NTU or more and 100 NTU or less (3) The turbidity at 40 ° C is less than 5 NTU [2]
Further comprising a polyol which is solid at 20 ° C.,
The polycarbonate diol is in a liquid form at 20 ° C.,
The polycarbonate diol composition as described in said [1] whose content of the said polyol in a polycarbonate diol composition is 0.05 to 10 weight%.
[3]
It further comprises a low molecular weight alcohol which is solid at 20 ° C.,
The polycarbonate diol is in a liquid form at 20 ° C.,
The polycarbonate diol composition according to item [1] or [2], wherein the content of the low molecular weight alcohol in the polycarbonate diol composition is 1% by weight or more and 20% by weight or less.
[4]
The polycarbonate diol composition according to any one of the above items [1] to [3], which satisfies the following formula (1).

90 ≦ Tt ₁ / Tt ₂ × 100 ≦ 100 (1)

Tt ₁ : total light transmittance Tt ₂ after the polyurethane film obtained by reacting the polycarbonate diol composition, the isocyanate compound, and the chain extender in a distilled water at 90 ° C. for one week Tt ₂ : the polyurethane Total light transmittance before soaking the film in 90 ° C distilled water for 1 week

  The polycarbonate diol composition of the present invention has good visibility and fluidity at normal temperature, and thus has a good handleability. In addition, when the polycarbonate diol composition of the present invention is used as a raw material of a resin (for example, a polyurethane resin) or a paint component, it is possible to obtain a resin or a coating film having excellent transparency. For this reason, the polycarbonate diol composition of the present invention can be suitably used as a raw material of a resin (for example, polyurethane resin) or a paint component.

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

[Polycarbonate diol composition]
The polycarbonate diol composition of the present embodiment contains a polycarbonate diol having one or more kinds of repeating units represented by the following formula (A) and a terminal hydroxyl group, and satisfies the following characteristics (1) to (3).
(In formula (A), R shows a bivalent hydrocarbon group.)

(1) Has fluidity at 20 ° C (2) The turbidity at 20 ° C is 5 NTU or more and 100 NTU or less (3) The turbidity at 40 ° C is less than 5 NTU

  The polycarbonate diol composition of the present embodiment has good visibility and fluidity at normal temperature, and thus has a good handleability. Moreover, when the polycarbonate diol composition of this embodiment is used for the raw material and coating material component of resin (for example, polyurethane resin), for example, resin and the coating film excellent in transparency can be obtained.

  The term "visibility" as used herein refers to the property of a polycarbonate diol composition that can be confirmed by visual observation at normal temperature (eg, 20 ° C.), for example, in the measurement methods described in the examples below. And the polycarbonate diol composition has a turbidity of 5 NTU or more. Moreover, "fluidity" refers to the property of flowing at normal temperature (for example, 20 ° C), and for example, the property of having a flow time of 90 seconds or less in the polycarbonate diol composition in the measurement method described in the examples described later. It is.

[Characteristic (1)]
The polycarbonate diol composition of the present embodiment has fluidity at 20 ° C. The term “having fluidity at 20 ° C.” as used herein means that, as described above, the flow time evaluated by the method described in the examples below is 90 seconds or less. The flow time is preferably within 70 seconds, more preferably within 50 seconds. When the flow time is within 90 seconds, the handleability is good.

[Characteristic (2)]
The polycarbonate diol composition of the present embodiment has a turbidity at 20 ° C. of 5 NTU or more and 100 NTU or less, preferably 15 NTU or more and 80 NTU or less, and more preferably 20 NTU or more and 50 NTU or less. When the turbidity is 5 NTU or more, the visibility of the polycarbonate diol composition is excellent, and when it is 100 NTU or less, the transparency of the resin (particularly polyurethane resin) obtained from the polycarbonate diol composition and the coating film is excellent.

[Characteristic (3)]
The polycarbonate diol composition of the present embodiment has a turbidity at 40 ° C. of less than 5 NTU, preferably less than 4 NTU, and more preferably less than 3 NTU. When the turbidity at 40 ° C. is less than 5 NTU, the transparency of the resin (in particular, polyurethane resin) obtained from the polycarbonate diol composition and the coating film is excellent.

  In the present embodiment, the turbidity is represented by NTU (Nephelometric Turbidity Unit) using formazin as a turbidity standard solution, and can be measured by the method described in the examples described later.

  The method of adjusting the turbidity at 20 ° C. and the turbidity at 40 ° C. is not particularly limited. For example, the method of containing solid polyol and / or solid low molecular weight alcohol described later in polycarbonate diol liquid at 20 ° C. It can be mentioned. Among these methods, it is preferable to contain a solid polyol because visibility can be improved even if the amount of addition is relatively small. On the other hand, in order to further improve the visibility, a method in which a solid polyol and a solid low molecular weight alcohol are contained is more preferable.

It is preferable that the polycarbonate diol composition of this embodiment satisfy | fills following formula (1).

90 ≦ Tt1 / Tt2 × 100 ≦ 100 (1)

Tt1: total light transmittance Tt2 after immersing the polycarbonate diol composition, an isocyanate compound, and a chain extender in a polyurethane film obtained by reacting in 90 ° C. distilled water for 1 week Tt 2: the polyurethane film , Total light transmittance before immersion in distilled water at 90 ° C for 1 week

  The evaluation standard of the transparency of the polyurethane obtained by using a polycarbonate diol composition includes a method of calculating Tt1 / Tt2 × 100 in the formula (1). With respect to the total light transmittance (Tt2) before immersion, it can be judged that the transparency is good because the total light transmittance (Tt1) after immersion is not lowered, and the total light transmittance (Tt1) after immersion Is preferably 90% or more and 100% or less of the total light transmittance (Tt2) before immersion, more preferably 92% or more and 100% or less, and still more preferably 95% or more and 100% or more.

