TWI546317B - Polycarbonate diol containing carbonate compounds - Google Patents

Polycarbonate diol containing carbonate compounds Download PDF

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TWI546317B
TWI546317B TW103145840A TW103145840A TWI546317B TW I546317 B TWI546317 B TW I546317B TW 103145840 A TW103145840 A TW 103145840A TW 103145840 A TW103145840 A TW 103145840A TW I546317 B TWI546317 B TW I546317B
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polycarbonate diol
diol composition
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carbonate
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TW201533082A (en
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Eizaburo Ueno
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Asahi Kasei Chemicals Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

含碳酸酯化合物之聚碳酸酯二醇 Polycarbonate diol containing carbonate compound

本發明係關於一種聚碳酸酯二醇。 This invention relates to a polycarbonate diol.

聚碳酸酯二醇例如係作為聚胺基甲酸酯或熱塑性彈性體等之軟段(soft segment)，且作為耐水解性、耐光性、耐氧化劣化性、耐熱性等優異之素材而為人所知。然而，關於聚碳酸酯二醇，於用作塗料之構成材料之情形時，由於聚碳酸酯二醇鍵間之相互作用較強，故而存在塗膜表面之平滑性受損之情形。 The polycarbonate diol is, for example, a soft segment such as a polyurethane or a thermoplastic elastomer, and is excellent in materials such as hydrolysis resistance, light resistance, oxidative degradation resistance, and heat resistance. Known. However, in the case where the polycarbonate diol is used as a constituent material of a coating material, since the interaction between the polycarbonate diol bonds is strong, the smoothness of the surface of the coating film may be impaired.

另一方面，揭示有具有環狀碳酸酯結構之各種添加劑。例如，揭示有不會使機械特性及/或耐溶劑性明顯惡化，減少環氧樹脂之黏性之具有環狀碳酸酯結構之添加劑(例如參照專利文獻1)。又，揭示有作為電解液等溶劑、高分子材料前驅物、添加劑而有用之新穎環狀碳酸酯(例如參照專利文獻2)。又，揭示有含有5-甲基-1,3-二烷-2-酮之聚碳酸酯二醇(例如參照專利文獻3)。 On the other hand, various additives having a cyclic carbonate structure are disclosed. For example, an additive having a cyclic carbonate structure which does not significantly deteriorate mechanical properties and/or solvent resistance and which reduces the viscosity of an epoxy resin is disclosed (for example, see Patent Document 1). Further, a novel cyclic carbonate which is useful as a solvent such as an electrolytic solution, a polymer material precursor, or an additive is disclosed (for example, see Patent Document 2). Also, it is revealed that it contains 5-methyl-1,3-di A polycarbonate diol of an alkyl-2-one (see, for example, Patent Document 3).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特表2013-528685號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-528685

[專利文獻2]日本專利特開2011-84512號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-84512

[專利文獻3]國際公開第2006-088152號 [Patent Document 3] International Publication No. 2006-088152

然而，關於專利文獻1及2中所記載之環狀碳酸酯，於用作塗料之構成材料之情形時，若少量添加，則無法提高塗膜之平滑性，若大量添加，則存在滲出之情形，而存在改善之餘地。又，關於專利文獻3中所記載之聚碳酸酯二醇，於用作塗料之構成材料之情形時，不會降低機械強度或耐油性等，但於塗膜之平滑性方面存在改善之餘地。 However, when the cyclic carbonate described in Patent Documents 1 and 2 is used as a constituent material of a coating material, if it is added in a small amount, the smoothness of the coating film cannot be improved, and if it is added in a large amount, there is a case of bleeding. And there is room for improvement. Further, in the case of using the polycarbonate diol described in Patent Document 3 as a constituent material of the coating material, mechanical strength, oil resistance, and the like are not lowered, but there is room for improvement in smoothness of the coating film.

如此，於迄今為止之技術中，尚未開發出可不降低機械強度或耐化學品性而獲得平滑之塗膜之聚碳酸酯二醇。 Thus, in the prior art, polycarbonate diol which can obtain a smooth coating film without lowering mechanical strength or chemical resistance has not been developed.

因此，本發明之目的在於提供一種例如於用作塗料之構成材料之情形時可不損及耐化學品性而獲得平滑之塗膜的聚碳酸酯二醇組合物。又，本發明之目的在於提供一種例如於用作聚胺基甲酸酯之原料之情形時，可不損及機械強度而獲得耐油性優異之聚胺基甲酸酯的聚碳酸酯二醇組合物。 Accordingly, an object of the present invention is to provide a polycarbonate diol composition which can obtain a smooth coating film without damaging chemical resistance, for example, when it is used as a constituent material of a coating material. Moreover, an object of the present invention is to provide a polycarbonate diol composition which can obtain a polyurethane having excellent oil resistance without damaging mechanical strength, for example, when it is used as a raw material of a polyurethane. .

本發明者為了解決上述課題而反覆進行努力研究，結果發現，藉由使用含有特定結構之碳酸酯化合物之聚碳酸酯二醇組合物，可達成目的，從而完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that a polycarbonate diol composition containing a carbonate compound having a specific structure can be used to achieve the object, and the present invention has been completed.

即，本發明之構成如下所述。 That is, the constitution of the present invention is as follows.

[1]一種聚碳酸酯二醇組合物，其包含含有下述式(A)所表示之重複單元與末端羥基之聚碳酸酯二醇、及 [1] A polycarbonate diol composition comprising a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and

(式(A)中，R表示碳數2~15之二價脂肪族或脂環族烴) (In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms)

下述式(B)所表示之碳酸酯化合物0.05~5重量%， 0.05 to 5% by weight of the carbonate compound represented by the following formula (B),

(式(B)中，l及m表示2~15之整數，且l≠m)。 (In the formula (B), l and m represent an integer of 2 to 15, and l≠m).

[2]如上述[1]之聚碳酸酯二醇組合物，其中上述式(B)所表示之碳酸酯化合物為下述式(C)所表示之碳酸酯化合物， [2] The polycarbonate diol composition according to the above [1], wherein the carbonate compound represented by the above formula (B) is a carbonate compound represented by the following formula (C).

(式(C)中，l及m表示4~6之整數，且l≠m)。 (In the formula (C), l and m represent an integer of 4 to 6, and l≠m).

[3]如上述[1]或[2]之聚碳酸酯二醇組合物，其中上述聚碳酸酯二醇中之末端OH基比率為95.0~99.9%。 [3] The polycarbonate diol composition according to the above [1] or [2] wherein the ratio of terminal OH groups in the above polycarbonate diol is from 95.0 to 99.9%.

[4]如上述[1]至[3]中任一項之聚碳酸酯二醇組合物，其中藉由ICP(Inductive Coupling Plasma，電感耦合電漿)進行測定時之選自由鈦、鐿、錫及鋯所組成之群中的至少1種金屬元素之含量為0.0001~0.02重量%。 [4] The polycarbonate diol composition according to any one of the above [1] to [3] wherein, when measured by ICP (Inductive Coupling Plasma), it is selected from the group consisting of titanium, tantalum, and tin. The content of at least one metal element in the group consisting of zirconium and zirconium is 0.0001 to 0.02% by weight.

[5]如上述[1]至[4]中任一項之聚碳酸酯二醇組合物，其中藉由ICP進行測定時之鈦、鐿、錫及鋯之總含量為0.0001~0.02重量%。 [5] The polycarbonate diol composition according to any one of the above [1] to [4] wherein the total content of titanium, bismuth, tin and zirconium when measured by ICP is 0.0001 to 0.02% by weight.

[6]如上述[1]至[5]中任一項之聚碳酸酯二醇組合物，其中藉由ICP進行測定時之磷元素之含量為0.0001~0.02重量%。 [6] The polycarbonate diol composition according to any one of the above [1] to [5] wherein the content of the phosphorus element when measured by ICP is 0.0001 to 0.02% by weight.

[7]如上述[1]至[6]中任一項之聚碳酸酯二醇組合物，其包含0.03~5重量%之下述式(H)所表示之碳酸酯化合物， [A] The polycarbonate diol composition according to any one of the above [1] to [6], which comprises 0.03 to 5% by weight of a carbonate compound represented by the following formula (H),

(式(H)中，i及k表示2~15之整數，且i≠k)。 (In the formula (H), i and k represent an integer of 2 to 15, and i ≠ k).

[8]如上述[1]至[7]中任一項之聚碳酸酯二醇組合物，其中選自由四氫呋喃、四氫吡喃及氧雜環庚烷所組成之群中之至少1種環狀醚化合物之含量為0.01~50ppm。 [8] The polycarbonate diol composition according to any one of the above [1] to [7] wherein at least one ring selected from the group consisting of tetrahydrofuran, tetrahydropyran and oxepane The content of the ether compound is from 0.01 to 50 ppm.

[9]如上述[1]至[8]中任一項之聚碳酸酯二醇組合物，其中四氫呋喃、四氫吡喃及氧雜環庚烷之總含量為0.01~50ppm。 [9] The polycarbonate diol composition according to any one of the above [1] to [8] wherein the total content of tetrahydrofuran, tetrahydropyran and oxepane is from 0.01 to 50 ppm.

[10]如上述[1]至[9]中任一項之聚碳酸酯二醇組合物，其包含0.01~3重量%之下述式(I)所表示之碳酸酯化合物，[化5] [10] The polycarbonate diol composition according to any one of the above [1] to [9], which comprises 0.01 to 3% by weight of a carbonate compound represented by the following formula (I), [Chemical 5]

(式(I)中，r表示2~15之整數)。 (In the formula (I), r represents an integer of 2 to 15).

[11]如上述[1]至[10]中任一項之聚碳酸酯二醇組合物，其中水分量為1~500ppm。 [11] The polycarbonate diol composition according to any one of the above [1] to [10] wherein the amount of water is from 1 to 500 ppm.

[12]如上述[1]至[11]中任一項之聚碳酸酯二醇組合物，其色值為5~100。 [12] The polycarbonate diol composition according to any one of [1] to [11] above which has a color value of from 5 to 100.

[13]一種塗佈組合物，其包含如上述[1]至[12]中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯。 [13] A coating composition comprising the polycarbonate diol composition according to any one of [1] to [12] above, and an organic polyisocyanate.

[14]一種塗佈組合物，其包含使如上述[1]至[12]中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯反應而獲得之胺基甲酸酯預聚物，且該胺基甲酸酯預聚物具有末端異氰酸酯基。 [14] A coating composition comprising a urethane prepolymer obtained by reacting a polycarbonate diol composition according to any one of the above [1] to [12] with an organic polyisocyanate, And the urethane prepolymer has a terminal isocyanate group.

[15]一種塗佈組合物，其包含使如上述[1]至[12]中任一項之聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯樹脂。 [15] A coating composition comprising the polycarbonate diol composition according to any one of the above [1] to [12], an organic polyisocyanate, and a chain extender obtained by reacting the polyaminocarboxylic acid. Ester resin.

[16]一種水系塗佈組合物，其包含使水、如上述[1]至[12]中任一項之聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯。 [16] An aqueous coating composition comprising a polyamine obtained by reacting water, a polycarbonate diol composition according to any one of the above [1] to [12], an organic polyisocyanate, and a chain extender. Carbamate.

[17]一種熱塑性聚胺基甲酸酯，其係使用如上述[1]至[12]中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯而獲得。 [17] A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of the above [1] to [12] and an organic polyisocyanate.

本發明之聚碳酸酯二醇組合物於用作塗料之構成材料之情形時，可不損及耐化學品性而獲得平滑之塗膜。又，本發明之聚碳酸酯二醇組合物於用作聚胺基甲酸酯之原料之情形時，可不損及機械強度而獲得耐油性優異之聚胺基甲酸酯。由於具有該等特性，故而本發明之聚碳酸酯二醇組合物可較佳地用作塗料之構成材料，進而，可較佳地用作聚胺基甲酸酯之原料。 When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, a smooth coating film can be obtained without impairing chemical resistance. Further, when the polycarbonate diol composition of the present invention is used as a raw material of a polyurethane, it is possible to obtain a polyurethane having excellent oil resistance without impairing mechanical strength. Because of these characteristics, the polycarbonate diol composition of the present invention can be preferably used as a constituent material of a coating material, and further, it can be preferably used as a raw material of a polyurethane.

以下，對用於實施本發明之形態(以下，簡稱為「本實施形態」)詳細地進行說明。再者，本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變化而實施。 Hereinafter, the form for carrying out the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

<聚碳酸酯二醇組合物> <Polycarbonate diol composition>

本實施形態之聚碳酸酯二醇組合物包含含有下述式(A)所表示之重複單元與末端羥基之聚碳酸酯二醇、及 The polycarbonate diol composition of the present embodiment contains a polycarbonate diol containing a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and

(式(A)中，R表示碳數2~15之二價脂肪族或脂環族烴) (In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms)

下述式(B)所表示之碳酸酯化合物0.05~5重量%。 The carbonate compound represented by the following formula (B) is 0.05 to 5% by weight.

(式(B)中，l及m表示2~15之整數，且l≠m) (In the formula (B), l and m represent integers from 2 to 15, and l≠m)

本實施形態中所使用之聚碳酸酯二醇具有上述式(A)所表示之重複單元與末端羥基。 The polycarbonate diol used in the present embodiment has a repeating unit represented by the above formula (A) and a terminal hydroxyl group.

式(A)中，R表示碳數2~15之二價脂肪族或脂環族烴，於所有重複單元中可選擇1種或2種以上。式(A)中，於R為不具有側鏈之二價脂肪族烴之情形時，聚胺基甲酸酯之耐化學品性或機械強度增高，故而較佳。進而，式(A)中，於R為選自下述式(D)中之1種或2種以上之二價脂肪族烴之情形時，可獲得耐化學品性與機械強度之平衡性良好，且成型性良好之聚胺基甲酸酯，故而較佳。 In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms, and one or two or more kinds of all repeating units may be selected. In the formula (A), when R is a divalent aliphatic hydrocarbon having no side chain, the chemical resistance or mechanical strength of the polyurethane is increased, which is preferable. Further, in the case of the formula (A), when R is one or two or more kinds of divalent aliphatic hydrocarbons selected from the following formula (D), good balance between chemical resistance and mechanical strength can be obtained. Further, a polyurethane having good moldability is preferred.

[化8]-(CH2)n- (D) [Chemical 8]-(CH 2 ) n - (D)

(式(D)中，n表示4~6之整數) (in the formula (D), n represents an integer from 4 to 6)

於R為於式(D)中n=5之情形時之二價脂肪族烴及n=6之情形時之二價脂肪族烴的2種之情形時，於-5℃之低溫下聚碳酸酯二醇組合物亦呈液狀，故而更佳。 When R is a divalent aliphatic hydrocarbon in the case of n=5 in the formula (D) and two kinds of divalent aliphatic hydrocarbons in the case of n=6, the polycarbonate is carbonated at a low temperature of -5 ° C. The ester diol composition is also liquid and therefore more preferred.

再者，於聚碳酸酯二醇中，關於式(A)所表示之重複單元之比率，就耐熱性或耐水解性之觀點而言，較佳為95莫耳%以上且100莫耳%以下，更佳為97莫耳%以上且100莫耳%以下，進而較佳為99莫耳 %以上且100莫耳%以下。 Further, 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 from the viewpoint of heat resistance or hydrolysis resistance. More preferably, it is more than 97% by mole and less than 100% by mole, and further preferably 99% by mole. More than % and less than 100% by mole.

本實施形態之聚碳酸酯二醇組合物較佳為於常溫下為液狀。關於本實施形態之聚碳酸酯二醇組合物，於用作塗料之構成成分之情形時，即便用於透明塗料中發生白濁之情形亦較少，故而用途受到限制之情形較少。再者，於本實施形態中，所謂液狀，係指將加熱至80℃之聚碳酸酯二醇組合物添加至透明樣品瓶中，以目測觀察冷卻至室溫之狀態為透明，且於使樣品瓶傾斜時即便略微傾斜亦存在流動性之狀態。 The polycarbonate diol composition of the present embodiment is preferably liquid at normal temperature. When the polycarbonate diol composition of the present embodiment is used as a constituent component of a coating material, even if it is used in a clear coating material, it is less likely to be white turbid, and thus the use is limited. In the present embodiment, the term "liquid" means that the polycarbonate diol composition heated to 80 ° C is added to a transparent sample vial, and is visually observed to be transparent to a room temperature, and is made transparent. When the sample bottle is tilted, there is a state of fluidity even if it is slightly inclined.