[Polycarbonate diol]
The polycarbonate diol contains one or more kinds of repeating units represented by the above-mentioned formula (A) and a terminal hydroxyl group.

  In said Formula (A), R shows a C2-C15 bivalent hydrocarbon group, for example.

  Although it does not specifically limit as a hydrocarbon group, For example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, etc. are mentioned, Preferably it is an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be in the form of linear or branched chain, but from the viewpoint of further excellent chemical resistance and mechanical strength, the linear form represented by the following formula (B) It is preferable that it is a form.

-(CH ₂ ) _n- (B)

  In said Formula (B), n is an integer of 2-15. It is preferable that it is 3-10 from a viewpoint which chemical resistance and mechanical strength are excellent in further more balanced, and it is more preferable that it is 3-6.

  In addition, the divalent hydrocarbon group represented by R may or may not have a substituent (for example, a halogen atom or the like) within the range that does not impair the effect of the present invention.

  In the polycarbonate diol of the present embodiment, the proportion of the repeating unit represented by the formula (A) is preferably 95 mol% or more based on the entire polycarbonate diol, from the viewpoint of further improving the heat resistance and hydrolysis resistance. It is 100 mol% or less, more preferably 97 mol% or more and 100 mol% or less, still more preferably 99 mol% or more and 100 mol% or less.

  The polycarbonate diol is preferably in a liquid form at 20 ° C. from the viewpoint of further improving the fluidity. The liquid form is evaluated at 20 ° C. by the method for evaluating the turbidity of the polycarbonate diol composition and the fluidity of the polycarbonate diol composition described in the following examples. Preferably, the flow time is within 90 seconds and the turbidity is less than 5 NTU.

  The number average molecular weight of the polycarbonate diol of the present embodiment is preferably 300 or more and 5000 or less, more preferably 400 or more and 4000 or less, and still more preferably 450 or more and 3000 or less. When the polycarbonate diol has a number average molecular weight of 300 or more, it tends to be able to impart excellent flexibility of the coating when used in a paint component. When used as a paint component, when the polycarbonate diol has a number average molecular weight of 5000 or less, there is no restriction on the solid concentration of the paint, etc. Moreover, when used as a raw material of a resin (eg polyurethane resin), a resin (eg And polyurethane resin) is preferable because the molding processability does not decrease. 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.

  In addition, the proportion of polycarbonate diol in the polycarbonate diol composition of the present embodiment is preferably 50% by weight or more and 100% by weight or less, and more preferably 85% by weight or more and 100% by weight, from the viewpoint of further excellent hydrolysis resistance and heat resistance. % By weight or less is more preferable, and 95% by weight or more and 100% by weight or less is more preferable.

  The method for producing the polycarbonate diol of the present embodiment is not particularly limited, and can be produced by various methods described in, for example, Schnell, Polymer Reviews Vol. 9, p9 to 20 (1994), for example, diol And carbonate as raw materials.

  The diol is not particularly limited, and, 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-tetradecanediol Diol having no side chain such as 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-diethy Diol having a side chain such as 1, 5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol And cyclic diols such as 2-bis (4-hydroxycyclohexyl) -propane. These diols can be used alone or in combination of two or more. Among these, it is preferable to use one or more types of diol having no side chain as a raw material because chemical resistance and mechanical strength are further improved. In addition, two or more (preferably two) diols selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are polycarbonates. More preferably, it is used as a raw material of a diol, and a combination of 1,5-pentanediol and 1,6-hexanediol is more preferred.

  When two or more diols are used as raw materials in the production of the polycarbonate diol of the present embodiment, the ratio of these raw materials is not particularly limited, but the ratio of the raw materials is selected so that the obtained polycarbonate diol becomes liquid at 20.degree. It is preferable to set. More specifically, when using 2 types of diols as a raw material, it is preferable to set preparation amount so that molar ratio may be 20/80-80/20. If the molar ratio is within the above range, the obtained polycarbonate diol tends to be liquid at 20 ° C. The molar ratio is more preferably 30/70 to 70/30, further preferably 40/60 to 60/40. In particular, when the molar ratio is 40/60 to 60/40, it becomes liquid even at 0 ° C. or less, and the handling property is further improved.

  Furthermore, compounds having three or more hydroxyl groups in one molecule (for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc.) can be used as polycarbonatediols as long as the performance of polycarbonatediols used in the present embodiment is not impaired. It can also be used as a raw material. When a compound having three or more hydroxyl groups in one molecule is used as a raw material of polycarbonate diol, there is a possibility that gelation may occur due to crosslinking during polymerization reaction of polycarbonate. Therefore, when a compound having three or more hydroxyl groups in one molecule is used as a raw material of polycarbonate diol, the ratio of the above compound is 0.1 to the number of moles of the entire diol used as a raw material of polycarbonate diol. It is preferable that it is 5 mol%, and it is more preferable that it is 0.1-1 mol%.

  The carbonate is not particularly limited, and examples thereof include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1 And alkylene carbonates such as 2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. These carbonates can be used singly or in combination of two or more. Among them, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate may be used from the viewpoint of easy availability and easy setting of conditions for polymerization reaction. preferable.