本實施形態之聚碳酸酯二醇組合物包含上述式(B)所表示之碳酸酯化合物，即，具有2個碳酸酯鍵之環狀化合物。本實施形態之聚碳酸酯二醇組合物藉由包含特定量之該結構之碳酸酯化合物，可獲得目標之塗膜。於本實施形態之組合物中，若式(B)所表示之碳酸酯化合物與上述聚碳酸酯二醇一併存在特定量，則該碳酸酯化合物之各碳酸酯鍵與上述聚碳酸酯二醇分子內之2個碳酸酯鍵或不同之上述聚碳酸酯二醇分子之碳酸酯鍵具有相互作用。其結果為，分子內或分子間之碳酸酯鍵距離擴大，聚碳酸酯二醇分子內或分子間之相互作用降低。其結果為，於使用本實施形態之聚碳酸酯二醇組合物，例如藉由噴霧塗裝而獲得塗膜之情形時，所噴霧之塗液之液滴不易凝聚，並且易附著於基材，而塗膜之平滑性提高。進而，上述碳酸酯化合物由於直接與聚碳酸酯二醇之碳酸酯鍵發生作用，故而少量即表現出效果，並且發生滲出之情形亦較少。又，本實施形態中所使用之碳酸酯化合物由於具有不同鏈長之亞甲基鏈，故而結晶性較低，於常溫下為液狀。因此，上述碳酸酯化合物於用於塗料之構成材料之情形時，亦不會損及塗膜之透明性。又，上述碳酸酯化合物由於分子內具有2個碳酸酯鍵，故而若發生分解則每1分子生成2分子二氧化碳。此種碳酸酯化合物亦具有可對塗膜或聚胺基甲酸酯賦予阻燃性之可能性。又，本實施 形態中所使用之碳酸酯化合物由於具有不同鏈長之亞甲基鏈，故而於環結構中具有變形，可期待於塗膜或聚胺基甲酸酯發生分解前生成二氧化碳。 The polycarbonate diol composition of the present embodiment contains the carbonate compound represented by the above formula (B), that is, a cyclic compound having two carbonate bonds. The polycarbonate diol composition of the present embodiment can obtain a target coating film by containing a specific amount of the carbonate compound having the structure. In the composition of the present embodiment, when the carbonate compound represented by the formula (B) is present in a specific amount together with the polycarbonate diol, each carbonate bond of the carbonate compound and the polycarbonate diol are The two carbonate linkages within the molecule or the carbonate linkages of the different polycarbonate diol molecules described above have an interaction. As a result, the distance between carbonate bonds in the molecule or the molecule is increased, and the intramolecular or intermolecular interaction of the polycarbonate diol is lowered. As a result, when the coating film is obtained by spray coating using the polycarbonate diol composition of the present embodiment, the droplets of the sprayed coating liquid are less likely to aggregate and adhere to the substrate. The smoothness of the coating film is improved. Further, since the above-mentioned carbonate compound acts directly on the carbonate bond of the polycarbonate diol, a small amount exhibits an effect, and a situation in which bleeding occurs is also small. Further, since the carbonate compound used in the present embodiment has a methylene chain having a different chain length, the crystallinity is low, and it is liquid at normal temperature. Therefore, the above-mentioned carbonate compound does not impair the transparency of the coating film when it is used as a constituent material of the coating material. Further, since the above carbonate compound has two carbonate bonds in the molecule, when it is decomposed, two molecules of carbon dioxide are generated per molecule. Such a carbonate compound also has a possibility of imparting flame retardancy to a coating film or a polyurethane. Also, this implementation Since the carbonate compound used in the form has a methylene chain having a different chain length, it has a deformation in the ring structure, and it is expected that carbon dioxide is generated before the coating film or the polyurethane is decomposed.

關於本實施形態中所使用之碳酸酯化合物，若碳酸酯鍵間之亞甲基鏈為2以上則較穩定，若碳酸酯鍵間之亞甲基鏈為15以下，則可獲得上述效果。作為上述碳酸酯化合物，並無特別限定，例如可列舉：1,3,6,8-四氧雜環十一烷-2,7-二酮、1,3,7,9-四氧雜環十三烷-2,8-二酮、1,3,8,10-四氧雜環十五烷-2,9-二酮、1,3,9,11-四氧雜環十七烷-2,10-二酮、1,3,10,12-四氧雜環十九烷-2,11-二酮、1,3,11,13-四氧雜環二十一烷-2,12-二酮、1,3,12,14-四氧雜環二十三烷-2,13-二酮、1,3,13,15-四氧雜環二十五烷-2,14-二酮、1,3,14,16-四氧雜環二十七烷-2,15-二酮、1,3,15,17-四氧雜環二十九烷-2,16-二酮、1,3,16,18-四氧雜環三十一烷-2,16-二酮、1,3,17,19-四氧雜環三十三烷-2,18-二酮、1,3,18,20-四氧雜環三十五烷-2,19-二酮等上述式(B)中之l與m之差為1之碳酸酯化合物；1,3,6,8-四氧雜環十二烷-2,7-二酮、1,3,7,9-四氧雜環十四烷-2,8-二酮、1,3,8,10-四氧雜環十六烷-2,9-二酮、1,3,9,11-四氧雜環十八烷-2,10-二酮、1,3,10,12-四氧雜環二十烷-2,11-二酮、1,3,11,13-四氧雜環二十二烷-2,12-二酮、1,3,12,14-四氧雜環二十四烷-2,13-二酮、1,3,13,15-四氧雜環二十六烷-2,14-二酮、1,3,14,16-四氧雜環二十八烷-2,15-二酮、1,3,15,17-四氧雜環三十烷-2,16-二酮、1,3,16,18-四氧雜環三十二烷-2,17-二酮、1,3,17,19-四氧雜環三十四烷-2,18-二酮等上述式(B)中之l與m之差為2之碳酸酯化合物；1,3,6,8-四氧雜環十三烷-2,7-二酮、1,3,7,9-四氧雜環十五烷-2,8-二酮、1,3,8,10-四氧雜環十七烷-2,9-二酮、1,3,9,11-四氧雜環十九烷-2,10-二酮、1,3,10,12-四氧雜環二十一烷-2,11-二酮、1,3,11,13-四氧雜環二十三烷-2,12-二酮、1,3,12,14-四氧雜環二十五烷-2,13-二酮、1,3,13,15-四氧 雜環二十七烷-2,14-二酮、1,3,14,16-四氧雜環二十九烷-2,15-二酮、1,3,15,17-四氧雜環三十一烷-2,16-二酮、1,3,16,18-四氧雜環三十三烷-2,17-二酮等上述式(B)中之l與m之差為3之碳酸酯化合物。於上述式(B)中之l與m之差為1之情形時，由於環結構之變形較小，碳酸酯化合物之穩定性較高，故而較佳。 The carbonate compound used in the present embodiment is stable when the methylene chain between the carbonate bonds is 2 or more, and the above effect can be obtained if the methylene chain between the carbonate bonds is 15 or less. The carbonate compound is not particularly limited, and examples thereof include 1,3,6,8-tetraoxacycloundecane-2,7-dione and 1,3,7,9-tetraoxane. Tridecane-2,8-dione, 1,3,8,10-tetraoxacyclopentadecane-2,9-dione, 1,3,9,11-tetraoxacyclohexadecane- 2,10-dione, 1,3,10,12-tetraoxacyclopentadecane-2,11-dione, 1,3,11,13-tetraoxacyclotetradecane-2,12 -dione, 1,3,12,14-tetraoxacyclohexadecane-2,13-dione, 1,3,13,15-tetraoxacyclopentadecane-2,14-di Ketone, 1,3,14,16-tetraoxacyclohexadecane-2,15-dione, 1,3,15,17-tetraoxacyclopentadecane-2,16-dione, 1,3,16,18-tetraoxacyclotridecane-2,16-dione, 1,3,17,19-tetraoxacyclotridecane-2,18-dione, 1, 3,18,20-tetraoxacyclotetradecane-2,19-dione, etc., in the above formula (B), a difference of 1 and m is a carbonate compound; 1,3,6,8-four Oxacyclododecane-2,7-dione, 1,3,7,9-tetraoxacyclotetradecane-2,8-dione, 1,3,8,10-tetraoxo-10- Hexane-2,9-dione, 1,3,9,11-tetraoxacyclooctadecane-2,10-dione, 1,3,10,12-tetraoxacyclopentadecane-2 , 11-diketone, 1,3,11,13-tetraoxacyclotetradecane-2, 12-diketone, 1,3,12,14-tetraoxacyclotetracosane-2,13-dione, 1,3,13,15-tetraoxacyclohexadecane-2,14- Diketone, 1,3,14,16-tetraoxacyclooctadecane-2,15-dione, 1,3,15,17-tetraoxacyclobutane-2,16-dione, 1,3,16,18-tetraoxacyclododecane-2,17-dione, 1,3,17,19-tetraoxacyclotritetradecane-2,18-dione, etc. (B) a carbonate compound in which the difference between l and m is 2; 1,3,6,8-tetraoxacyclotridecane-2,7-dione, 1,3,7,9-tetraoxy Heterocyclic pentadecane-2,8-dione, 1,3,8,10-tetraoxacyclohexadecane-2,9-dione, 1,3,9,11-tetraoxo-19 Alkane-2,10-dione, 1,3,10,12-tetraoxacyclohexadecane-2,11-dione, 1,3,11,13-tetraoxacyclohexadecane- 2,12-dione, 1,3,12,14-tetraoxacyclopentadecane-2,13-dione, 1,3,13,15-tetraoxy Heterocyclic heptacosane-2,14-dione, 1,3,14,16-tetraoxacyclopentadecane-2,15-dione, 1,3,15,17-tetraoxocyclo The difference between l and m in the above formula (B) such as tridecane-2,16-dione, 1,3,16,18-tetraoxacyclotrisyl-2,17-dione is 3 Carbonate compound. In the case where the difference between l and m in the above formula (B) is 1, it is preferred because the deformation of the ring structure is small and the stability of the carbonate compound is high.

又，於本實施形態中所使用之碳酸酯化合物為下述式(C)所表示之碳酸酯化合物之情形時，即，若碳酸酯鍵間之亞甲基之數量為4~6，則碳酸酯鍵間之距離及碳酸酯化合物中之碳酸酯鍵之比率變得較佳。 In the case where the carbonate compound used in the present embodiment is a carbonate compound represented by the following formula (C), that is, if the number of methylene groups between the carbonate bonds is 4 to 6, carbonic acid The distance between the ester bonds and the ratio of the carbonate bonds in the carbonate compound are preferred.

(式(C)中，l及m表示4~6之整數，且l≠m) (In the formula (C), l and m represent integers from 4 to 6, and l≠m)

進而，於式(B)所表示之碳酸酯化合物為下述式(E)或(F)所表示之碳酸酯化合物之情形時，碳酸酯化合物之穩定性較高，碳酸酯鍵間之距離及碳酸酯化合物中之碳酸酯鍵之比率變得更佳。 Further, when the carbonate compound represented by the formula (B) is a carbonate compound represented by the following formula (E) or (F), the stability of the carbonate compound is high, and the distance between the carbonate bonds is The ratio of carbonate bonds in the carbonate compound becomes better.

[化11] [11]

本實施形態之聚碳酸酯二醇組合物中所含之碳酸酯化合物之含量為0.05~5重量%。若該碳酸酯化合物之含量為0.05重量%以上，則可獲得平滑之塗膜，若該碳酸酯化合物之含量為5重量%以下，則可獲得具有耐化學品性之透明塗膜。若該碳酸酯化合物之含量為0.07~4重量%，則更佳，若為0.08~2重量%，則進而較佳。關於本實施形態之聚碳酸酯二醇組合物，由於碳酸酯化合物之含量少於通常之塑化劑之添加量，故而機械特性或耐化學品性等不會降低。本實施形態中所使用之碳酸酯化合物於聚碳酸酯二醇之製造中亦會產生，但較佳為以成為上述特定量之方式添加至聚碳酸酯二醇中。 The content of the carbonate compound 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 smooth coating film can be obtained, and when the content of the carbonate compound is 5% by weight or less, a clear coating film having chemical resistance can be obtained. More preferably, the content of the carbonate compound is from 0.07 to 4% by weight, more preferably from 0.08 to 2% by weight. In the polycarbonate diol composition of the present embodiment, since the content of the carbonate compound is less than the amount of the usual plasticizer, the mechanical properties, chemical resistance, and the like are not lowered. The carbonate compound used in the present embodiment is also produced in the production of polycarbonate diol, but it is preferably added to the polycarbonate diol so as to have the above specific amount.

本實施形態之聚碳酸酯二醇組合物亦可包含下述式(I)所表示之碳酸酯化合物、即，具有相同長度之亞甲基鏈且具有2個碳酸酯鍵之環狀化合物。若下述式(I)所表示之碳酸酯化合物與聚碳酸酯二醇一起存在特定量，則使用本實施形態之聚碳酸酯二醇組合物而獲得之聚胺基甲酸酯之流動起始溫度增高，不易發生黏連，並且樹脂表面之平滑性增高。又，若下述式(I)所表示之碳酸酯化合物與聚碳酸酯二醇一起存在特定量，則於使用本實施形態之聚碳酸酯二醇組合物作為塗料之構成材料之情形時，可獲得平滑且強韌之塗膜。於下述式(I)中之r為4~6之情形時，即，若碳酸酯鍵間之亞甲基之數量為4~6，則上述效果變得顯著，故而較佳。 The polycarbonate diol composition of the present embodiment may further contain a carbonate compound represented by the following formula (I), that is, a cyclic compound having a methylene chain of the same length and having two carbonate bonds. When the carbonate compound represented by the following formula (I) is present in a specific amount together with the polycarbonate diol, the flow initiation of the polyurethane obtained by using the polycarbonate diol composition of the present embodiment is started. The temperature is increased, adhesion is less likely to occur, and the smoothness of the surface of the resin is increased. Further, when the carbonate compound represented by the following formula (I) is present in a specific amount together with the polycarbonate diol, when the polycarbonate diol composition of the present embodiment is used as a constituent material of the coating material, A smooth and strong coating is obtained. In the case where r in the following formula (I) is 4 to 6, that is, when the number of methylene groups between the carbonate bonds is 4 to 6, the above effects are remarkable, and therefore it is preferable.

(式(I)中，r表示2~15之整數) (In the formula (I), r represents an integer from 2 to 15)

本實施形態之聚碳酸酯二醇組合物中所含之式(I)所表示之碳酸酯化合物的含量較佳為0.01~3重量%。本實施形態之聚碳酸酯二醇組合物中，若該碳酸酯化合物之含量為0.01重量%以上，則使用本實施形態之聚碳酸酯二醇組合物而獲得之聚胺基甲酸酯之流動起始溫度增高，不易發生黏連，並且樹脂表面之平滑性增高，若該碳酸酯化合物之含量為3重量%以下，則可獲得具有耐化學品性之透明塗膜。若該碳酸酯化合物之含量為0.01~0.5重量%，則更佳，若為0.01~0.05重量%，則進而較佳。 The content of the carbonate compound represented by the formula (I) contained in the polycarbonate diol composition of the present embodiment is preferably 0.01 to 3% by weight. In the polycarbonate diol composition of the present embodiment, when the content of the carbonate compound is 0.01% by weight or more, the flow of the polyurethane obtained by using the polycarbonate diol composition of the present embodiment is used. When the initial temperature is increased, adhesion is less likely to occur, and the smoothness of the surface of the resin is increased. When the content of the carbonate compound is 3% by weight or less, a transparent coating film having chemical resistance can be obtained. The content of the carbonate compound is preferably from 0.01 to 0.5% by weight, more preferably from 0.01 to 0.05% by weight.

再者，於本實施形態中，各碳酸酯化合物之含量可藉由下述實施例中所記載之方法而求出。 Further, in the present embodiment, the content of each carbonate compound can be determined by the method described in the following examples.

本實施形態之聚碳酸酯二醇組合物可包含下述式(J)所表示之碳酸酯多聚體、即，具有3~10之碳酸酯鍵之環狀化合物。 The polycarbonate diol composition of the present embodiment may contain a carbonate polymer represented by the following formula (J), that is, a cyclic compound having a carbonate bond of 3 to 10.

(式(J)中，l表示2~15之整數，p表示3~10之整數) (In the formula (J), l represents an integer from 2 to 15, and p represents an integer from 3 to 10)

於碳酸酯多聚體為下述式(H)所表示之碳酸酯化合物、即，具有3個碳酸酯鍵且具有2個不同長度之亞甲基鏈之環狀化合物之情形時，包含該環狀化合物之本實施形態之聚碳酸酯二醇組合物可不降低所獲得之聚胺基甲酸酯之強度而提高成型性，並且成為更平滑之塗膜，故而較佳。進而，碳酸酯多聚體為下述式(H)所表示之碳酸酯化合物， 於i及k係以4~6之整數表示之情形時，其效果更大。 When the carbonate polymer is a carbonate compound represented by the following formula (H), that is, a cyclic compound having three carbonate bonds and having two methylene chains of different lengths, the ring is included The polycarbonate diol composition of the present embodiment is preferred because it can improve the moldability without lowering the strength of the obtained polyurethane, and is a smoother coating film. Further, the carbonate polymer is a carbonate compound represented by the following formula (H). When i and k are represented by integers of 4 to 6, the effect is greater.