  In the production of the polycarbonate diol used in the present embodiment, it is preferable to add a catalyst. Although it does not specifically limit as said catalyst, Usually, the catalyst (transesterification catalyst) used for transesterification is mentioned. Examples of the ester exchange reaction catalyst include metal compounds of alkali metals and alkaline earth metals (eg, metal alcoholates (metal alkoxides), metal oxides such as metal oxides, metal amides, etc .; metal hydrides, metal hydroxides, etc. Inorganic metal compounds; metal carbonates, nitrogen-containing metal borates, and metal salts such as basic alkali metal salts and alkaline earth metal salts of organic acids). The alkali metals include, for example, lithium, sodium and potassium, the alkaline earth metals include, for example, magnesium, calcium, strontium and barium, and the other metals include 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, There may be mentioned thallium, lead, bismuth and ytterbium. These catalysts can be used alone or in combination of two or more. Among these, when using an organic compound (especially metal alkoxide) and / or a salt containing at least one metal selected from the group consisting of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead and ytterbium The polymerization reaction of polycarbonate diol is favorably performed, and it is preferable because it hardly affects the production of a resin such as a polyurethane resin using the obtained polycarbonate diol. In particular, it is more preferable to use, as the catalyst, an organic compound (particularly metal alkoxide) and / or a salt containing at least one metal selected from the group consisting of titanium, tin, zirconium, and ytterbium.

  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 in two stages, for example. Diol and carbonate are mixed in a molar ratio (diol: carbonate), for example, in a ratio of 20: 1 to 1:10, and the first stage reaction is performed at 100 to 250 ° C. under normal pressure or reduced pressure. 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 produced 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, ethylene glycol produced can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate diol. Next, in the second reaction, the first reaction product 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 is to obtain a polycarbonate diol of a predetermined molecular weight.

[Polyol]
The polycarbonate diol composition of the present embodiment preferably contains a polyol which is solid at 20 ° C. (hereinafter, also referred to as “solid polyol”). The term "polyol" as used herein refers to, for example, a compound having a number average molecular weight of 300 or more and having two or more hydroxyl groups. The polycarbonate diol composition of the present embodiment can be adjusted to have a turbidity at 20 ° C. and a turbidity at 40 ° C. in a suitable range by containing a specific amount of solid polyol, and has visibility and fluidity to handle. There is a tendency that the property is good, and when it is used as a raw material of a resin (for example, a polyurethane resin) or a coating component, it is possible to obtain a resin or a coating film having excellent transparency.

  In the polycarbonate diol composition of the present embodiment, the content of the solid polyol in the polycarbonate diol composition is preferably 0.05% by weight or more and 10% by weight or less. When the content of the solid polyol is 0.05% by weight or more, the turbidity of the polycarbonate diol composition at 20 ° C. can be increased, and the visibility tends to be excellent. If the content of the solid polyol is 10% by weight or less, the flowability of the polycarbonate diol composition at 20 ° C. tends to be maintained. If the content of the solid polyol is 0.1% by weight or more and 8% by weight or less, it is preferable because the fluidity and the visibility can be further improved in a balanced manner.

  The polycarbonate diol composition of the present embodiment includes the polycarbonate diol which is in a liquid form at 20 ° C., and the solid polyol, and the ratio of the solid polyol in the polycarbonate diol composition is in the above range, and thus the handleability is improved. In addition to being excellent in (flowability and visibility), when used as a raw material of a resin (for example, a polyurethane resin) or a coating component, a resin or a coating film excellent in transparency tends to be obtained.

  The number average molecular weight of the solid polyol of the present embodiment is preferably 300 to 10000, more preferably 400 to 8000, and more preferably 500 to 5000, from the viewpoint of exerting the effects of the present embodiment more effectively and reliably. It is further preferred that

  In the polycarbonate diol composition of the present embodiment, the melting point of the solid polyol is preferably 30 ° C. to 100 ° C., more preferably 35 ° C. to 80 ° C., and 35 ° C. to 60 ° C. Is more preferred. When the melting point is 30 ° C. or more, the turbidity of the polycarbonate diol composition at 20 ° C. can be increased, and the visibility at normal temperature (eg, 20 ° C.) tends to be excellent. When the melting point is 100 ° C. or less, the transparency of a resin (for example, a polyurethane resin such as a thermoplastic polyurethane resin) obtained from the polycarbonate diol composition of the present embodiment or a coating film tends to be excellent. In addition, in this embodiment, melting | fusing point of solid polyol can be measured by the method as described in the below-mentioned Example.

  Although it does not specifically limit as a kind of solid polyol, For example, polyether polyol, polyester polyol, polycaprolactone polyol, acrylic polyol, polyalkylene polyol, and polycarbonate polyol are mentioned. These solid polyols can be used singly or in combination of two or more.

  The polyether polyol is not particularly limited. For example, one or more alkylene oxides such as ethylene oxide and propylene oxide may be used alone or in combination of two or more polyhydroxy compounds (for example, ethylene glycol, propylene glycol, tri) Examples thereof include polyether polyols obtained by addition to methylol propane, glycerin, pentaerythritol, and ring-opening polymers such as tetrahydrofuran.

  The polyester polyol is not particularly limited, but polyester polyols obtained by direct esterification reaction and / or transesterification reaction of polyhydric alcohol and polyhydric carboxylic acid or ester-forming derivative such as ester, anhydride or halide thereof Can be mentioned. Examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Diol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2 -Methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol , 2-Methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol Aliphatic diols such as triethylene glycol; Alicyclic diols such as cyclohexanedimethanol, cyclohexanediol; trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, pentaerythritol, tetramethylolpropane, etc. 3 Alcohols with higher prices are included. Examples of the polyvalent carboxylic acid or ester-forming derivative thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid Acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid Aliphatic dicarboxylic acids such as dimer acid; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid; 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1, 2 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as acid, 1,4-dicarboxymethylene cyclohexane, nadic acid, methyl nadic acid; polycarboxylic acids such as trimellitic acid, trimesic acid, tricarboxylic acid such as trimer of castor oil fatty acid; Acid anhydrides of polyvalent carboxylic acids, halides of polyvalent carboxylic acids, halides such as bromide, methyl esters of polyvalent carboxylic acids, ethyl esters, propyl esters, isopropyl esters, butyl esters and isobutyl esters.

  The polycaprolactone polyol is not particularly limited, and examples thereof include ring-opening polymers of caprolactone such as polycaprolactone diol.

  The acrylic polyol is not particularly limited, but, for example, a homopolymer of an ethylenically unsaturated bond-containing monomer (for example, hydroxyethyl acrylate, hydroxypropyl acrylate) having one or more kinds of hydroxyl groups, An ethylenically unsaturated bond-containing monomer having one or more types of hydroxyl groups, and another ethylenically unsaturated bond-containing monomer copolymerizable with the ethylenically unsaturated bond-containing monomer (for example, Copolymers with (methyl acrylate, ethyl acrylate).

  The polyalkylene polyol is not particularly limited, and examples thereof include polybutadiene polyol and polyisoprene polyol.

These solid polyols can be used singly or in combination of two or more. Among these, the solid polyol is preferably a polycarbonate polyol from the viewpoint of maintaining the excellent mechanical strength, hydrolysis resistance and heat resistance of the polycarbonate diol.
As a polycarbonate polyol, the compound obtained by making a polyol component and a carbonate compound react can be mentioned. Examples of the polyol component include polyhydric alcohols such as diols and tri- or higher alcohols. Examples of the diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like. Linear diols such as 1,9-nonanediol and 1,10-decanediol; 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1 , 6-hexanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4 Branched diols such as -trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 1,3-cyclohexanediol, 1,- Alicyclic-based diols such as cyclohexanediol and 1,4-cyclohexanedimethanol; 4-benzenedimethanol, 1,4-benzenediethanol, 1,4-benzenedipropanol, 1,4-benzenedibutanol, 3-benzenedimethanol, 1,3-benzenediethanol, 1,3-benzenedipropanol, 1,3-benzenedibutanol, 4- (4-hydroxymethylphenyl) butanol, 3- [4- (2-hydroxyethyl) Compounds having a linear or branched divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms such as phenyl) propanol and the like can be mentioned. Aromatic diols such as p-xylene diol and p-tetrachloroxylene diol; ether based diols such as diethylene glycol and dipropylene glycol, and the like. These diols may be used alone or in combination of two or more. Can be used in combination. Examples of the carbonate compound include alkylene carbonates such as ethylene carbonate and propylene carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, diaryl carbonates such as diphenyl carbonate, and phosgene.

[Low-molecular-weight alcohol]
The polycarbonate diol composition of the present embodiment may further contain a low molecular weight alcohol (hereinafter also referred to as “solid low molecular weight alcohol”) which is solid at 20 ° C. The solid low molecular weight alcohol as referred to herein means, for example, an alcohol having a number average molecular weight of less than 300.

  The polycarbonate diol composition of the present embodiment can adjust the turbidity at 20 ° C. and the turbidity at 40 ° C. to a suitable range by including a solid low molecular weight alcohol, and has handleability by having visibility and fluidity. When used as a raw material of a resin (for example, a polyurethane resin) or as a coating component, it tends to be possible to obtain a resin or a coating film having excellent transparency.

  In the polycarbonate diol composition of the present embodiment, the content of the solid low molecular weight alcohol is preferably 1% by weight or more and 20% by weight or less, more preferably 1% by weight or more and 15% by weight or less, and 1% by weight It is more preferable that the content is 10% by weight or more. When the content of the solid low molecular weight alcohol is 1% by weight or more, the visibility tends to be excellent even when the content of the solid polyol is reduced when used in combination with the solid polyol. When the content of the solid low molecular weight alcohol is 20% by weight or less, the fluidity of the polycarbonate diol composition tends to be better maintained. In addition, when the content of the solid low molecular weight alcohol is 1% by weight or more and 15% by weight or less, fluidity and visibility tend to be further excellent in balance.

  The polycarbonate diol composition of the present embodiment further includes a polycarbonate diol which is in a liquid form at 20 ° C. and the solid low molecular weight alcohol, and the ratio of the solid low molecular weight alcohol in the polycarbonate diol composition is within the above range. As a result, the handleability (flowability and visibility) tends to be further excellent.