(式(H)中，i及k表示2~15之整數，且i≠k) (In the formula (H), i and k represent integers from 2 to 15, and i≠k)

本實施形態之聚碳酸酯二醇組合物中所含之碳酸酯多聚體之含量較佳為0.03~5重量%。 The content of the carbonate polymer contained in the polycarbonate diol composition of the present embodiment is preferably 0.03 to 5% by weight.

關於本實施形態之聚碳酸酯二醇組合物，若該碳酸酯多聚體之含量為0.03重量%以上，則所獲得之聚胺基甲酸酯之成型性變得更良好，若該碳酸酯多聚體之含量為5重量%以下，則可獲得具有良好之附著性、強韌且平滑之塗膜。若該碳酸酯多聚體之含量為0.03~3重量%，則較佳，若為0.03~0.5重量%，則更佳，若為0.03~0.2重量%，則進而較佳，若為0.03~0.1重量，則進一步較佳。 In the polycarbonate diol composition of the present embodiment, when the content of the carbonate polymer is 0.03% by weight or more, the moldability of the obtained polyurethane is further improved. When the content of the polymer is 5% by weight or less, a coating film having good adhesion, toughness, and smoothness can be obtained. The content of the carbonate polymer is preferably from 0.03 to 3% by weight, more preferably from 0.03 to 0.5% by weight, more preferably from 0.03 to 0.2% by weight, even more preferably from 0.03 to 0.1. The weight is further preferred.

再者，於本實施形態中，各碳酸酯多聚體之含量之定量可藉由下述實施例中所記載之碳酸酯化合物的定量方法而進行。 Further, in the present embodiment, the content of each carbonate multimer can be determined by a quantitative method of the carbonate compound described in the following examples.

本實施形態之聚碳酸酯二醇組合物亦可包含下述式(K)所表示之環狀醚化合物。 The polycarbonate diol composition of the present embodiment may further contain a cyclic ether compound represented by the following formula (K).

(式(K)中，q表示3~15之整數) (in the formula (K), q represents an integer from 3 to 15)

於該環狀醚化合物為四氫呋喃(式(K)中q為4之情形時)、四氫吡 喃(式(K)中q為5之情形時)、氧雜環庚烷(式(K)中q為6之情形時)之情形時，包含該環狀醚化合物之聚碳酸酯二醇組合物與溶劑之相溶性變得良好，因與利用式(B)所表示之碳酸酯化合物之效果之協同效應而成為更平滑之塗膜，故而較佳。 When the cyclic ether compound is tetrahydrofuran (when q is 4 in the formula (K)), tetrahydropyridin In the case of m (in the case where q is 5 in the formula (K)) or oxepane (in the case where q in the formula (K) is 6), the polycarbonate diol combination containing the cyclic ether compound The compatibility between the substance and the solvent is good, and it is preferable because it has a synergistic effect with the effect of the carbonate compound represented by the formula (B) to form a smoother coating film.

於本實施形態之聚碳酸酯二醇組合物中，環狀醚化合物之含量較佳為0.01~50ppm。於該環狀醚化合物之含量為0.01~5ppm之情形時，由於該環狀醚化合物亦不會自碳酸酯化合物中揮發，故而更佳，於0.01~0.5ppm之情形時，進而較佳。 In the polycarbonate diol composition of the present embodiment, the content of the cyclic ether compound is preferably from 0.01 to 50 ppm. When the content of the cyclic ether compound is 0.01 to 5 ppm, the cyclic ether compound is not preferably volatilized from the carbonate compound, and is more preferably in the case of 0.01 to 0.5 ppm.

於本實施形態之聚碳酸酯二醇組合物中，選自由四氫呋喃、四氫吡喃及氧雜環庚烷所組成之群中之至少1種環狀醚化合物之含量較佳為0.01~50ppm，更佳為0.01~5ppm，進而較佳為0.01~0.5ppm。又，於本實施形態之聚碳酸酯二醇組合物中，四氫呋喃、四氫吡喃及氧雜環庚烷之總含量較佳為0.01~50ppm，更佳為0.01~5ppm，進而較佳為0.01~0.5ppm。 In the polycarbonate diol composition of the present embodiment, the content of at least one cyclic ether compound selected from the group consisting of tetrahydrofuran, tetrahydropyran and oxepane is preferably 0.01 to 50 ppm. More preferably, it is 0.01 to 5 ppm, and further preferably 0.01 to 0.5 ppm. Further, in the polycarbonate diol composition of the present embodiment, the total content of tetrahydrofuran, tetrahydropyran and oxepane is preferably 0.01 to 50 ppm, more preferably 0.01 to 5 ppm, still more preferably 0.01. ~0.5ppm.

再者，於本實施形態中，環狀醚化合物之含量可藉由下述實施例中所記載之方法而求出。 Further, in the present embodiment, the content of the cyclic ether compound can be determined by the method described in the following examples.

為了賦予柔軟性，本實施形態中所使用之聚碳酸酯二醇亦可於其分子內包含下述式(G)之重複單元所表示之結構。 In order to impart flexibility, the polycarbonate diol used in the present embodiment may have a structure represented by a repeating unit of the following formula (G) in its molecule.

(式(G)中，R'表示伸烷基，於所有重複單元中，該伸烷基亦可存在2種以上。又，x表示2以上之整數) (In the formula (G), R' represents an alkylene group, and in any of the repeating units, the alkylene group may exist in two or more kinds. Further, x represents an integer of 2 or more)

於聚碳酸酯二醇之分子內導入上述式(G)之重複單元之方法並無 特別限定，例如可將聚氧乙二醇、聚氧乙烯丙二醇、聚氧乙烯四亞甲基二醇、聚氧四亞甲基二醇、聚氧丙二醇等醚系多元醇添加至原料二醇中，亦可於聚合中途加成環氧乙烷及/或環氧丙烷等環氧烷。 The method of introducing the repeating unit of the above formula (G) into the molecule of the polycarbonate diol is not In particular, for example, an ether polyol such as polyoxyethylene glycol, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, polyoxytetramethylene glycol or polyoxypropylene glycol may be added to the raw material diol. Further, an alkylene oxide such as ethylene oxide and/or propylene oxide may be added in the middle of the polymerization.

於本實施形態中所使用之聚碳酸酯二醇中，分子中之式(G)之重複單元之含量若為不對本發明造成影響之範圍，則並無特別限定，若其量增加，則存在所獲得之聚胺基甲酸酯之耐熱性或耐化學品性降低之情形。因此，於在聚碳酸酯二醇中導入式(G)所表示之重複單元之情形時，相對於式(A)所表示之碳酸酯之重複單元，式(G)所表示(具有源自醚之結構)之重複單元較佳為0.05~5莫耳%，更佳為0.05~3莫耳%。 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, and if the amount thereof is increased, it is present. The heat resistance or chemical resistance of the obtained polyurethane is lowered. Therefore, when a repeating unit represented by the formula (G) is introduced into the polycarbonate diol, it is represented by the formula (G) with respect to the repeating unit of the carbonate represented by the formula (A) (having an ether derived from The repeating unit of the structure) is preferably 0.05 to 5 mol%, more preferably 0.05 to 3 mol%.

本實施形態中所使用之聚碳酸酯二醇之數量平均分子量較佳為300~5000。若聚碳酸酯二醇之數量平均分子量為300以上，則可獲得塗膜之柔軟性。若聚碳酸酯二醇之數量平均分子量為5000以下，則於用作塗料之構成材料之情形時，塗料固形物成分濃度等亦不會受到限制，又，所獲得之聚胺基甲酸酯之成型加工性亦不會降低，故而較佳。聚碳酸酯二醇之數量平均分子量進而較佳為450~3000。 The number average molecular weight of the polycarbonate diol used in the present embodiment is preferably from 300 to 5,000. 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 5,000 or less, the concentration of the solid content of the coating material or the like is not limited when used as a constituent material of the coating material, and the obtained polyurethane is also used. It is preferred that the moldability is not lowered. The number average molecular weight of the polycarbonate diol is further preferably from 450 to 3,000.

再者，於本實施形態中，聚碳酸酯二醇之數量平均分子量可藉由下述實施例中所記載之方法而進行測定。 Further, in the present embodiment, the number average molecular weight of the polycarbonate diol can be measured by the method described in the following examples.

本實施形態中所使用之聚碳酸酯二醇中，末端OH基比率較佳為95.0~99.9%。若該末端OH基比率為99.9%以下，則會生成微細之高分子量凝膠等，塗膜表面之平滑性不會降低，若該末端OH基比率為95.0%以上，則進行塗膜之硬化，亦不會於塗膜表面殘留滑溜感，故而較佳。該末端OH基比率更佳為97.0~99.9%，進而較佳為98.0~99.9%。 In the polycarbonate diol used in the present embodiment, the terminal OH group ratio is preferably from 95.0 to 99.9%. When the ratio of the terminal OH group is 99.9% or less, a fine high molecular weight gel or the like is formed, and the smoothness of the surface of the coating film is not lowered. When the ratio of the terminal OH group is 95.0% or more, the coating film is cured. It is also preferable because the slipperiness is not left on the surface of the coating film. The terminal OH group ratio is more preferably from 97.0 to 99.9%, further preferably from 98.0 to 99.9%.

再者，於本實施形態中，末端OH基比率係以如下方式進行定義。於0.4kPa以下之壓力下將70g~100g之聚碳酸酯二醇加熱至160 ℃~200℃之溫度，並進行攪拌，而獲得相當於該聚碳酸酯二醇之約1~2重量%之餾分、即約1g(0.7~2g)之初始餾分。使所獲得之餾分溶解於約100g(95~105g)之乙醇中而以溶液之形式回收。係指對所回收之溶液進行氣相層析分析(以下亦稱為「GC(Gas Chromatography)分析」)，根據所獲得之層析圖之峰面積之值，藉由下述式(1)而計算出之末端OH基比率。再者，關於GC分析，係使用附有DB-WAX(美國J & W公司製造)(30m，膜厚0.25μm)作為管柱之氣相層析儀6890(美國惠普製造)，檢測器使用火焰游離偵檢器(FID，Flame Ionization Detector)而進行。關於管柱之升溫曲線，係設為於10℃/min之條件下自60℃升溫至250℃後，於該溫度下保持15分鐘之曲線。GC分析中之各波峰之鑑定係使用下述GC-MS裝置進行。GC裝置係使用附有DB-WAX(美國J & W公司製造)作為管柱之6890(美國惠普製造)。於GC裝置中，係於升溫速度10℃/min之條件下自初始溫度40℃升溫至220℃而進行測定。MS裝置使用Auto-mass SUN(日本JEOL製造)。於MS裝置中，於游離電壓(ionization voltage)：70eV、掃描範圍m/z=10~500、光電倍增管增益(photomultiplier gain)450V之條件下進行測定。 Further, in the present embodiment, the terminal OH group ratio is defined as follows. Heating 70g~100g of polycarbonate diol to 160 under the pressure of 0.4kPa The temperature is between ° C and 200 ° C and stirred to obtain an initial fraction corresponding to about 1 to 2% by weight of the polycarbonate diol, that is, about 1 g (0.7 to 2 g). The obtained fraction was dissolved in about 100 g (95 to 105 g) of ethanol to be recovered as a solution. Refers to gas chromatography analysis (hereinafter also referred to as "GC (Gas Chromatography) analysis) of the recovered solution, and according to the value of the peak area of the obtained chromatogram, by the following formula (1) Calculate the ratio of terminal OH groups. In addition, regarding the GC analysis, a gas chromatograph 6890 (manufactured by Hewlett-Packard Co., Ltd.) with DB-WAX (manufactured by J & W, USA) (30 m, film thickness: 0.25 μm) was used as a column, and the detector used a flame. The free detector (FID, Flame Ionization Detector) is performed. Regarding the temperature rise curve of the column, the temperature was raised from 60 ° C to 250 ° C under conditions of 10 ° C / min, and the curve was maintained at this temperature for 15 minutes. The identification of each peak in the GC analysis was carried out using the following GC-MS apparatus. The GC apparatus used was 6890 (manufactured by Hewlett Packard, USA) with DB-WAX (manufactured by J & W, USA) as a column. In the GC apparatus, the temperature was raised from the initial temperature of 40 ° C to 220 ° C under the conditions of a temperature increase rate of 10 ° C / min. The MS device used Auto-mass SUN (manufactured by JEOL, Japan). The measurement was carried out in an MS apparatus under the conditions of an ionization voltage of 70 eV, a scanning range of m/z of 10 to 500, and a photomultiplier gain of 450 V.

末端OH基比率(%)=B÷A×100 (1) Terminal OH group ratio (%) = B÷A × 100 (1)

A：包括二醇在內之醇類(乙醇除外)之峰面積之總和 A: the sum of the peak areas of alcohols (excluding ethanol) including diols

B：二醇之峰面積之總和 B: the sum of the peak areas of the diol

末端OH基比率係與OH基於聚碳酸酯二醇之全部末端基中所占之比率相應。即，如上述所示，若於0.4kPa以下之壓力下，將聚碳酸酯二醇加熱至160℃~200℃之溫度，則聚碳酸酯二醇之末端部分以醇類之形式餾出(參照下述式(a))。作為所餾出之醇類，並無特別限定，例如可列舉：原料中所使用之二醇、環己二醇或1,5-己二醇等原料中所含之雜質、甲醇等源自原料之碳酸酯化合物之單醇、於聚合中之副反應中所生成之具有不飽和烴之單醇。 The terminal OH group ratio corresponds to the ratio of OH based on the total terminal groups of the polycarbonate diol. That is, as described above, when the polycarbonate diol is heated to a temperature of from 160 ° C to 200 ° C under a pressure of 0.4 kPa or less, the terminal portion of the polycarbonate diol is distilled off as an alcohol (refer to The following formula (a)). The alcohol to be distilled is not particularly limited, and examples thereof include impurities contained in raw materials such as diol, cyclohexanediol, and 1,5-hexanediol used in the raw materials, and methanol derived from raw materials. a monool of a carbonate compound, a monool having an unsaturated hydrocarbon formed in a side reaction in the polymerization.

(式(a)中，X為-R2-OH或-R2，R1及R2表示烴) (In the formula (a), X is -R 2 -OH or -R 2 , and R 1 and R 2 represent a hydrocarbon)

該餾分中之全部醇類中之二醇之比率為末端OH基比率。 The ratio of the diol in all of the alcohols in the fraction is the terminal OH group ratio.

於本實施形態之聚碳酸酯二醇組合物中，水分量較佳為1~500ppm。若本實施形態之聚碳酸酯二醇組合物之水分量為500ppm以下，則藉由水與異氰酸酯之反應亦不會發生白濁，可獲得平滑之塗膜，故而較佳。又，若本實施形態之聚碳酸酯二醇組合物之水分量為1ppm以上，則可使碳酸酯化合物容易地分散於聚碳酸酯二醇中，故而較佳。若該水分量為5~250ppm，則其效果變得更明顯，若為10~150ppm，則進而較佳。 In the polycarbonate diol composition of the present embodiment, the moisture content is preferably from 1 to 500 ppm. When the water content of the polycarbonate diol composition of the present embodiment is 500 ppm or less, it is preferred that the smooth coating film can be obtained by the reaction of water and isocyanate without causing white turbidity. Further, when the water content of the polycarbonate diol composition of the present embodiment is 1 ppm or more, the carbonate compound can be easily dispersed in the polycarbonate diol, which is preferable. If the water content is 5 to 250 ppm, the effect becomes more conspicuous, and if it is 10 to 150 ppm, it is further preferable.

再者，於本實施形態中，聚碳酸酯二醇組合物之水分量可藉由下述實施例中所記載之方法而求出。 Further, in the present embodiment, the moisture content of the polycarbonate diol composition can be determined by the method described in the following examples.

本實施形態之聚碳酸酯二醇組合物之色值較佳為5~100。若本實施形態之聚碳酸酯二醇組合物之色值為100以下，則於塗膜中未見著色，故而較佳。又，若本實施形態之聚碳酸酯二醇組合物之色值為5以上，則聚碳酸酯二醇之生產條件不會受到制約而較佳。若該色值為5~50，則其效果變得更明顯，若為5~30，則進而較佳。 The color ratio of the polycarbonate diol composition of the present embodiment is preferably from 5 to 100. When the color value of the polycarbonate diol composition of the present embodiment is 100 or less, coloring is not observed in the coating film, which is preferable. Moreover, when the color value of the polycarbonate diol composition of this embodiment is 5 or more, the production conditions of the polycarbonate diol are not restricted, and it is preferable. If the color value is 5 to 50, the effect becomes more conspicuous, and if it is 5 to 30, it is further preferable.

作為獲得色值為上述範圍內之聚碳酸酯二醇組合物之方法，並無特別限定，例如可列舉於200℃以下、較佳為170℃以下之溫度下進行聚合之方法。 The method for obtaining the polycarbonate diol composition in the above range is not particularly limited, and examples thereof include a method of performing polymerization at a temperature of 200 ° C or lower, preferably 170 ° C or lower.

再者，於本實施形態中，聚碳酸酯二醇組合物之色值可藉由確定下述實施例中所記載之聚碳酸酯二醇組合物的色值而求出。 Further, in the present embodiment, the color value of the polycarbonate diol composition can be determined by determining the color value of the polycarbonate diol composition described in the following examples.