  In the polycarbonate diol composition of the present embodiment, the melting point of the solid low molecular weight alcohol is preferably 30 ° C. to 100 ° C., more preferably 35 ° C. to 80 ° C., and 35 ° C. to 60 ° C. It is further preferred that When the melting point is 30 ° C. or more, the visibility at normal temperature (eg, 20 ° C.) tends to be further excellent by mixing with a polycarbonate diol (in particular, a polycarbonate diol which is a liquid form). When the melting point of the solid low molecular weight alcohol is 100 ° C. or less, the transparency of the resin obtained from the polycarbonate diol composition of the present embodiment (in particular, a polyurethane resin such as a thermoplastic polyurethane resin) and the coating tends to be further excellent. is there. In addition, in this embodiment, melting | fusing point of solid low molecular weight alcohol can be measured by the method as described in the below-mentioned Example.

  The type of solid low molecular weight alcohol according to this embodiment is not particularly limited, and examples thereof include pentadecane-1-ol, hexadecane-1-ol, heptadecane-1-ol, octadecane-1-ol, nonandecane-1-ol, Monoalcohols such as itanas-1-ol; hexane-1,6-diol, octane-1,8-diol, nonane-1,9-diol, decane-1,10-diol, decane-1,2-diol, Diols such as undecane-1, 11-diol, dodecane-1, 12-diol, dodecane-1, 2-diol and the like can be mentioned.

[Method of producing polycarbonate diol composition]
The method for preparing the polycarbonate diol composition of the present embodiment is not particularly limited. For example, a solid polyol and / or a solid low molecular weight alcohol is added to a polycarbonate diol (for example, a polycarbonate diol which is a liquid form at 20 ° C.) The method of stirring is mentioned. The stirring temperature and the stirring time are not particularly limited, and the stirring temperature may be, for example, 50 to 150 ° C., and the stirring time may be, for example, 10 minutes to 5 hours.

<Use>
The polycarbonate diol composition of the present embodiment is suitably used as a raw material of resin (for example, polyurethane resin or thermoplastic elastomer), component such as paint or adhesive, modifier for resin (for example, polyester resin or polyimide resin), etc. It can be used. In particular, the polycarbonate diol composition of the present embodiment is not only excellent in transparency, but also tends to be excellent in strength and chemical resistance, and thus particularly a paint component, a resin (for example, a polyurethane resin or a thermoplastic elastomer, preferably polyurethane It can be suitably used as a raw material of resin).

(Polyurethane resin)
The polyurethane resin (for example, a thermoplastic polyurethane resin) of the present embodiment can be obtained by reacting at least the polycarbonate diol composition of the present embodiment and an organic polyisocyanate, and further obtained by reacting a chain extender. be able to.

  The organic polyisocyanate is not particularly limited. 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'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), aromatic diisocyanates such as phenylene diisocyanate 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI), etc. Aliphatic diisocyanates, and isocyanurated modified products, carbodiimidized modified products, biuret modified modified products of these isocyanates, and the like. These organic polyisocyanates can be used alone or in combination of two or more. In addition, these organic polyisocyanates may be used by masking (protecting) isocyanate groups with a blocking agent.

  Although it does not specifically limit as a chain extender, For example, the well-known chain extender used for polyurethane resin (For example, water, low molecular weight polyol, a polyamine etc.) can be used. More specific chain extenders include, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10 Low-molecular polyols such as decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, ethylene diamine, hexamethylene Polyamines such as diamine, isophorone diamine, xylylene diamine, diphenyl diamine, diamino diphenyl methane and the like can be mentioned. These chain extenders can be used alone or in combination of two or more.

  The thermoplastic polyurethane of the present embodiment is added with a stabilizer such as a heat stabilizer (for example, an antioxidant), a light stabilizer, a plasticizer, an inorganic filler, a lubricant, a colorant, a silicone oil, a foaming agent, a flame retardant, etc. It is preferable to add stabilizers such as heat stabilizers and light stabilizers.

  It does not specifically limit as a method to manufacture the polyurethane resin of this embodiment, You may carry out based on a well-known polyurethane according to a manufacturing method. Specifically, a polyurethane resin can be produced by reacting the polycarbonate diol composition of the present embodiment with an organic polyisocyanate at normal temperature to 200 ° C. under atmospheric pressure. Furthermore, when using a chain extender, it may be added before the polymerization reaction of a polycarbonate diol composition and organic polyisocyanate, and may be added during a polymerization reaction. As a specific example of still another method for producing the thermoplastic polyurethane of the present embodiment, for example, US Pat. No. 5,070,173 can be referred to.

  In the production of the polyurethane resin, known polymerization catalysts and solvents may be used. The polymerization catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate.

(Coating composition)
The coating composition of the present embodiment may be, for example, any of the following forms (1) to (3), and is preferably in the form of (2) or (3), (3) More preferred is a form.
(1) Two-component solvent-based or water-based coating composition containing a polycarbonate diol composition of the present embodiment and an organic polyisocyanate (2) Urethane obtained by reacting the polycarbonate diol composition of the present embodiment with an organic polyisocyanate One-component solvent-based or water-based coating composition containing prepolymer (3) One-component solvent-based or polyurethane resin obtained by reacting the polycarbonate diol composition of the present embodiment, organic polyisocyanate and chain extender or Water-based coating composition

  It does not specifically limit as a method to manufacture the coating composition (paint) of this embodiment, A well-known manufacturing method can be used.

  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 flowability adjuster, depending on various uses. , Plasticizers, antioxidants, ultraviolet light absorbers, light stabilizers, antifoaming agents, leveling agents, coloring agents and the like.

  The coating composition (paint) of the present embodiment may contain a solvent. The solvent is not particularly limited. For example, dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, xylene, ethyl cellosolve, ethyl acetate, acetic acid Examples include butyl, ethanol, isopropanol, n-butanol, water and the like. These solvents may be used alone or in combination of two or more.

  Hereinafter, the present embodiment will be described in more detail by way of specific examples and comparative examples, but the present embodiment is not limited at all by the following examples and comparative examples as long as the gist thereof is not exceeded. Various physical properties in Examples and Comparative Examples described later were measured by the methods shown below.

1. Turbidity of Polycarbonate Diol Composition The polycarbonate diol composition is placed in a measuring cell and allowed to stand in a freezer at -5 ° C for 8 hours. Thereafter, the cell is removed from the freezer and allowed to stand at room temperature of 20 ± 5 ° C. for 24 hours. After wiping off the dirt on the surface of the measuring cell, the turbidity was measured in an automatic mode using a turbidimeter (2100P type, manufactured by HACH). The cell was reset and measured three times, and the average value was taken as the turbidity at normal temperature.
The turbidity at 40 ° C. was measured within 3 minutes after leaving the measuring cell containing the polycarbonate diol composition in a dryer at 40 ° C. for 12 hours and taking it out.

2. Evaluation of Flowability of Polycarbonate Diol Composition A flat-bottomed cylindrical transparent glass test specimen with an inner diameter of 30 mm and a height of 120 mm was marked at a height of 55 mm (A line) and 85 mm (B line) from the tube bottom. A sample (polycarbonate diol composition) heated for 8 hours in a dryer at 50 ° C. is weighed to line A, and then allowed to stand upright for 24 hours at a room temperature of 20 ± 5 ° C. Then, the sample was immediately turned horizontally on a table, and the time taken for the tip of the liquid surface of the sample to pass the B line after the test tube was turned over was taken as the flow time (seconds) to evaluate the fluidity.

3. Determination of Composition of Polycarbonate Diol The composition of 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 the mixture was cooled to room temperature, 1 to 2 drops of phenolphthalein as an indicator were added to the mixture and neutralized with hydrochloric acid. Thereafter, the mixture was cooled in a refrigerator for 3 hours, and after removing precipitated salts by filtration, the filtrate was analyzed by gas chromatography (GC). In addition, GC analysis is performed using a gas chromatography GC14B (manufactured by Shimadzu Corp.) with a DB-WAX (manufactured by J & W Corporation) 30 m and a film thickness of 0.25 μm as a column and a detector using diethylene glycol diethyl ester as an internal standard The hydrogen 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 for 5 minutes at 60 ° C.
The composition of the polycarbonate diol composition was determined based on the area value of the diol obtained by GC analysis.

4. Determination of the number average molecular weight of polycarbonate diol and solid polyol The number average molecular weight of polycarbonate diol and solid polyol is titrated with an ethanol solution of potassium hydroxide using acetic anhydride and pyridine. “Neutralitative titration method (JIS K 0070-1992) The hydroxyl value (OH value) was determined according to “,” and calculated using the following formula (1a).

Number average molecular weight = 2 / (OH number × 10 ⁻³ /56.1) (1a)

5. Determination of melting point of solid polyol and solid low molecular weight alcohol The melting point of the solid polyol and solid low molecular weight alcohol was measured according to JIS K0064.

6. Mechanical Properties of Polyurethane Film The polyurethane film obtained from the polycarbonate diol composition was cut into a 10 mm × 80 mm strip and was cured for 3 days in a thermostatic chamber at 23 ° C. and 50% RH as a test body. About the obtained test body, breaking strength (unit: MPa) and breaking elongation (unit:%) at a check distance of 50 mm and a tensile speed of 100 mm / min using a Tensilon tensile tester (manufactured by ORIENTEC, RTC-1250A) Was measured.

7. Hydrolysis resistance of polyurethane film The polyurethane film obtained from the polycarbonate diol composition was cut into a 10 mm × 80 mm strip to obtain a test body. The obtained test body was immersed in warm water at 90 ° C. for 7 days. After removing water, those which were aged for 3 days in a constant temperature room at 23 ° C. and 50% RH were used as test specimens. The breaking strength (unit: MPa) of the obtained test body was measured using a Tensilon tensile tester (RTC-1250A, manufactured by ORIENTEC) at a distance between checks of 50 mm and a tensile speed of 100 mm / min, and the following formula (2a) Were used to determine the hydrolysis resistance of the polyurethane film.

Hydrolysis resistance (%)
= (Breaking strength after immersion in warm water) / (Breaking strength before immersion in warm water) × 100 (2a)

8. Transparency of the polyurethane film _{(Tt 1 / Tt 2 × 100} )
The polyurethane film obtained from the polycarbonate diol composition was immersed in distilled water at 90 ° C. for one week. After that, the moisture was wiped off from the polyurethane film, and the polyurethane film was aged for 3 days in a temperature-controlled room at 23 ° C. and 50% RH. According to JIS K 7105, the total light transmittance (Tt ₁ ) of the polyurethane film after immersion and the total light transmittance (Tt ₂ ) of the polyurethane film after immersion are determined, and the transparency of the polyurethane film is determined from the following formula (1) It asked for (%).

Transparency (%) = Tt ₁ / Tt ₂ × 100 (1)

9. Transparency of coating film (visual evaluation)
The coating film obtained from the polycarbonate diol composition was allowed to stand at 50 ° C. for 30 days, and then aged for 1 day in a thermostatic chamber at 23 ° C. and 50% RH. Thereafter, the transparency of the coating was observed visually. The case where it had high transparency was made into "1", and the case where it does not have transparency was made into "5", and the transparency of the coating film was evaluated by 5-step evaluation.