本實施形態中所使用之聚碳酸酯二醇之製造方法並無特別限定。本實施形態中所使用之聚碳酸酯二醇例如可藉由Schnell編著之聚合物評論(Polymer Reviews)第9卷，p9~20(1994年)中所記載之各種方法而製造。 The method for producing the polycarbonate diol used in the present embodiment is not particularly limited. The polycarbonate diol used in the present embodiment can be produced, for example, by various methods described in Polymer Reviews, Vol. 9, p9-20 (1994), edited by Schnell.

本實施形態中所使用之聚碳酸酯二醇並無特別限定，例如係以二醇與碳酸酯為原料而製造。 The polycarbonate diol used in the present embodiment is not particularly limited, and is produced, for example, by using a diol and a carbonate as a raw material.

本實施形態中所使用之二醇並無特別限定，例如可列舉：乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇、1,13-十三烷二醇、1,14-十四烷二醇、1,15-十五烷二醇等不具有側鏈之二醇；2-甲基-1,8-辛二醇、2-乙基-1,6-己二醇、2-甲基-1,3-丙二醇、3-甲基-1,5-戊二醇、2,4-二甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇等具有側鏈之二醇；1,4-環己烷二甲醇、2-雙(4-羥基環己基)-丙烷等環狀二醇。該二醇亦可使用一種或兩種以上作為聚碳酸酯二醇之原料。於自不具有側鏈之二醇中，使用一種或兩種以上之二醇作為聚碳酸酯二醇之原料之情形時，塗膜之耐化學品性或機械強度增高，故而較佳。於使用選自由1,4-丁二醇、1,5-戊二醇及1,6-己二醇所組成之群中之兩種二醇作為聚碳酸酯二醇的原料之情形時更佳。於使用1,5-戊二醇、1,6-己二醇作為二醇原料之情形時，進而較佳。 The diol used in the present embodiment is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-tweldium Alkane having no side chain such as alkanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 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-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1, a diol having a side chain such as 3-propanediol; a cyclic diol such as 1,4-cyclohexanedimethanol or 2-bis(4-hydroxycyclohexyl)-propane. One or two or more kinds of the diol may be used as a raw material of the polycarbonate diol. In the case where one or two or more kinds of diols are used as the raw material of the polycarbonate diol from the diol having no side chain, the chemical resistance or mechanical strength of the coating film is increased, which is preferable. More preferably when two diols selected from the group consisting of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are used as a raw material of the polycarbonate diol . When using 1,5-pentanediol and 1,6-hexanediol as a diol raw material, it is further preferable.

於本實施形態中所使用之聚碳酸酯二醇之製造中，於使用兩種以上之二醇作為原料之情形時，該等原料之比並無特別限定。較佳為以使所獲得之聚碳酸酯二醇於常溫下呈液狀之方式設定所使用的原料之比。於使用2種二醇作為原料之情形時，較佳為以莫耳比計於20/80~80/20之間設定添加量。若為該範圍，則所獲得之聚碳酸酯二醇呈液狀。若設為30/70~70/30，則進而較佳，若設為40/60~60/40，則 於0℃以下亦呈液狀，故而更佳。 In the production of the polycarbonate diol used in the present embodiment, when two or more kinds of diols are used as a raw material, the ratio of the raw materials is not particularly limited. It is preferred to set the ratio of the raw materials to be used so that the obtained polycarbonate diol is liquid at normal temperature. When two kinds of diols are used as a raw material, it is preferred to set the addition amount between 20/80 and 80/20 in terms of a molar ratio. If it is this range, the polycarbonate diol obtained is liquid. If it is set to 30/70~70/30, it is further preferable. If it is set to 40/60~60/40, then It is also liquid below 0 ° C, so it is more preferable.

進而，於不損及本實施形態中所使用之聚碳酸酯二醇之性能之範圍內，亦可使用1分子中具有3個以上羥基之化合物、例如三羥甲基乙烷、三羥甲基丙烷、己三醇、季戊四醇等作為聚碳酸酯二醇之原料。若過量使用該1分子中具有3個以上羥基之化合物作為聚碳酸酯二醇之原料，則會於聚碳酸酯之聚合反應中進行交聯而引起凝膠化。因此，於使用1分子中具有3個以上羥基之化合物作為聚碳酸酯二醇之原料之情形時，該化合物相對於用作聚碳酸酯二醇之原料之二醇之合計莫耳數，較佳為設為0.1~5莫耳%。該比率更佳為0.1~1莫耳%。 Further, a compound having three or more hydroxyl groups in one molecule, such as trimethylolethane or trimethylol, may be used insofar as the performance of the polycarbonate diol used in the present embodiment is not impaired. Propane, hexanetriol, pentaerythritol or the like is used as a raw material of the polycarbonate diol. When a compound having three or more hydroxyl groups in the above molecule is used in excess as a raw material of the polycarbonate diol, crosslinking occurs in the polymerization reaction of the polycarbonate to cause gelation. Therefore, when a compound having three or more hydroxyl groups in one molecule is used as a raw material of the polycarbonate diol, the total number of moles of the compound relative to the diol used as a raw material of the polycarbonate diol is preferably It is set to 0.1 to 5 mol%. The ratio is more preferably 0.1 to 1 mol%.

於本實施形態中所使用之聚碳酸酯二醇之製造中，原料之碳酸酯並無特別限定，例如可列舉：碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯等碳酸二烷基酯；碳酸二苯酯等碳酸二芳酯；碳酸乙二酯、碳酸三亞甲酯、碳酸1,2-丙二酯、碳酸1,2-丁二酯、碳酸1,3-丁二酯、碳酸1,2-戊二酯等碳酸伸烷酯等。可自該等之中使用1種或2種以上之碳酸酯作為聚碳酸酯二醇之原料。就容易獲取性或聚合反應之條件設定之容易性之觀點而言，較佳為使用碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸二丁酯、碳酸乙二酯。 In the production of the polycarbonate diol used in the present embodiment, the carbonate of the raw material is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate. Dialkyl carbonate; diaryl carbonate such as diphenyl carbonate; ethylene carbonate, trimethylene carbonate, 1,2-propylene diester, 1,2-butyl dicarbonate, 1,3-butyl carbonate A alkyl ester such as a diester or a 1,2-pentane dicarbonate. One or two or more kinds of carbonates can be used as a raw material of the polycarbonate diol. From the viewpoint of easiness of availability or ease of setting conditions of the polymerization reaction, it is preferred to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate or ethylene carbonate.

於本實施形態中所使用之聚碳酸酯二醇之製造中，較佳為添加觸媒。作為該觸媒，並無特別限定，例如可列舉：鋰、鈉、鉀等鹼金屬、鎂、鈣、鍶、鋇等鹼土金屬之醇化物、氫化物、氧化物、醯胺、碳酸鹽、氫氧化物、含氮之硼酸鹽、進而有機酸之鹼性鹼金屬鹽及鹼土金屬鹽。又，作為上述觸媒，並無特別限定，例如可列舉：鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、鋯、鈮、鉬、釕、銠、鈀、銀、銦、錫、銻、鎢、錸、鋨、銥、鉑、金、鉈、鉛、鉍、鐿之金屬、鹽、烷氧化物、有機化合物。可自該等中選擇1種或複數種觸媒而使用。於自鈉、鉀、鎂、鉀、鈦、鋯、錫、鉛、鐿之金屬、 鹽、烷氧化物、有機化合物中使用1種或複數種觸媒之情形時，良好地進行聚碳酸酯二醇之聚合，對使用所獲得之聚碳酸酯二醇之胺基甲酸酯反應之影響亦較少，故而較佳。於使用鈦、鐿、錫、鋯作為上述觸媒之情形時，進而較佳。 In the production of the polycarbonate diol used in the present embodiment, it is preferred to add a catalyst. The catalyst is not particularly limited, and examples thereof include alkali metals such as lithium, sodium, and potassium, and alcoholic compounds, hydrides, oxides, guanamines, carbonates, and hydrogens of alkaline earth metals such as magnesium, calcium, barium, and strontium. An oxide, a nitrogen-containing borate, a basic alkali metal salt of an organic acid, and an alkaline earth metal salt. Further, the catalyst is not particularly limited, and examples thereof include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, lanthanum, zirconium, hafnium, molybdenum, niobium, tantalum, and the like. Palladium, silver, indium, tin, antimony, tungsten, antimony, bismuth, antimony, platinum, gold, antimony, lead, antimony, antimony metal, salt, alkoxide, organic compound. One or a plurality of catalysts can be selected from these. From sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead, antimony, When one or a plurality of catalysts are used for the salt, the alkoxide, and the organic compound, the polymerization of the polycarbonate diol is favorably carried out, and the urethane of the obtained polycarbonate diol is reacted. The effect is also less, so it is better. When titanium, tantalum, tin, or zirconium is used as the above-mentioned catalyst, it is further preferable.

本實施形態之聚碳酸酯二醇組合物中，以使用ICP測得之金屬元素之量計，亦可含有0.0001~0.02重量%之上述觸媒。若該觸媒之含量為上述範圍，則良好地進行聚碳酸酯二醇之聚合，對使用所獲得之聚碳酸酯二醇組合物之胺基甲酸酯反應之影響亦較少。於該觸媒之含量為0.0005~0.01重量%之情形時更佳。 In the polycarbonate diol composition of the present embodiment, the catalyst may be contained in an amount of 0.0001 to 0.02% by weight based on the amount of the metal element measured by ICP. When the content of the catalyst is in the above range, the polymerization of the polycarbonate diol is favorably performed, and the effect of the urethane reaction using the obtained polycarbonate diol composition is also small. It is more preferable when the content of the catalyst is 0.0005 to 0.01% by weight.

關於本實施形態之聚碳酸酯二醇組合物，藉由ICP進行測定時之選自由鈦、鐿、錫及鋯所組成之群中的至少1種金屬元素之含量較佳為0.0001~0.02重量%，更佳為0.0005~0.01重量%。又，關於本實施形態之聚碳酸酯二醇組合物，藉由ICP進行測定時之鈦、鐿、錫及鋯之總含量較佳為0.0001~0.02重量%，更佳為0.0005~0.01重量%。 In the polycarbonate diol composition of the present embodiment, the content of at least one metal element selected from the group consisting of titanium, tantalum, tin, and zirconium when measured by ICP is preferably 0.0001 to 0.02% by weight. More preferably, it is 0.0005 to 0.01% by weight. Further, in the polycarbonate diol composition of the present embodiment, the total content of titanium, tantalum, tin and zirconium when measured by ICP is preferably 0.0001 to 0.02% by weight, more preferably 0.0005 to 0.01% by weight.

再者，於本實施形態中，聚碳酸酯二醇組合物中之金屬元素之含量可藉由下述實施例中所記載之方法而進行測定。 Further, in the present embodiment, the content of the metal element in the polycarbonate diol composition can be measured by the method described in the following examples.

關於本實施形態中所使用之聚碳酸酯二醇，例如，於用作聚胺基甲酸酯之原料之情形時，較佳為利用磷化合物對聚碳酸酯二醇之製造中所使用之觸媒進行處理。作為磷化合物，並無特別限定，例如可列舉：磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸二-2-乙基己酯、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯基二苯酯等磷酸三酯；酸式磷酸甲酯、酸式磷酸乙酯、酸式磷酸丙酯、酸式磷酸異丙酯、酸式磷酸丁酯、酸式磷酸月桂酯、酸式磷酸硬脂酯、酸式磷酸2-乙基己酯、酸式磷酸異癸酯、酸式磷酸丁氧基乙酯、酸式磷酸油酯、酸式磷酸二十四基酯、酸式磷酸乙二醇酯、2-羥乙基甲基丙烯酸酯酸式磷酸酯、磷酸二丁酯、磷酸單丁酯、磷酸單異癸酯、磷酸雙(2-乙基己基) 酯等酸式磷酸酯；亞磷酸三苯酯、亞磷酸三壬基苯酯、亞磷酸三甲苯酯、亞磷酸三乙酯、亞磷酸三(2-乙基己基)酯、亞磷酸十三烷基酯、亞磷酸三月桂酯、亞磷酸三(十三烷基)酯、亞磷酸三油酯、亞磷酸二苯基單(2-乙基己基)酯、亞磷酸二苯基單癸酯、亞磷酸二苯基(單癸基)酯、亞磷酸三月桂酯、二乙基氫亞磷酸酯、雙(2-乙基己基)氫亞磷酸酯、二月桂基氫亞磷酸酯、二油基氫亞磷酸酯、二苯基氫亞磷酸酯、四苯基二丙二醇二亞磷酸酯、雙(癸基)季戊四醇二亞磷酸酯、亞磷酸三硬脂酯、二硬脂基季戊四醇二亞磷酸酯、亞磷酸三(2,4-二-第三丁基苯基)酯等亞磷酸酯類；進而，磷酸、亞磷酸、次亞磷酸等。 The polycarbonate diol used in the present embodiment is preferably used as a raw material for a polyurethane, for example, in the use of a phosphorus compound for the production of a polycarbonate diol. The media is processed. The phosphorus compound is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and toluene phosphate. Phosphate triester such as diphenyl ester; acid methyl phosphate, acid ethyl phosphate, acid propyl phosphate, acid isopropyl phosphate, acid butyl phosphate, acid lauryl phosphate, acid phosphate Lipid ester, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, acid acid phosphate, tetracosyl acid phosphate, acid acid ethylene glycol Ester, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate Acid phosphate such as ester; triphenyl phosphite, tridecyl phenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecane phosphite a base ester, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, Diphenyl(monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl)hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl Hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis(indenyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite a phosphite such as tris(2,4-di-tert-butylphenyl)phosphite; further, phosphoric acid, phosphorous acid, hypophosphorous acid, or the like.

關於本實施形態中所使用之聚碳酸酯二醇組合物中所含之磷化合物之量，以使用ICP測定時之磷元素之含量計，較佳為0.0001~0.02重量%。關於本實施形態之聚碳酸酯二醇組合物，若磷化合物之量為上述範圍，則例如於用作聚胺基甲酸酯之原料之情形時，於該聚胺基甲酸酯之製造反應中，可幾乎消除聚碳酸酯二醇製造中所使用之觸媒之影響，又，磷化合物對聚胺基甲酸酯之製造反應或反應產物之物性造成影響之情形亦較少。進而，於在聚碳酸酯二醇中存在酯交換反應觸媒之情形時，可抑制聚碳酸酯二醇組合物中所存在之碳酸酯化合物之分解。於本實施形態之聚碳酸酯二醇組合物中，藉由ICP進行測定時之磷元素之含量進而較佳為0.0005~0.01重量%。 The amount of the phosphorus compound contained in the polycarbonate diol composition used in the present embodiment is preferably 0.0001 to 0.02% by weight based on the content of the phosphorus element in the measurement by ICP. In the polycarbonate diol composition of the present embodiment, when the amount of the phosphorus compound is in the above range, for example, when it is used as a raw material of a polyurethane, the production reaction of the polyurethane is carried out. Among them, the influence of the catalyst used in the production of the polycarbonate diol can be almost eliminated, and the phosphorus compound has little influence on the production reaction of the polyurethane or the physical properties of the reaction product. Further, in the case where a transesterification catalyst is present in the polycarbonate diol, decomposition of the carbonate compound present in the polycarbonate diol composition can be suppressed. In the polycarbonate diol composition of the present embodiment, the content of the phosphorus element in the measurement by ICP is more preferably 0.0005 to 0.01% by weight.