10. Ethanol resistance of coating film The coating film appearance after immersion in a 50% EtOH aqueous solution at room temperature for 4 hours was visually evaluated for the coating film obtained from the polycarbonate diol composition. According to JIS K 5600-8-1, the degree and the amount of defects are represented by grades 0 to 5 and are regarded as ethanol resistance of the coating film.

11. Content of solid low-molecular alcohol 1 g of a polycarbonate diol composition (sample) was dissolved in 10 ml of acetone and subjected to GC analysis under the same conditions for determining the composition of the polycarbonate diol described above. Based on the area value, the content of solid low molecular weight alcohol in the polycarbonate diol composition was determined.

[Polymerization Example 1]
680 g (7.6 mol) of dimethyl carbonate, 400 g (3.9 mol) of 1,5-pentanediol, 1,6- in a 2 L glass flask equipped with a rectification column packed with ordered packing and a stirrer. 480 g (4.1 mol) of hexanediol was charged. To the flask was further added 0.14 g of titanium tetraisopropoxide as a catalyst, and the mixture in the flask was stirred and heated at normal pressure to initiate a reaction. The reaction was carried out for 20 hours by distilling off the mixture of methanol and dimethyl carbonate generated while raising the temperature to 90 to 140 ° C. Thereafter, the pressure was reduced to 17 kPa, and the reaction was further performed at 150 ° C. for 15 hours while distilling off the mixture of methanol and dimethyl carbonate. A polycarbonate diol (referred to as PC-1) was obtained by adding 0.39 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours. The polycarbonate diol contained 0.2% of 1,6-hexanediol which is a solid alcohol as a residual monomer.

Polymerization Example 2
Polymerization was carried out using the apparatus shown in Polymerization Example 1. 800 g (9.1 mol) of ethylene carbonate and 700 g (9.2 mol) of 1,3-propanediol were charged. As a catalyst, 0.13 g of titanium tetrabutoxide was added, and the mixture was stirred and heated under normal pressure. The reaction temperature was gradually raised to 160 ° C., and the reaction was carried out for 20 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure was reduced to 15 kPa, and reaction was further performed at 160 ° C. for 12 hours while distilling off the diol and ethylene carbonate. A polycarbonate diol (referred to as PC-2) was obtained by adding 0.35 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours.

[Polymerization Example 3]
Polymerization was carried out using the apparatus shown in Polymerization Example 1. 580 g (6.6 mol) of ethylene carbonate, 400 g (4.4 mol) of 1,4-butanediol, and 250 g (2.1 mol) of 1,6-hexanediol were charged. As a catalyst, 0.11 g of titanium tetrabutoxide was added, and the mixture was stirred and heated under normal pressure. The reaction temperature was gradually raised to 160 ° C., and the reaction was carried out for 20 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure was reduced to 15 kPa, and reaction was further performed at 160 ° C. for 6 hours while distilling off the diol and ethylene carbonate. A polycarbonate diol (referred to as PC-3) was obtained by adding 0.33 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours. The polycarbonate diol contained 1.0% of 1,6-hexanediol which is a solid alcohol as a residual monomer, and 0.6% of 1,4-butanediol.

Polymerization Example 4
Polymerization was carried out using the apparatus shown in Polymerization Example 1. 570 g (6.3 mol) of dimethyl carbonate, 400 g (3.4 mol) of 3-methyl-1,5-pentanediol, and 400 g (3.4 mol) of 1,6-hexanediol were charged. As a catalyst, 0.12 g of titanium tetrabutoxide was added, and the mixture was stirred and heated under normal pressure. The reaction temperature was gradually raised to 160 ° C., and the reaction was carried out for 20 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure was reduced to 15 kPa, and reaction was further performed at 160 ° C. for 12 hours while distilling off the diol and ethylene carbonate. A polycarbonate diol (referred to as PC-4) was obtained by adding 0.34 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours. The polycarbonate diol contained 0.3% of 1,6-hexanediol which is a solid alcohol as a residual monomer.

Polymerization Example 5
Polymerization was carried out using the apparatus shown in Polymerization Example 1. 820 g (7.0 mol) of diethyl carbonate and 860 g (7.3 mol) of 1,6-hexanediol were charged. 0.14 g of titanium tetrabutoxide was added as a catalyst, and the mixture was stirred at normal pressure, and the mixture of ethanol and diethyl carbonate formed was distilled off while raising the temperature to 90 to 160 ° C., and reaction was carried out for 20 hours. Thereafter, the pressure was reduced to 17 kPa, and the mixture was reacted at 160 ° C. for 12 hours while distilling off the mixture of ethanol and diethyl carbonate. A polycarbonate diol (referred to as PC-5) was obtained by adding 0.34 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours. The polycarbonate diol contained 0.2% of 1,6-hexanediol which is a solid alcohol as a residual monomer.

Polymerization Example 6
Polymerization was carried out using the apparatus shown in Polymerization Example 1. 820 g (7.0 mol) of diethyl carbonate and 770 g (7.4 mol) of 1,5-hexanediol were charged. 0.14 g of titanium tetrabutoxide was added as a catalyst, and the mixture was stirred at normal pressure, and while raising the temperature to 90 to 160 ° C., the mixture of ethanol and diethyl carbonate formed was distilled off and the reaction was carried out for 20 hours. Thereafter, the pressure was reduced to 17 kPa, and the mixture was reacted at 160 ° C. for 12 hours while distilling off the mixture of ethanol and diethyl carbonate. A polycarbonate diol (referred to as PC-5) was obtained by adding 0.34 g of 2-ethylhexyl acid phosphate and heating at 120 ° C. for 5 hours.