將本實施形態中所使用之聚碳酸酯二醇之製造方法之具體例示於以下。本實施形態中所使用之聚碳酸酯二醇之製造並無特別限定，例如可分成2階段進行。對二醇與碳酸酯以莫耳比(二醇：碳酸酯)計，例如以20：1~1：10之比例、較佳為以10：1~1：2之比例進行溶混，於常壓或減壓下，於100~250℃下進行第1階段之反應。於使用碳酸二甲酯作為碳酸酯之情形時，可以與碳酸二甲酯之混合物之形式去除所生成之甲醇，而獲得低分子量聚碳酸酯二醇。於使用碳酸二 乙酯作為碳酸酯之情形時，可以與碳酸二乙酯之混合物之形式去除所生成之乙醇而獲得低分子量聚碳酸酯二醇。又，於使用碳酸乙二酯作為碳酸酯之情形時，可以與碳酸乙二酯之混合物之形式去除所生成之乙醇而獲得低分子量聚碳酸酯二醇。繼而，第2階段之反應係如下反應，即，於減壓下，於160~250℃下將上述第1階段之反應產物加熱，將未反應之二醇與碳酸酯去除，並使低分子量聚碳酸酯二醇縮合，而獲得特定分子量之聚碳酸酯二醇。於100~150℃之溫度下開始第1階段之反應，於反應起始溫度下進行5小時以上之反應後，一面以每1小時15℃以下之速度進行升溫，一面於120~170℃之溫度下，於15kPa以下之壓力下進行第2階段之反應，藉此反應中所生成之碳酸酯化合物之量可抑制為較低，藉由在所獲得之聚碳酸酯二醇中添加特定量之碳酸酯化合物，可對聚碳酸酯二醇中所含之碳酸酯化合物控制量，故而更佳。又，關於本實施形態中所使用之聚碳酸酯二醇之末端OH基比率，可藉由自原料中之雜質、溫度或時間等製造條件、進而，於使用碳酸二烷基酯及/或碳酸二芳基酯作為原料之碳酸酯之情形時，自原料中之二醇與碳酸酯之添加比等條件中選擇1種方法，或適當組合而加以調整。於使用碳酸二烷基酯及/或碳酸二芳基酯作為原料之碳酸酯之情形時，若使之與目標之聚碳酸酯二醇之分子量相應，以化學計量或接近其之比例添加作為原料之二醇與碳酸酯並使之反應，則多數情況下會於聚碳酸酯二醇之末端殘留源自碳酸酯之烷基或芳基。因此，例如藉由將相對於碳酸酯之二醇之量設為化學計量之1.01~1.10倍，聚碳酸酯二醇之末端烷基或末端芳基減少，可增加末端羥基。進而，藉由副反應，聚碳酸酯二醇之末端成為乙烯基，或例如於使用碳酸二甲酯作為碳酸酯之情形時，成為甲基酯或甲基醚。通常，副反應係反應溫度越高，反應時間越長，越容易發生。 Specific examples of the method for producing the polycarbonate diol used in the present embodiment are shown below. The production of the polycarbonate diol used in the present embodiment is not particularly limited, and can be carried out, for example, in two stages. For example, the diol and the carbonate are miscible in a ratio of 20:1 to 1:10, preferably in a ratio of 10:1 to 1:2, in terms of molar ratio (diol: carbonate). The first stage reaction is carried out at 100 to 250 ° C under pressure or reduced pressure. In the case where dimethyl carbonate is used as the carbonate, the methanol formed can be removed in the form of a mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate diol. For the use of carbonic acid In the case of ethyl ester as the carbonate, the produced ethanol can be removed in the form of a mixture with diethyl carbonate to obtain a low molecular weight polycarbonate diol. Further, in the case where ethylene carbonate is used as the carbonate, the produced ethanol can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate diol. Then, the second stage reaction is a reaction in which the reaction product of the first stage is heated at 160 to 250 ° C under reduced pressure to remove unreacted diol and carbonate, and to make low molecular weight poly The carbonate diol is condensed to obtain a polycarbonate diol of a specific molecular weight. The first stage reaction is started at a temperature of 100 to 150 ° C, and after the reaction is carried out for 5 hours or more at the reaction starting temperature, the temperature is raised at a rate of 15 ° C or less per hour, and the temperature is 120 to 170 ° C. The second stage reaction is carried out at a pressure of 15 kPa or less, whereby the amount of the carbonate compound formed in the reaction can be suppressed to be low, by adding a specific amount of carbonic acid to the obtained polycarbonate diol. The ester compound is more preferably controlled by the amount of the carbonate compound contained in the polycarbonate diol. Further, the terminal OH group ratio of the polycarbonate diol used in the present embodiment can be produced by using impurities such as impurities, temperature or time in the raw material, and further, using dialkyl carbonate and/or carbonic acid. In the case where the diaryl ester is used as a carbonate of a raw material, one method is selected from the conditions such as the ratio of addition of the diol to the carbonate in the raw material, or the like, or an appropriate combination. In the case of using a carbonate of a dialkyl carbonate and/or a diaryl carbonate as a raw material, if it is made to correspond to the molecular weight of the target polycarbonate diol, it is added as a raw material at a stoichiometric or close ratio. The diol and the carbonate react and react, and in many cases, an alkyl group or an aryl group derived from a carbonate remains at the terminal of the polycarbonate diol. Therefore, for example, by setting the amount of the diol relative to the carbonate to 1.01 to 1.10 times the stoichiometric amount, the terminal alkyl group or the terminal aryl group of the polycarbonate diol is reduced, and the terminal hydroxyl group can be increased. Further, by the side reaction, the terminal of the polycarbonate diol becomes a vinyl group, or, for example, when dimethyl carbonate is used as the carbonate, it is a methyl ester or a methyl ether. Generally, the higher the reaction temperature of the side reaction system, the longer the reaction time is, and the more likely it is to occur.

<用途> <Use>

關於本實施形態之聚碳酸酯二醇組合物，作為塗料或接著劑之構成材料，又，作為聚胺基甲酸酯或熱塑性彈性體之原料，可進而用於聚酯或聚醯亞胺之改質劑等用途。尤其是本實施形態之聚碳酸酯二醇組合物於用作塗料之構成材料之情形時，可獲得表面平滑且強度、耐化學品性等性能之平衡性良好之塗膜。又，本實施形態之聚碳酸酯二醇組合物於用作聚胺基甲酸酯或熱塑性彈性體之原料之情形時，可獲得表面平滑、強韌且耐化學品性優異之聚胺基甲酸酯或熱塑性彈性體。 The polycarbonate diol composition of the present embodiment can be further used as a constituent material of a coating material or an adhesive, or as a raw material of a polyurethane or a thermoplastic elastomer, and can be further used for polyester or polyimine. Modifiers and other uses. 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 a smooth surface and excellent balance of properties such as strength and chemical resistance can be obtained. Further, when the polycarbonate diol composition of the present embodiment is used as a raw material of a polyurethane or a thermoplastic elastomer, a polyamine base having a smooth surface, strong toughness, and excellent chemical resistance can be obtained. An acid ester or a thermoplastic elastomer.

本實施形態之熱塑性聚胺基甲酸酯可使用上述聚碳酸酯二醇組合物與有機聚異氰酸酯而獲得。 The thermoplastic polyurethane of the present embodiment can be obtained by using the above polycarbonate diol composition and an organic polyisocyanate.

又，本實施形態之塗佈組合物包含上述聚碳酸酯二醇組合物與有機聚異氰酸酯。 Further, the coating composition of the present embodiment comprises the above polycarbonate diol composition and an organic polyisocyanate.

進而，較佳為本實施形態之塗佈組合物包含使上述聚碳酸酯二醇組合物與有機聚異氰酸酯反應而獲得之胺基甲酸酯預聚物，且該胺基甲酸酯預聚物具有異氰酸酯末端基。 Further, it is preferable that the coating composition of the present embodiment contains a urethane prepolymer obtained by reacting the polycarbonate diol composition with an organic polyisocyanate, and the urethane prepolymer Has an isocyanate terminal group.

又，進而，本實施形態之塗佈組合物更佳為包含使上述聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯樹脂，進而較佳為包含使上述聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯之水系塗佈組合物。 Further, the coating composition of the present embodiment more preferably contains a polyurethane resin obtained by reacting the polycarbonate diol composition, the organic polyisocyanate, and a chain extender, and further preferably contains An aqueous coating composition of a polyurethane obtained by reacting the above polycarbonate diol composition, an organic polyisocyanate, and a chain extender.

作為所使用之有機聚異氰酸酯，並無特別限定，例如可列舉：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、及其混合物(TDI(Toluene Diisocyanate，甲苯二異氰酸酯))、粗製TDI、二苯基甲烷-4,4'-二異氰酸酯(MDI，Diphenyl-methane-4,4'-diisocyanate)、粗製MDI、萘-1,5-二異氰酸酯(NDI，Naphthalene-1,5-diisocyanate)、3,3'-二甲基-4,4'-伸聯苯基二異氰酸酯、聚亞甲基聚苯基異氰酸酯、苯二甲基二異氰酸酯(XDI，Xylene Diisocyanate)、伸苯基二異氰酸酯等公知之芳香族二異 氰酸酯、4,4'-亞甲基雙環己基二異氰酸酯(氫化MDI)、六亞甲基二異氰酸酯(HMDI，Hexamethylene Diisocyanate)、異佛爾酮二異氰酸酯(IPDI，Isophorone diisocyanate)、環己烷二異氰酸酯(氫化XDI)等公知之脂肪族二異氰酸酯、及該等異氰酸酯類之異氰尿酸酯化改性品、碳二醯亞胺化改性品、縮二脲化改性品等。該等有機聚異氰酸酯可單獨使用，亦可組合使用兩種以上。又，該等有機聚異氰酸酯亦可利用封端劑掩蔽異氰酸酯基而使用。 The organic polyisocyanate to be used is not particularly limited, and examples thereof include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and a mixture thereof (TDI (Toluene Diisocyanate, toluene diisocyanate)), and a crude TDI. , Diphenyl-methane-4, 4'-diisocyanate, crude MDI, naphthalene-1,5-diisocyanate (NDI, Naphthalene-1, 5-diisocyanate) , 3,3'-dimethyl-4,4'-extended biphenyl diisocyanate, polymethylene polyphenyl isocyanate, benzodimethyl diisocyanate (XDI, Xylene Diisocyanate), phenyl diisocyanate, etc. Aromatic divalent Cyanate ester, 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI, Hexamethylene Diisocyanate), isophorone diisocyanate (IPDI, Isophorone diisocyanate), cyclohexane A known aliphatic diisocyanate such as a diisocyanate (hydrogenated XDI), an isocyanurate modified product of the isocyanate, a carbon diimide modified product, a biuret modified product, and the like. These organic polyisocyanates may be used singly or in combination of two or more. Further, these organic polyisocyanates may also be used by masking an isocyanate group with a blocking agent.

又，於聚碳酸酯二醇組合物與有機聚異氰酸酯之反應中，視需要可使用鏈伸長劑作為共聚成分。作為鏈伸長劑，並無特別限定，例如可使用聚胺基甲酸酯業界中之常用之鏈伸長劑、即水、低分子多元醇、聚胺等。作為鏈伸長劑之例，並無特別限定，例如可列舉：乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,10-癸二醇、1,1-環己烷二甲醇、1,4-環己烷二甲醇、苯二甲醇、雙(對羥基)二苯基、雙(對羥苯基)丙烷等低分子多元醇，乙二胺、六亞甲基二胺、異佛爾酮二胺、苯二甲基二胺、二苯基二胺、二胺基二苯基甲烷等聚胺。該等鏈伸長劑可單獨使用，亦可組合使用兩種以上。 Further, in the reaction between the polycarbonate diol composition and the organic polyisocyanate, a chain extender may be used as a copolymerization component as needed. 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 polyol, a polyamine or the like can be used. The chain extender is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, benzenedimethanol, bis(p-hydroxy)diphenyl, bis(p-hydroxyl Low molecular polyol such as phenyl)propane, polyethylenediamine, hexamethylenediamine, isophoronediamine, dimethylenediamine, diphenyldiamine, diaminodiphenylmethane, etc. amine. These chain extenders may be used singly or in combination of two or more.

作為製造本實施形態之塗佈組合物(塗料)之方法，可使用業界中公知之製造方法。例如可製造：於即將塗敷前將由上述聚碳酸酯二醇組合物獲得之塗料主劑與包含有機聚異氰酸酯之硬化劑混合之二液型溶劑系塗佈組合物；包含使上述聚碳酸酯二醇組合物與有機聚異氰酸酯反應而獲得之具有異氰酸酯末端基之胺基甲酸酯預聚物之一液型溶劑系塗佈組合物；包含使上述聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯樹脂之一液型溶劑系塗佈組合物；或一液型水系塗佈組合物。 As a method of producing the coating composition (coating) of the present embodiment, a production method known in the art can be used. For example, a two-liquid solvent-based coating composition in which a coating base agent obtained from the above polycarbonate diol composition and a hardener containing an organic polyisocyanate are mixed before being applied; a liquid type solvent-based coating composition of a urethane prepolymer having an isocyanate terminal group obtained by reacting an alcohol composition with an organic polyisocyanate; comprising the above polycarbonate diol composition, an organic polyisocyanate, and One of the polyurethane resin resins obtained by the reaction of the chain extender is a liquid type solvent-based coating composition; or a one-liquid aqueous coating composition.

於本實施形態之塗佈組合物(塗料)中，例如可根據各種用途而添加硬化促進劑(觸媒)、填充劑、分散劑、阻燃劑、染料、有機或無機 顏料、脫模劑、流動性調整劑、塑化劑、抗氧化劑、紫外線吸收劑、光穩定劑、消泡劑、調平劑、著色劑、溶劑等。 In the coating composition (coating material) of the present embodiment, for example, a curing accelerator (catalyst), a filler, a dispersing agent, a flame retardant, a dye, an organic or inorganic agent may be added according to various uses. A pigment, a mold release agent, a fluidity adjuster, a plasticizer, an antioxidant, a UV absorber, a light stabilizer, an antifoaming agent, a leveling agent, a colorant, a solvent, and the like.

作為本實施形態之塗佈組合物(塗料)之溶劑，並無特別限定，例如可列舉：二甲基甲醯胺、二乙基甲醯胺、二甲基乙醯胺、二甲基亞碸、四氫呋喃、丙酮、甲基乙基酮、甲基異丁基酮、二烷、環己酮、苯、甲苯、二甲苯、乙基溶纖素、乙酸乙酯、乙酸丁酯、乙醇、異丙醇、正丁醇、水等。該等溶劑可使用一種或混合使用複數種。 The solvent of the coating composition (coating material) of the present embodiment is not particularly limited, and examples thereof include dimethylformamide, diethylformamide, dimethylacetamide, and dimethylammonium. , tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, two Alkane, cyclohexanone, benzene, toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol, n-butanol, water, and the like. These solvents may be used alone or in combination of plural kinds.

作為製造本實施形態之熱塑性聚胺基甲酸酯之方法，並無特別限定，可使用聚胺基甲酸酯業界中公知之聚胺基甲酸酯化反應之技術。例如，藉由使上述聚碳酸酯二醇組合物與有機聚異氰酸酯於大氣壓下於常溫至200℃下進行反應，可製造熱塑性聚胺基甲酸酯。於使用鏈延長劑之情形時，可自反應之最初起預先添加，亦可自反應之中途添加。關於本實施形態之熱塑性聚胺基甲酸酯之製造方法，例如可參照美國專利第5,070,173號。 The method for producing the thermoplastic polyurethane of the present embodiment is not particularly limited, and a technique known as a polyurethane reaction in the polyurethane industry can be used. For example, a thermoplastic polyurethane can be produced by reacting the above polycarbonate diol composition with an organic polyisocyanate under normal pressure to 200 ° C under atmospheric pressure. In the case of using a chain extender, it may be added in advance 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, U.S. Patent No. 5,070,173 can be referred to.

於聚胺基甲酸酯化反應中，亦可使用公知之聚合觸媒或溶劑。所使用之聚合觸媒並無特別限定，例如可列舉二月桂酸二丁基錫。 A known polymerization catalyst or solvent can also be used in the polyurethane modification reaction. The polymerization catalyst to be used is not particularly limited, and examples thereof include dibutyltin dilaurate.

較佳為於本實施形態之熱塑性聚胺基甲酸酯中添加熱穩定劑(例如抗氧化劑)或光穩定劑等穩定劑。又，亦可添加塑化劑、無機填充劑、潤滑劑、著色劑、矽油、發泡劑、阻燃劑等。 It is preferred 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, an emu oil, a foaming agent, a flame retardant, or the like may be added.

[實施例] [Examples]

繼而，藉由實施例及比較例，對本發明進行說明。 Next, the present invention will be described by way of examples and comparative examples.

以下之實施例係用於例示本發明而記載者，並非對本發明之範圍進行任何限定。 The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

以下之實施例及比較例中所示之物性值係藉由下述方法進行測定。 The physical property values shown in the following examples and comparative examples were measured by the following methods.

1.碳酸酯化合物之定量 1. Quantification of carbonate compounds

以下述方式進行碳酸酯化合物之定量。首先，將樣品溶解於乙腈中而製成1%之溶液。對該溶液使用液相層析質譜儀(LC/MS，Liquid Chromatography-Mass Spectrometry)進行分析。基於藉由該分析而獲得之面積值，使用預先製作之校準曲線而進行樣品中之各碳酸酯化合物之定量。LC(Liquid Chromatography，液相層析)裝置使用附有Waters Symmetory C8(Waters公司製造)作為管柱之Waters2690(Waters公司製造)。於LC裝置中，將流量設為0.5ml/min，自乙腈：水=30：70至乙腈：水=100：0花費15分鐘施加梯度而進行測定。MS(Mass Spectrometry，質譜分析)裝置使用Waters ZMD(Waters公司製造)。於MS裝置中，於離子化：APCl+、光電倍增管電壓650V之條件下進行測定。 The quantification of the carbonate compound was carried out in the following manner. First, the sample was dissolved in acetonitrile to prepare a 1% solution. The solution was analyzed using a liquid chromatography mass spectrometer (LC/MS, Liquid Chromatography-Mass Spectrometry). The quantification of each carbonate compound in the sample was carried out based on the area value obtained by the analysis using a calibration curve prepared in advance. An LC (Liquid Chromatography) apparatus was used with Waters 2690 (manufactured by Waters Co., Ltd.) attached with Waters Symmetory C8 (manufactured by Waters Corporation). In the LC apparatus, the flow rate was set to 0.5 ml/min, and the measurement was performed by applying a gradient from acetonitrile:water = 30:70 to acetonitrile:water = 100:0 for 15 minutes. A MS (Mass Spectrometry) apparatus used Waters ZMD (manufactured by Waters Corporation). The measurement was carried out in an MS apparatus under the conditions of ionization: APCl+ and photomultiplier tube voltage of 650V.

2.聚碳酸酯二醇之組成之確定 2. Determination of the composition of polycarbonate diol

以下述方式確定聚碳酸酯二醇之組成。首先，量取樣品1g置於100ml茄形燒瓶中，添加乙醇30g、氫氧化鉀4g，而獲得混合物。藉由100℃之油浴將所獲得之混合物加熱1小時。於將上述混合物冷卻至室溫後，於上述混合物中添加1~2滴作為指示劑之酚酞，並利用鹽酸進行中和。其後，利用冰箱將上述混合物冷卻3小時，藉由過濾將所沈澱之鹽去除後，對濾液進行氣相層析(GC)分析。再者，GC分析係使用附有DB-WAX(美國J & W公司製造)(30m，膜厚0.25μm)作為管柱之氣相層析儀GC14B(島津製作所製造)，使用二乙二醇二乙酯作為內部標準，檢測器使用火焰游離偵檢器(FID)而進行。管柱之升溫曲線係設為於60℃下保持5分鐘後，以10℃/min升溫至250℃之曲線。 The composition of the polycarbonate diol was determined in the following manner. First, 1 g of the sample was weighed and placed in a 100 ml eggplant-shaped flask, and 30 g of ethanol and 4 g of potassium hydroxide were added to obtain a mixture. The obtained mixture was heated by an oil bath at 100 ° C for 1 hour. After cooling the mixture to room temperature, 1 to 2 drops of phenolphthalein as an indicator were added to the above mixture, and neutralized with hydrochloric acid. Thereafter, the mixture was cooled by a refrigerator for 3 hours, and the precipitated salt was removed by filtration, and the filtrate was subjected to gas chromatography (GC) analysis. In addition, GC analysis was performed using a gas chromatograph GC14B (manufactured by Shimadzu Corporation) equipped with DB-WAX (manufactured by J & W, USA) (30 m, film thickness: 0.25 μm) as a column, using diethylene glycol II. Ethyl ester was used as an internal standard and the detector was operated using a flame free detector (FID). The temperature rise curve of the column was set to be maintained at 60 ° C for 5 minutes, and then heated to a temperature of 250 ° C at 10 ° C / min.

基於藉由GC分析而獲得之二醇之面積值，確定聚碳酸酯二醇之組成。 The composition of the polycarbonate diol was determined based on the area value of the diol obtained by GC analysis.

3.聚碳酸酯二醇之數量平均分子量之確定 3. Determination of the number average molecular weight of polycarbonate diol

關於聚碳酸酯二醇之數量平均分子量，藉由使用乙酸酐及吡 啶，於氫氧化鉀之乙醇溶液中進行滴定之「中和滴定法(JIS K0070-1992)」而確定羥值(OH值)，並使用下述式(2)進行計算。 Regarding the number average molecular weight of polycarbonate diol, by using acetic anhydride and pyridyl The hydride value (OH value) was determined by a "neutralization titration method (JIS K0070-1992)" which was titrated in a solution of potassium hydroxide in ethanol, and was calculated using the following formula (2).

數量平均分子量=2/(OH值×10-3/56.1) (2) Number average molecular weight = 2 / (OH value × 10 -3 /56.1) (2)

4.聚碳酸酯二醇組合物之性狀之確認 4. Confirmation of the properties of the polycarbonate diol composition

將加熱至80℃之聚碳酸酯二醇組合物添加至透明樣品瓶中，以目測觀察冷卻至室溫之狀態。將透明且於使樣品瓶傾斜時即便略微傾斜亦存在流動性之情形表示為液狀，將不透明或即便使樣品瓶傾斜狀態亦不會發生變化之任一情形及兩種情形表示為固體。 The polycarbonate diol composition heated to 80 ° C was added to a transparent sample bottle, and the state of cooling to room temperature was visually observed. The case where the fluidity is transparent even when the sample bottle is tilted is indicated as liquid, and it is opaque or does not change even if the sample bottle is tilted, and the two cases are expressed as solid.

5.末端OH基比率之確定 5. Determination of the ratio of terminal OH groups

以下述方式確定聚碳酸酯二醇中之末端OH基比率。首先，稱取70g~100g之聚碳酸酯二醇置於300ml茄形燒瓶中。使用連接有餾分回收用之存液球之旋轉蒸發器，於0.4kPa以下之壓力下，將上述茄形燒瓶中之聚碳酸酯二醇加熱至約180℃之溫度，進行攪拌而於存水球中獲得相當於該聚碳酸酯二醇之約1~2重量%之餾分、即約1g(0.7~2g)之初始餾分。使所獲得之餾分溶解於約100g(95~105g)之乙醇中而以溶液之形式回收。對所回收之溶液進行氣相層析分析(以下亦稱為「GC分析」)，根據所獲得之層析圖之峰面積之值，藉由下述式(1)計算聚碳酸酯二醇中之末端OH基比率。再者，GC分析係使用附有DB-WAX(美國J & W公司製造)(30m，膜厚0.25μm)作為管柱之氣相層析儀6890(美國惠普製造)，檢測器使用火焰游離偵檢器(FID)而進行。管柱之升溫曲線係設為於10℃/min之條件下自60℃升溫至250℃後，於該溫度下保持15分鐘之曲線。GC分析中之各波峰之鑑定係使用下述GC-MS裝置進行。GC裝置使用附有DB-WAX(美國J & W公司製造)作為管柱之6890(美國惠普製造)。於GC裝置中，於升溫速度10℃/min之條件下自初始溫度40℃升溫至220℃。MS裝置使用Auto-mass SUN(日本JEOL製造)。於MS裝置中，於游離電壓70eV、掃描範圍 m/z=10~500、光電倍增管增益450V之條件下進行測定。 The ratio of terminal OH groups in the polycarbonate diol was determined in the following manner. First, 70 g to 100 g of polycarbonate diol was weighed and placed in a 300 ml eggplant-shaped flask. The polycarbonate diol in the eggplant-shaped flask is heated to a temperature of about 180 ° C under a pressure of 0.4 kPa or less using a rotary evaporator to which a liquid storage ball for fraction recovery is connected, and stirred in a water ball. An initial fraction corresponding to about 1 to 2% by weight of the polycarbonate diol, i.e., about 1 g (0.7 to 2 g), is obtained. The obtained fraction was dissolved in about 100 g (95 to 105 g) of ethanol to be recovered as a solution. The recovered solution is subjected to gas chromatography analysis (hereinafter also referred to as "GC analysis"), and the polycarbonate diol is calculated by the following formula (1) based on the value of the peak area of the obtained chromatogram. The terminal OH group ratio. In addition, the GC analysis system uses a gas chromatograph 6890 (manufactured by Hewlett-Packard Co., Ltd.) with DB-WAX (manufactured by J & W, USA) (30 m, film thickness 0.25 μm) as a column, and the detector uses flame free detection. Check with the detector (FID). The temperature rise curve of the column was set to a temperature of 60 ° C to 250 ° C under conditions of 10 ° C / min, and the curve was maintained at this temperature for 15 minutes. The identification of each peak in the GC analysis was carried out using the following GC-MS apparatus. The GC device used 6890 (manufactured by Hewlett Packard, USA) with DB-WAX (manufactured by J & W, USA) as a column. In the GC apparatus, the temperature was raised from the initial temperature of 40 ° C to 220 ° C under the conditions of a temperature increase rate of 10 ° C / min. The MS device used Auto-mass SUN (manufactured by JEOL, Japan). In the MS device, at a free voltage of 70eV, scanning range The measurement was carried out under the conditions of m/z = 10 to 500 and a photomultiplier tube gain of 450V.

末端OH基比率(%)=B÷A×100 (1) Terminal OH group ratio (%) = B÷A × 100 (1)

A：包括二醇在內之醇類(乙醇除外)之峰面積之總和 A: the sum of the peak areas of alcohols (excluding ethanol) including diols

B：二醇之峰面積之總和 B: the sum of the peak areas of the diol

6.所含元素之利用電感耦合電漿(ICP)之分析 6. Analysis of the contained elements using inductively coupled plasma (ICP)

以下述方式分析聚碳酸酯二醇組合物中所含之各元素。首先，稱取樣品置於鐵氟龍製分解容器中，添加高純度硝酸(關東化學製造)，使用微波分解裝置(Milestone General公司製造，ETHOS TC)進行分解。再者，樣品完全被分解，所獲得之分解液呈無色透明。於分解液中添加純水而製成試液。對所獲得之試液使用電感耦合電漿分析裝置(Thermo Fisher Scientific公司製造，iCAP6300 Duo)，基於各元素之標準液進行定量。 Each element contained in the polycarbonate diol composition was analyzed in the following manner. First, the sample was weighed and placed in a Teflon-made decomposition vessel, and high-purity nitric acid (manufactured by Kanto Chemical Co., Ltd.) was added and decomposed using a microwave decomposing apparatus (manufactured by Milestone General Co., Ltd., ETHOS TC). Furthermore, the sample was completely decomposed and the obtained decomposition liquid was colorless and transparent. A test solution was prepared by adding pure water to the decomposition liquid. The obtained test solution was quantified using an inductively coupled plasma analyzer (manufactured by Thermo Fisher Scientific, iCAP6300 Duo) based on a standard solution of each element.

7.塗膜之平滑性 7. Smoothness of the coating film

對由聚碳酸酯二醇組合物獲得之塗膜，使用雷射顯微鏡(Olympus製造，OLS4100)求出表面之凸凹之振幅(μm)。平滑性係將比較應用例2中獲得之塗膜之振幅設為1而以其比表示。 The amplitude (μm) of the convex and concave of the surface was determined using a laser microscope (manufactured by Olympus, OLS 4100) for the coating film obtained from the polycarbonate diol composition. The smoothness was expressed by the ratio of the amplitude of the coating film obtained in Comparative Application Example 2 to 1 .

8.塗膜之耐酸性 8. Acid resistance of the coating film

對由聚碳酸酯二醇組合物獲得之塗膜，目測評價於0.1mol/L之H2SO4水溶液中於室溫下浸漬24h後之塗膜外觀。依據JIS K5600-8-1，以等級0~5表示缺陷之程度及量，而設為塗膜之耐酸性。 The coating film obtained from the polycarbonate diol composition was visually evaluated for the appearance of the coating film after immersion in a 0.1 mol/L aqueous solution of H 2 SO 4 at room temperature for 24 hours. According to JIS K5600-8-1, the degree and amount of defects are indicated by grades 0 to 5, and the acid resistance of the coating film is set.

9.塗膜之耐鹼性 9. The alkali resistance of the coating film

對由聚碳酸酯二醇組合物獲得之塗膜，目測評價於0.1mol/L之NaOH水溶液中於室溫下浸漬24h後之塗膜外觀。依據JIS K5600-8-1，以等級0~5表示缺陷之程度及量，而設為塗膜之耐鹼性。 The coating film obtained from the polycarbonate diol composition was visually evaluated for the appearance of the coating film after immersion in a 0.1 mol/L NaOH aqueous solution at room temperature for 24 hours. According to JIS K5600-8-1, the degree and amount of defects are indicated by grades 0 to 5, and the alkali resistance of the coating film is set.

10.塗膜之耐乙醇性 10. The ethanol resistance of the coating film

對由聚碳酸酯二醇組合物獲得之塗膜，目測評價於50%EtOH水 溶液中於室溫下浸漬4h後之塗膜外觀。依據JIS K5600-8-1，以等級0~5表示缺陷之程度及量，而設為塗膜之耐乙醇性。 The coating film obtained from the polycarbonate diol composition was visually evaluated in 50% EtOH water. The appearance of the coating film after immersion in the solution at room temperature for 4 hours. According to JIS K5600-8-1, the degree and amount of defects are indicated by grades 0 to 5, and the ethanol resistance of the coating film is set.

11.塗膜之透明性 11. The transparency of the film

將由聚碳酸酯二醇組合物獲得之塗膜於90℃之蒸餾水中浸漬1週。其後，自塗膜上擦拭水分，於23℃、50%RH之恆溫室中將塗膜固化3天。依據JIS K 7105，求出浸漬前後之塗膜之全光線透過率，並根據下述式(3)求出塗膜之透明性。 The coating film obtained from the polycarbonate diol composition was immersed in distilled water at 90 ° C for 1 week. Thereafter, the film was wiped off from the coating film, and the coating film was cured in a thermostatic chamber at 23 ° C and 50% RH for 3 days. The total light transmittance of the coating film before and after the immersion was determined in accordance with JIS K 7105, and the transparency of the coating film was determined according to the following formula (3).

透明性=F/E×100 (3) Transparency = F / E × 100 (3)

E：浸漬前之塗膜之全光線透過率(%) E: total light transmittance (%) of the coating film before immersion

F：浸漬後之塗膜之全光線透過率(%) F: total light transmittance (%) of the film after immersion

12.塗膜之附著性 12. Coating adhesion

使用由聚碳酸酯二醇組合物獲得之塗膜，依據JIS K5600-5-6(交叉切割法)，藉由0~5之6等級之分類對塗膜之附著性進行評價。 Using the coating film obtained from the polycarbonate diol composition, the adhesion of the coating film was evaluated by classification of 0 to 5 according to JIS K5600-5-6 (cross cutting method).

13.聚胺基甲酸酯膜之機械物性 13. Mechanical properties of polyurethane film

將由聚碳酸酯二醇組合物獲得之聚胺基甲酸酯膜切割為10mm×80mm之短條型，並於23℃、50%RH之恆溫室中固化3天，並將以上述方法獲得者設為試驗體。對所獲得之試驗體，使用Tensilon拉伸試驗器(ORIENTEC製造，RTC-1250A)，於夾頭間距離50mm、拉伸速度100mm/min之條件下測定斷裂強度(單位：MPa)及斷裂伸長率(單位：%)。 The polyurethane film obtained from the polycarbonate diol composition was cut into a short strip of 10 mm × 80 mm, and cured in a constant temperature chamber at 23 ° C, 50% RH for 3 days, and obtained by the above method. Set as the test body. For the obtained test body, the Tensilon tensile tester (manufactured by ORIENTEC, RTC-1250A) was used, and the breaking strength (unit: MPa) and elongation at break were measured under the conditions of a distance between the chucks of 50 mm and a tensile speed of 100 mm/min. (unit:%).

14.聚胺基甲酸酯膜之耐油性 14. Oil resistance of polyurethane film

將由聚碳酸酯二醇組合物獲得之聚胺基甲酸酯膜切割為10mm×80mm之短條型而獲得試驗體。使0.1g之油酸附著於所獲得之試驗體上，於20℃下放置4小時，目測評價試驗體之外觀。依據JISK5600-8-1，以等級0~5表示缺陷之程度及量，而設為耐油性。 The test piece was obtained by cutting a polyurethane film obtained from a polycarbonate diol composition into a short strip shape of 10 mm × 80 mm. 0.1 g of oleic acid was attached to the obtained test body, and allowed to stand at 20 ° C for 4 hours, and the appearance of the test piece was visually evaluated. According to JIS K5600-8-1, the degree and amount of defects are indicated by grades 0 to 5, and oil resistance is set.

15.聚碳酸酯二醇組合物中之水分量之測定 15. Determination of moisture content in polycarbonate diol compositions

使用水分測定裝置(KF-100型，Mitsubishi Chemical Analytech製造)，依據JIS K0068，藉由容量分析法測定聚碳酸酯二醇組合物中之水分量。 The moisture content in the polycarbonate diol composition was measured by a volumetric analysis method using a moisture measuring device (KF-100 type, manufactured by Mitsubishi Chemical Analytech) in accordance with JIS K0068.