  The evaluation results of the polycarbonate diol obtained in Polymerization Examples 1 to 5 are shown in Table 1 below.

  In the following examples and comparative examples, PC-5 and 6 were used as the solid polyol, and 1,6-hexanediol (melting point: 41 ° C.) was used as the solid low molecular weight alcohol.

※ The composition of each repeating unit in the table shows only R.
※ The melting point is not measured when the fluidity at 20 ° C in the table is 90 seconds or less

[Examples 1-1 to 1-10, Comparative Example 1-1, and Comparative Example 1-2]
The raw materials shown in Table 2 are added in the addition amounts shown in Table 2 to a 1 L glass flask equipped with a stirrer, heated to 80, stirred for 5 hours, and polycarbonate diol composition (hereinafter referred to as composition-1 The composition −10, the composition 20, and the composition 21) were obtained.

  Various properties of the polycarbonate diol compositions of Examples 1-1 to 1-10, Comparative Examples 1-1, and Comparative Example 1-2 are shown in Table 3.

[Examples 2-1 to 2-7]
In a reactor equipped with a stirrer, a thermometer and a condenser, 200 g of the polycarbonate diol composition obtained in each of Examples 1 to 7, 34 g of hexamethylene diisocyanate, and 0.02 g of dibutyltin dilaurate as a catalyst are charged. The reaction was carried out for time to obtain a urethane prepolymer having a terminal isocyanate (NCO) group. To the above urethane prepolymer, 600 g of dimethylformamide was added as a solvent to obtain a solution. Thereafter, 17 g of isophorone diamine as a chain extender was added to the obtained solution, and the mixture was 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 remove the solvent, and then placed in a dryer at 100 ° C. for 2 hours for drying to obtain a polyurethane film (Example 2) -1 to 2-7). Physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 4.
[Comparative Examples 2-1 and 2-2]
Polyurethane films were obtained in the same manner as in Example 2-1 except that the polycarbonate diol compositions obtained in Comparative Examples 1 and 2 were used as the polycarbonate diol composition (Comparative Examples 2-1 and 2-2). ). Physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 4.

[Examples 3-1 to 3-4]
40 g of the polycarbonate diol composition obtained in Examples 1-1 to 1-4, 0.75 g of BYK-331 (manufactured by BYK Chemical Co., Ltd.) as a leveling agent, and thinner (xylene / butyl acetate = 70/30 (weight ratio)) The mixture was stirred with 1.25 g of a dibutyltin dilaurate solution dissolved to 2% by weight) and 40 g of the thinner to obtain a paint base. A coating liquid was prepared by adding 7.5 g of organic polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals, isocyanate (NCO) content: 23.1%) as a curing agent to the obtained paint base. The coating solution was spray-coated on an acrylonitrile-butadiene-styrene (ABS) resin plate, the thinner was blown at room temperature for 2 hours, and then heat cured at 80 ° C. for 2 hours to obtain a coated film. Physical properties were evaluated using the coating film. The evaluation results are shown in Table 5.

[Comparative Examples 3-1 and 3-2]
A coating was obtained in the same manner as in Example 3-1 except that the polycarbonate diol compositions obtained in Comparative Examples 1-1 and 1-2 were used as the polycarbonate diol composition. Physical properties were evaluated using the coating film. The evaluation results are shown in Table 5.

  The polycarbonate diol composition of the present invention is excellent in flowability and visibility, is easy to handle, and when used as a resin (for example, a polyurethane resin) raw material or a paint component, it is a resin or a coating film excellent in transparency. Since it can be obtained, it can be suitably used as a raw material of resin (for example, polyurethane resin) or a paint component.

Claims (4)

The polycarbonate diol composition which contains the polycarbonate diol which has 1 or more types of repeating units represented by following formula (A), and a terminal hydroxyl group, and satisfy | fills the following characteristics (1)-(3).
(In formula (A), R shows a bivalent hydrocarbon group.)

(1) Has fluidity at 20 ° C (2) The turbidity at 20 ° C is 5 NTU or more and 100 NTU or less (3) The turbidity at 40 ° C is less than 5 NTU Further comprising a polyol which is solid at 20 ° C.,
The polycarbonate diol is in a liquid form at 20 ° C.,
The polycarbonate diol composition according to claim 1, wherein the content of the polyol in the polycarbonate diol composition is 0.05% by weight or more and 10% by weight or less. It further comprises a low molecular weight alcohol which is solid at 20 ° C.,
The polycarbonate diol is in a liquid form at 20 ° C.,
The polycarbonate diol composition according to claim 1 or 2, wherein the content of the low molecular weight alcohol in the polycarbonate diol composition is 1% by weight or more and 20% by weight or less. The polycarbonate diol composition according to any one of claims 1 to 3, which satisfies the following formula (1).

90 ≦ Tt ₁ / Tt ₂ × 100 ≦ 100 (1)

Tt ₁ : total light transmittance Tt ₂ after the polyurethane film obtained by reacting the polycarbonate diol composition, the isocyanate compound, and the chain extender in a distilled water at 90 ° C. for one week Tt ₂ : the polyurethane Total light transmittance before soaking the film in 90 ° C distilled water for 1 week