16.聚碳酸酯二醇組合物中之環狀醚化合物之定量 16. Quantification of cyclic ether compounds in polycarbonate diol compositions

以下述方式確定聚碳酸酯二醇組合物中之環狀醚化合物之量。精確稱量樣品2g，添加至20ml小玻璃瓶中並塞緊。於100℃下將小玻璃瓶加熱3小時，利用加熱至100℃之氣密型注射器提取氣相1ml，並藉由GC/MS進行測定。GC裝置使用7890A(Agilent公司製造)，管柱使用Equity-1(Sigma-Aldrich公司製造)(30m，膜厚0.25μm)。升溫曲線係設為於40℃下保持7分鐘後，以10℃/min升溫至280℃，於該溫度下保持5分鐘之升溫曲線。MS裝置使用Jms-Q1000GC(日本電子股份有限公司製造)，於游離電壓70eV、掃描範圍m/z=10~500、光電倍增管增益1300V之條件下進行測定。定量係利用1-丁醇製作校準曲線而進行。 The amount of the cyclic ether compound in the polycarbonate diol composition was determined in the following manner. 2 g of the sample was accurately weighed, added to a 20 ml vial and stoppered. The vial was heated at 100 ° C for 3 hours, and 1 ml of the gas phase was extracted with a gas-tight syringe heated to 100 ° C, and measured by GC/MS. The GC device used 7890A (manufactured by Agilent Co., Ltd.), and the column used Equity-1 (manufactured by Sigma-Aldrich Co., Ltd.) (30 m, film thickness: 0.25 μm). The temperature rise curve was set at 40 ° C for 7 minutes, and then the temperature was raised to 280 ° C at 10 ° C / min, and the temperature rise curve was maintained at this temperature for 5 minutes. The MS apparatus was measured using Jms-Q1000GC (manufactured by JEOL Ltd.) under the conditions of a free voltage of 70 eV, a scanning range of m/z of 10 to 500, and a photomultiplier tube gain of 1300V. The quantification was carried out by making a calibration curve using 1-butanol.

環狀醚化合物量(ppm)=G/H×1000 (4) Amount of cyclic ether compound (ppm) = G / H × 1000 (4)

G：環狀醚化合物之總和(mg) G: sum of cyclic ether compounds (mg)

H：樣品量(g) H: sample amount (g)

17.聚碳酸酯二醇組合物之色值之確定 17. Determination of the color value of the polycarbonate diol composition

使用比色管，依據JIS K 0071-1，確定聚碳酸酯二醇組合物之色值。 The color value of the polycarbonate diol composition was determined in accordance with JIS K 0071-1 using a colorimetric tube.

18.熱塑性聚胺基甲酸酯之流動特性 18. Flow characteristics of thermoplastic polyurethanes

對熱塑性聚胺基甲酸酯，使用毛細管流變儀(Capillograph1D，東洋精機製作所製造)，依據JIS K7199，於升溫速度：3℃/min、模具：1mm ×10mmL、荷重：5.5MPa之條件下進行測定，藉此獲得溫度[℃]-黏度[dPa‧s]曲線。基於流動起始溫度[℃]、及流動起始溫度+10℃下之黏度相對於流動起始溫度下之黏度之比(參照下述式(5))，評價 熱塑性聚胺基甲酸酯之流動特性。評價為流動起始溫度越高黏度比越較小，越不易發生黏連，進而成型性越優異。 For the thermoplastic polyurethane, a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used, according to JIS K7199, at a temperature increase rate of 3 ° C/min, and a mold: 1 mm. The measurement was carried out under the conditions of ×10 mmL and a load of 5.5 MPa, whereby a temperature [°C]-viscosity [dPa‧s] curve was obtained. The thermoplastic polyurethane was evaluated based on the flow initiation temperature [° C.] and the ratio of the viscosity at the flow initiation temperature + 10 ° C to the viscosity at the flow initiation temperature (refer to the following formula (5)). Flow characteristics. It was evaluated that the higher the flow initiation temperature, the smaller the viscosity ratio, and the more the adhesion is less likely to occur, and the more excellent the moldability.

黏度比=(流動起始溫度+10℃之黏度)/(流動起始溫度之黏度) (5) Viscosity ratio = (flow start temperature + 10 ° C viscosity) / (flow start temperature viscosity) (5)

[實施例1] [Example 1]

於具備填充有規則填充物之精餾塔與攪拌裝置的2L玻璃製燒瓶中添加碳酸乙二酯640g(7.3mol)、1,5-戊二醇400g(3.9mol)、及1,6-己二醇410g(3.5mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.35g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。 將反應起始溫度設為140℃，並於該溫度下進行15小時反應。其後，花費15小時將反應溫度緩慢提昇至160℃，一面餾去所生成之乙二醇與碳酸乙二酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至10kPa，一面餾去二醇與碳酸乙二酯之混合物，一面於164℃下進而進行15小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.39g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)2g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-1。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Add 640 g (7.3 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, and 1,6-hexane to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. The diol was 410 g (3.5 mol). Further, 0.35 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 15 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 15 hours, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 10 kPa, and the mixture of the diol and ethylene carbonate was distilled off, and the reaction was further carried out at 164 ° C for 15 hours. Thereafter, 0.39 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 In the case of a carbonate compound) 2 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. 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 R and ratio of each repeating unit are shown in Table 1.

[實施例2] [Embodiment 2]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為0.5g，除此以外，藉由與實施例1相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC- 2。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as Example 1 except 0.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. The polycarbonate diol composition is simply referred to as PC- 2. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例3] [Example 3]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為11g，除此以外，藉由與實施例1相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-3。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as that of Example 1 except for 11 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-3. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例4] [Example 4]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為20.5g，除此以外，藉由與實施例1相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-4。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as Example 1 except for 20.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-4. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[比較例1] [Comparative Example 1]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為26g，除此以外，藉由與實施例1相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-21。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as in Example 1 except for 26 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-21. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例5] [Example 5]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸二甲酯550g(6.1mol)、1,5-戊二醇400g(3.9mol)、及1,6- 己二醇460g(3.9mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.50g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行20小時反應。其後，花費15小時將反應溫度緩慢提昇至160℃，一面餾去所產生之甲醇與碳酸二甲酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至11kPa，一面餾去二醇與碳酸二甲酯，一面於165℃下進而進行20小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.55g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)5.5g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-5。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。進而，PC-5之水分量為41ppm，四氫吡喃之含量為0.9ppm，氧雜環庚烷之含量為0.04ppm。又，PC-5之色值為10。 550 g (6.1 mol) of dimethyl carbonate, 400 g (3.9 mol) of 1,5-pentanediol, and 1,6- were added to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. Hexanediol 460 g (3.9 mol). Further, 0.50 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 20 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 15 hours, and the resulting mixture of methanol and dimethyl carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 11 kPa, and the diol and dimethyl carbonate were distilled off, and the reaction was further carried out at 165 ° C for 20 hours. Thereafter, 0.55 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 In the case of a carbonate compound, 5.5 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-5. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1. Further, the water content of PC-5 was 41 ppm, the content of tetrahydropyran was 0.9 ppm, and the content of oxepane was 0.04 ppm. Also, the color value of PC-5 is 10.

[比較例2] [Comparative Example 2]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為0.1g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-22。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as Example 5 except 0.1 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-22. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例6] [Embodiment 6]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為0.25g，除此以外，藉由與實施例 5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-6。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to 0.25 g, in addition to the examples 5 The same method was used to obtain a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is abbreviated as PC-6. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例7] [Embodiment 7]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之添加量設為0.3g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-7。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The addition amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) is set to A polycarbonate diol composition was obtained by the same method as Example 5 except 0.3 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-7. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[比較例3] [Comparative Example 3]

添加作為碳酸酯化合物之1,3,10,12-四氧雜環十八烷-2,11-二酮(式(B)中，l=6、m=6之情形時之碳酸酯化合物)9.5g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-23。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Addition of 1,3,10,12-tetraoxacyclooctadecane-2,11-dione as a carbonate compound (carbonate compound in the case of l=6, m=6 in the formula (B)) A polycarbonate diol composition was obtained by the same method as Example 5 except 9.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-23. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例8] [Embodiment 8]

添加作為碳酸酯化合物之1,3,11,13-四氧雜環二十一烷-2,12-二酮(式(B)中，l=7、m=8之情形時之碳酸酯化合物)0.5g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-8。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Addition of 1,3,11,13-tetraoxacyclohexadecane-2,12-dione as a carbonate compound (in the case of formula (B), a carbonate compound in the case of l=7, m=8 A polycarbonate diol composition was obtained by the same method as Example 5 except 0.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-8. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例9] [Embodiment 9]

添加作為碳酸酯化合物之1,3,6,8-四氧雜環十一烷-2,7-二酮(式(B)中，l=2、m=3之情形時之碳酸酯化合物)0.5g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-9。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Addition of 1,3,6,8-tetraoxacycloundecyl-2,7-dione as a carbonate compound (carbonate compound in the case of l=2, m=3 in the formula (B)) A polycarbonate diol composition was obtained by the same method as Example 5 except 0.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. 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 R and ratio of each repeating unit are shown in Table 1.

[比較例4] [Comparative Example 4]

添加作為碳酸酯化合物之1,3,19,21-四氧雜環七-三十烷-2,20-二酮(式(B)中，l=15、m=16之情形時之碳酸酯化合物)0.5g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-24。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Addition of 1,3,19,21-tetraoxacyclo-7-triacontan-2,20-dione as a carbonate compound (in the case of the formula (B), the carbonate in the case of l=15, m=16 A polycarbonate diol composition was obtained by the same method as in Example 5 except that 0.5 g of the compound was used. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-24. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例10] [Embodiment 10]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸二乙酯820g(7.0mol)、1,5-戊二醇350g(3.4mol)、及1,6-己二醇420g(3.6mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.30g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行20小時反應。其後，花費15小時將反應溫度緩慢提昇至160℃，一面餾去所產生之乙醇與碳酸二乙酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至13kPa，一面餾去二醇與碳酸二乙酯，一面於160℃下進而進行25小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.33g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化 合物)2g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-10。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 825 g (7.0 mol) of diethyl carbonate, 350 g (3.4 mol) of 1,5-pentanediol, and 1,6-hexane were added to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. Diol 420 g (3.6 mol). Further, 0.30 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 20 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 15 hours, and the resulting mixture of ethanol and diethyl carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 13 kPa, and the diol and diethyl carbonate were distilled off, and the reaction was further carried out at 160 ° C for 25 hours. Thereafter, 0.33 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 Carbonation in the case 2 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. 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 R and ratio of each repeating unit are shown in Table 1.

[實施例11] [Example 11]

將碳酸二乙酯之添加量設為860g(7.3mol)，除此以外，於與實施例10相同之條件下進行反應而獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)2g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-11。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 A polycarbonate diol was obtained under the same conditions as in Example 10 except that the amount of the diethyl carbonate added was 860 g (7.3 mol). To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 In the case of a carbonate compound) 2 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. 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 R and ratio of each repeating unit are shown in Table 1.

[實施例12] [Embodiment 12]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸乙二酯670g(7.6mol)、1,5-戊二醇400g(3.9mol)、及3-甲基-1,5-戊二醇450g(3.8mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.10g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行18小時反應。其後，花費15小時將反應溫度緩慢提昇至160℃，一面餾去乙二醇與碳酸乙二酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至10kPa，一面餾去二醇與碳酸乙二酯之混合物，一面於165℃下進而進行15小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.11g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時 之碳酸酯化合物)2g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-12。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 To a 2L glass flask equipped with a rectification column and a stirring device filled with a regular filler, 670 g (7.6 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, and 3-methyl- were added. 1,5-pentanediol 450 g (3.8 mol). Further, 0.10 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 18 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 15 hours, and the reaction was carried out while distilling off a mixture of ethylene glycol and ethylene carbonate. Thereafter, the pressure in the flask was reduced to 10 kPa, and the mixture of the diol and ethylene carbonate was distilled off, and the reaction was further carried out at 165 ° C for 15 hours. Thereafter, 0.11 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 Situation 2 g of the carbonate compound) was stirred at 100 ° C for 5 hours, whereby a polycarbonate diol composition was obtained. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-12. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例13] [Example 13]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸二甲酯450g(5.0mol)、及1,9-壬二醇1000g(6.2mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.90g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行15小時反應。其後，花費13小時將反應溫度緩慢提昇至160℃，一面餾去所產生之甲醇與碳酸二甲酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至13kPa，一面餾去二醇與碳酸二甲酯，一面於162℃下進而進行18小時反應。其後，於上述燒瓶中添加作為磷化合物之磷酸單-2-乙基己酯1.0g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,8,10-四氧雜環十五烷-2,9-二酮(式(B)中，l=4、m=5之情形時之碳酸酯化合物)5.5g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-13。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 To a 2 L glass flask equipped with a rectification column and a stirring apparatus filled with a regular filler, 450 g (5.0 mol) of dimethyl carbonate and 1000 g (6.2 mol) of 1,9-nonanediol were added. Further, 0.90 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 15 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 13 hours, and the resulting mixture of methanol and dimethyl carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 13 kPa, and the diol and dimethyl carbonate were distilled off, and the reaction was further carried out at 162 ° C for 18 hours. Thereafter, 1.0 g of mono-2-ethylhexyl phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,8,10-tetraoxacyclopentadecane-2,9-dione was added (in the formula (B), l=4, m=5 In the case of a carbonate compound, 5.5 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-13. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例14] [Embodiment 14]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸乙二酯650g(7.4mol)、1,4-丁二醇410g(4.6mol)、及1,5-戊二醇300g(2.9mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦 0.6g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行15小時反應。其後，花費15小時將反應溫度緩慢提昇至160℃，一面餾去所產生之乙二醇與碳酸乙二酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至10kPa，一面餾去二醇與碳酸乙二酯之混合物，一面於166℃下進而進行15小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.67g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,8,10-四氧雜環十五烷-2,9-二酮(式(B)中，l=4、m=5之情形時之碳酸酯化合物)1.52g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-14。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 650 g (7.4 mol) of ethylene carbonate, 410 g (4.6 mol) of 1,4-butanediol, and 1,5-pentane were added to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. The diol was 300 g (2.9 mol). Further adding titanium tetraisopropoxide as a catalyst to the above flask 0.6 g, the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 15 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 15 hours, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 10 kPa, and the mixture of the diol and ethylene carbonate was distilled off, and the reaction was further carried out at 166 ° C for 15 hours. Thereafter, 0.67 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours, whereby a polycarbonate diol was obtained. To 500 g of the obtained polycarbonate diol, 1,3,8,10-tetraoxacyclopentadecane-2,9-dione was added (in the formula (B), l=4, m=5 In the case of a carbonate compound, 1.52 g, and stirred at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-14. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[實施例15] [Example 15]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸乙二酯630g(7.2mol)、1,4-丁二醇140g(1.6mol)、及1,6-己二醇670g(6.7mol)。於上述燒瓶中進而添加作為觸媒之酸式磷酸2-乙基己酯0.3g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為140℃，並於該溫度下進行15小時反應。其後，花費13小時將反應溫度緩慢提昇至160℃，一面餾去所產生之乙二醇與碳酸乙二酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至10kPa，一面餾去二醇與碳酸乙二酯之混合物，一面於164℃下進而進行15小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.33g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g 中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)2.0g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-15。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 2-3 g of ethylene carbonate (7.2 mol), 140 g of 1,4-butanediol (1.6 mol), and 1,6-hex were added to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. The diol was 670 g (6.7 mol). Further, 0.3 g of 2-ethylhexyl acid phosphate as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 140 ° C, and the reaction was carried out at this temperature for 15 hours. Thereafter, the reaction temperature was slowly raised to 160 ° C over 13 hours, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 10 kPa, and the mixture of the diol and ethylene carbonate was distilled off, and the reaction was further carried out at 164 ° C for 15 hours. Thereafter, 0.33 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. The obtained polycarbonate diol 500g In the case of adding 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (carbonate compound in the case of l=5, m=6 in the formula (B)), 2.0 g, And stirring at 100 ° C for 5 hours, thereby obtaining a polycarbonate diol composition. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. 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 R and ratio of each repeating unit are shown in Table 1.

[比較例5] [Comparative Example 5]

添加5-甲基-1,3-二烷-2-酮0.5g代替式(B)所表示之碳酸酯化合物，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-25。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Add 5-methyl-1,3-di A polycarbonate diol composition was obtained by the same method as that of Example 5 except that 0.5% of the alkyl-2-one was used instead of the carbonate compound represented by the formula (B). The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-25. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[比較例6] [Comparative Example 6]

於具備填充有規則填充物之精餾塔與攪拌裝置之2L玻璃製燒瓶中添加碳酸乙二酯640g(7.3mol)、1,5-戊二醇400g(3.9mol)、及1,6-己二醇410g(3.5mol)。於上述燒瓶中進而添加作為觸媒之四異丙醇鈦0.50g，於常壓下將上述燒瓶內之混合物攪拌及加熱而使反應開始。將反應起始溫度設為135℃，並於該溫度下進行22小時反應。其後，花費20小時將反應溫度緩慢提昇至155℃，一面餾去所產生之乙二醇與碳酸乙二酯之混合物一面進行反應。其後，將上述燒瓶內之壓力減壓至7kPa，一面餾去二醇與碳酸乙二酯之混合物，一面於158℃下進而進行25小時反應。其後，於上述燒瓶中添加作為磷化合物之酸式磷酸2-乙基己酯0.55g，並於120℃下將上述燒瓶內之混合物加熱5小時，藉此獲得聚碳酸酯二醇。於所獲得之聚碳酸酯二醇500g中，添加1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時 之碳酸酯化合物)0.1g，並於100℃下攪拌5小時，藉此獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-26。 Add 640 g (7.3 mol) of ethylene carbonate, 400 g (3.9 mol) of 1,5-pentanediol, and 1,6-hexane to a 2 L glass flask equipped with a rectification column and a stirring device filled with a regular filler. The diol was 410 g (3.5 mol). Further, 0.50 g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the mixture in the flask was stirred and heated under normal pressure to start the reaction. The reaction initiation temperature was set to 135 ° C, and the reaction was carried out at this temperature for 22 hours. Thereafter, the reaction temperature was slowly raised to 155 ° C over 20 hours, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off while reacting. Thereafter, the pressure in the flask was reduced to 7 kPa, and the mixture of the diol and ethylene carbonate was distilled off, and the reaction was further carried out at 158 ° C for 25 hours. Thereafter, 0.55 g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120 ° C for 5 hours to obtain a polycarbonate diol. To 500 g of the obtained polycarbonate diol, 1,3,9,11-tetraoxacyclohexadecane-2,10-dione was added (in the formula (B), l=5, m=6 Situation The carbonate compound) was 0.1 g, and stirred at 100 ° C for 5 hours, whereby a polycarbonate diol composition was obtained. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is abbreviated as PC-26.

[實施例16] [Example 16]

將1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)之量設為1.5g，除此以外，藉由與比較例6相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-16。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 The amount of 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (the carbonate compound in the case where l=5 and m=6 in the formula (B)) was set to 1.5. Further, a polycarbonate diol composition was obtained by the same method as Comparative Example 6, except for the above. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-16. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[比較例7] [Comparative Example 7]

對應於1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)，添加1,3,9,11,17,19-六氧雜環二十五烷-2,10,18-三酮(式(H)中，i=5、k=6之情形時之碳酸酯化合物)13g、及1,3,9,11,18,20-六氧雜環二十六烷-2,10,19-三酮(式(H)中，i=6、k=5之情形時之碳酸酯化合物)13.5g，除此以外，藉由與比較例6相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-27。 Corresponding to 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (carbonate compound in the case of l=5, m=6 in the formula (B)), adding 1, 3,9,11,17,19-hexaoxacyclopentadecane-2,10,18-trione (carbonate compound in the case of i=5, k=6 in the formula (H)) 13 g And 1,3,9,11,18,20-hexaoxacyclohexadecane-2,10,19-trione (in the formula (H), i=6, k=5 in the case of carbonic acid A polycarbonate diol composition was obtained by the same method as Comparative Example 6, except that the ester compound was 13.5 g. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-27.

[實施例17] [Example 17]

對應於1,3,9,11-四氧雜環十七烷-2,10-二酮(式(B)中，l=5、m=6之情形時之碳酸酯化合物)5.5g，添加1,3,10,12-四氧雜環十八烷-2,11-二酮(式(I)中，r=6之情形時之碳酸酯化合物)0.4g，除此以外，藉由與實施例5相同之方法獲得聚碳酸酯二醇組合物。將對所獲得之聚碳酸酯二醇組合物進行分析之結果示於表1。將該聚碳酸酯二醇組合物簡稱為PC-17。所獲得之聚碳酸酯二醇具有式(A)所表示之重複單元與末端羥基，各重複單元之R及比率如表1所示。 Corresponding to 1,3,9,11-tetraoxacyclohexadecane-2,10-dione (carbonate compound in the case of l=5, m=6 in the formula (B)) 5.5 g, added 1,3,10,12-tetraoxacyclooctadecane-2,11-dione (carbonate compound in the case of r=6 in the formula (I)) 0.4 g, in addition to The polycarbonate diol composition was obtained in the same manner as in Example 5. The results of analysis of the obtained polycarbonate diol composition are shown in Table 1. This polycarbonate diol composition is simply referred to as PC-17. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and R and ratio of each repeating unit are shown in Table 1.

[應用例1] [Application Example 1]

將聚碳酸酯二醇組合物PC-1 40g、作為調平劑之BYK-331(BYK化學製造)0.75g、以成為2重量%之方式溶解於稀釋劑(二甲苯/乙酸丁酯=70/30(重量比))中而成之二月桂酸二丁基錫溶液1.25g、以及稀釋劑40g混合攪拌，而獲得塗料主劑。於所獲得之塗料主劑中，添加作為硬化劑之有機聚異氰酸酯(Duranate TPA-100，Asahi Kasei Chemicals製造，異氰酸酯(NCO)含量：23.1%)7.5g，而製備塗佈液。將該塗佈液噴霧塗佈於丙烯腈-丁二烯-苯乙烯(ABS，Acrylonitrile-Butadiene-Styrene)樹脂板上，於室溫下將稀釋劑吹散2小時後，於80℃下進行加熱硬化2小時而獲得塗膜。使用該塗膜進行物性之評價。將該評價結果示於表2。 40 g of the polycarbonate diol composition PC-1 and 0.75 g of BYK-331 (manufactured by BYK Chemical Co., Ltd.) as a leveling agent were dissolved in a diluent (xylene/butyl acetate = 70/) so as to be 2% by weight. A coating main agent was obtained by mixing and stirring 1.25 g of a dibutyltin dilaurate solution and 30 g of a diluent obtained in 30 (by weight). To the obtained coating main agent, 7.5 g of an organic polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals, isocyanate (NCO) content: 23.1%) as a hardener was added to prepare a coating liquid. The coating liquid was spray-coated on an ABS (Acrylonitrile-Butadiene-Styrene) resin plate, and the diluent was blown off at room temperature for 2 hours, and then heated at 80 ° C. The coating film was obtained by hardening for 2 hours. The coating film was used to evaluate the physical properties. The evaluation results are shown in Table 2.

[應用例2~17] [Application Examples 2 to 17]

使用PC-2~17作為聚碳酸酯二醇組合物，除此以外，以與應用例1相同之方式獲得塗膜。使用該塗膜進行物性之評價。將該評價結果示於表2。 A coating film was obtained in the same manner as in Application Example 1, except that PC-2 to 17 was used as the polycarbonate diol composition. The coating film was used to evaluate the physical properties. The evaluation results are shown in Table 2.

[比較應用例1~7] [Comparative Application Examples 1~7]

使用PC-21~27作為聚碳酸酯二醇組合物，除此以外，以與應用例1相同之方式獲得塗膜。使用該塗膜進行物性之評價。將該評價結果示於表2。 A coating film was obtained in the same manner as in Application Example 1, except that PC-21-27 was used as the polycarbonate diol composition. The coating film was used to evaluate the physical properties. The evaluation results are shown in Table 2.

[應用例18] [Application Example 18]

於附有攪拌裝置、溫度計及冷凝管之反應器中，添加實施例1中獲得之PC-1200g、六亞甲基二異氰酸酯34g、及作為觸媒之二月桂酸二丁基錫0.02g，於70℃下使之反應5小時而獲得具有末端異氰酸酯(NCO)基之胺基甲酸酯預聚物。於上述胺基甲酸酯預聚物中添加作為溶劑之二甲基甲醯胺600g而獲得溶液。其後，於所獲得之溶液中，添加作為鏈延長劑之異佛爾酮二胺17g，並於35℃下攪拌1小時，藉此獲得聚胺基甲酸酯樹脂溶液。使所獲得之聚胺基甲酸酯樹脂溶液流延於玻璃板上，於室溫下放置30分鐘而將溶劑吹散後，放入至100℃之乾燥機中，使之乾燥2小時而獲得聚胺基甲酸酯膜。使用該聚胺基 甲酸酯膜進行物性之評價。將該評價結果示於表3。 To the reactor equipped with the stirring device, the thermometer and the condenser, PC-1200 g obtained in Example 1, 34 g of hexamethylene diisocyanate, and 0.02 g of dibutyltin dilaurate as a catalyst were added at 70 ° C. The reaction was carried out for 5 hours to obtain a urethane prepolymer having a terminal isocyanate (NCO) group. To the above urethane prepolymer, 600 g of dimethylformamide as a solvent was added to obtain a solution. Thereafter, 17 g of isophoronediamine as a chain extender was added to the obtained solution, and the mixture was stirred at 35 ° C for 1 hour, whereby a polyurethane resin solution was obtained. The obtained polyurethane resin solution was cast on a glass plate, left at room temperature for 30 minutes, and the solvent was blown off, and then placed in a dryer at 100 ° C, and dried for 2 hours to obtain Polyurethane film. Using the polyamine group The formate film was evaluated for physical properties. The evaluation results are shown in Table 3.

[應用例19~34] [Application Examples 19 to 34]

使用PC-2~17作為聚碳酸酯二醇組合物，除此以外，以與應用例16相同之方式獲得聚胺基甲酸酯膜。使用該聚胺基甲酸酯膜進行物性之評價。將該評價結果示於表3。 A polyurethane film was obtained in the same manner as in Application Example 16, except that PC-2 to 17 was used as the polycarbonate diol composition. The physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 3.

[比較應用例8~14] [Comparative Application Examples 8~14]

使用PC-21~27作為聚碳酸酯二醇組合物，除此以外，以與應用例16相同之方式獲得聚胺基甲酸酯膜。使用該聚胺基甲酸酯膜進行物性之評價。將該評價結果示於表3。 A polyurethane film was obtained in the same manner as in Application Example 16, except that PC-21-27 was used as the polycarbonate diol composition. The physical properties were evaluated using the polyurethane film. The evaluation results are shown in Table 3.

[應用例35] [Application Example 35]

將實施例5中獲得之PC-5 800g、及六亞甲基二異氰酸酯255g添加至附有攪拌裝置、溫度計及冷凝管之反應器中，於100℃下使之反應4小時而獲得具有末端異氰酸酯(NCO)基之胺基甲酸酯預聚物。於該預聚物中添加作為鏈延長劑之1,4-丁二醇107g、及作為觸媒之二月桂酸二丁基錫0.05g，使用內置有捏合機之LABO用萬能擠出機(日本笠松化工研究所股份有限公司製造之LABO用萬能擠出機KR-35型)，於140℃下進行60分鐘反應而獲得熱塑性聚胺基甲酸酯。其後，利用擠出機將所獲得之熱塑性聚胺基甲酸酯製成顆粒。對所獲得之熱塑性聚胺基甲酸酯，評價流動特性，結果流動起始溫度為168℃，黏度比為0.046。 PC-5 800 g obtained in Example 5 and 255 g of hexamethylene diisocyanate were added to a reactor equipped with a stirring device, a thermometer and a condenser, and reacted at 100 ° C for 4 hours to obtain a terminal isocyanate. (NCO) based urethane prepolymer. To the prepolymer, 107 g of 1,4-butanediol as a chain extender and 0.05 g of dibutyltin dilaurate as a catalyst were added, and a universal extruder of LABO with a kneading machine was used (Japan Hamamatsu Chemical Co., Ltd.) The LABO manufactured by the Institute Co., Ltd. was subjected to a reaction at 140 ° C for 60 minutes to obtain a thermoplastic polyurethane. Thereafter, the obtained thermoplastic polyurethane was pelletized by an extruder. The flow characteristics were evaluated for the obtained thermoplastic polyurethane, and as a result, the flow initiation temperature was 168 ° C and the viscosity ratio was 0.046.

[應用例36] [Application Example 36]

使用PC-17代替PC-5作為聚碳酸酯二醇組合物，除此以外，以與應用例35相同之方式獲得熱塑性聚胺基甲酸酯。對所獲得之熱塑性聚胺基甲酸酯，評價流動特性，結果流動起始溫度為172℃，黏度比為0.033。 A thermoplastic polyurethane was obtained in the same manner as in Application Example 35 except that PC-17 was used instead of PC-5 as the polycarbonate diol composition. The flow characteristics were evaluated for the obtained thermoplastic polyurethane, and as a result, the flow initiation temperature was 172 ° C and the viscosity ratio was 0.033.

[產業上之可利用性] [Industrial availability]

本發明之聚碳酸酯二醇組合物於用作塗料之構成材料之情形時，可不損及耐化學品性而獲得平滑之塗膜。又，本發明之聚碳酸酯二醇組合物於用作聚胺基甲酸酯之原料之情形時，可不損及機械強度而獲得耐油性優異之聚胺基甲酸酯。由於具有該等特性，故而本發明之聚碳酸酯二醇組合物可較佳地用作塗料之構成材料，進而，可較佳地用作聚胺基甲酸酯之原料。 When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, a smooth coating film can be obtained without impairing chemical resistance. Further, when the polycarbonate diol composition of the present invention is used as a raw material of a polyurethane, it is possible to obtain a polyurethane having excellent oil resistance without impairing mechanical strength. Because of these characteristics, the polycarbonate diol composition of the present invention can be preferably used as a constituent material of a coating material, and further, it can be preferably used as a raw material of a polyurethane.

Claims (17)

一種聚碳酸酯二醇組合物，其包含含有下述式(A)所表示之重複單元與末端羥基之聚碳酸酯二醇、及 (式(A)中，R表示碳數2~15之二價脂肪族或脂環族烴)下述式(B)所表示之碳酸酯化合物0.05~5重量%， (式(B)中，l及m表示2~15之整數，且l≠m)。 A polycarbonate diol composition comprising a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group, and (In the formula (A), R represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 15 carbon atoms; and 0.05 to 5% by weight of the carbonate compound represented by the following formula (B), (In the formula (B), l and m represent an integer of 2 to 15, and l≠m). 如請求項1之聚碳酸酯二醇組合物，其包含0.03~5重量%之下述式(H)所表示之碳酸酯化合物， (式(H)中，i及k表示2~15之整數，且i≠k)。 The polycarbonate diol composition of claim 1, which comprises 0.03 to 5% by weight of a carbonate compound represented by the following formula (H), (In the formula (H), i and k represent an integer of 2 to 15, and i ≠ k). 如請求項1之聚碳酸酯二醇組合物，其中上述式(B)所表示之碳酸酯化合物為下述式(C)所表示之碳酸酯化合物， (式(C)中，l及m表示4~6之整數，且l≠m)。 The polycarbonate diol composition of claim 1, wherein the carbonate compound represented by the above formula (B) is a carbonate compound represented by the following formula (C). (In the formula (C), l and m represent an integer of 4 to 6, and l≠m). 如請求項1或2之聚碳酸酯二醇組合物，其中上述聚碳酸酯二醇中之末端OH基比率為95.0~99.9%。 The polycarbonate diol composition of claim 1 or 2, wherein the terminal OH group ratio in the above polycarbonate diol is from 95.0 to 99.9%. 如請求項1或2之聚碳酸酯二醇組合物，其中藉由ICP進行測定時之選自由鈦、鐿、錫及鋯所組成之群中的至少1種金屬元素之含量為0.0001~0.02重量%。 The polycarbonate diol composition according to claim 1 or 2, wherein the content of at least one metal element selected from the group consisting of titanium, tantalum, tin and zirconium when measured by ICP is 0.0001 to 0.02 by weight. %. 如請求項1或2之聚碳酸酯二醇組合物，其中藉由ICP進行測定時之鈦、鐿、錫及鋯之總含量為0.0001~0.02重量%。 The polycarbonate diol composition according to claim 1 or 2, wherein the total content of titanium, bismuth, tin and zirconium when measured by ICP is 0.0001 to 0.02% by weight. 如請求項1或2之聚碳酸酯二醇組合物，其中藉由ICP進行測定時之磷元素之含量為0.0001~0.02重量%。 The polycarbonate diol composition according to claim 1 or 2, wherein the content of the phosphorus element when measured by ICP is 0.0001 to 0.02% by weight. 如請求項1或2之聚碳酸酯二醇組合物，其中選自由四氫呋喃、四氫吡喃及氧雜環庚烷所組成之群中之至少1種環狀醚化合物之含量為0.01~50ppm。 The polycarbonate diol composition according to claim 1 or 2, wherein a content of at least one cyclic ether compound selected from the group consisting of tetrahydrofuran, tetrahydropyran and oxepane is 0.01 to 50 ppm. 如請求項1或2之聚碳酸酯二醇組合物，其中四氫呋喃、四氫吡喃及氧雜環庚烷之總含量為0.01~50ppm。 The polycarbonate diol composition of claim 1 or 2, wherein the total content of tetrahydrofuran, tetrahydropyran and oxepane is from 0.01 to 50 ppm. 如請求項1或2之聚碳酸酯二醇組合物，其包含0.01~3重量%之下述式(I)所表示之碳酸酯化合物， (式(I)中，r表示2~15之整數)。 The polycarbonate diol composition according to claim 1 or 2, which comprises 0.01 to 3% by weight of a carbonate compound represented by the following formula (I), (In the formula (I), r represents an integer of 2 to 15). 如請求項1或2之聚碳酸酯二醇組合物，其中水分量為1~500ppm。 The polycarbonate diol composition of claim 1 or 2 wherein the amount of water is from 1 to 500 ppm. 如請求項1或2之聚碳酸酯二醇組合物，其色值為5~100。 The polycarbonate diol composition of claim 1 or 2, which has a color value of 5 to 100. 一種塗佈組合物，其包含如請求項1至12中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯。 A coating composition comprising the polycarbonate diol composition according to any one of claims 1 to 12 and an organic polyisocyanate. 一種塗佈組合物，其包含使如請求項1至12中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯反應而獲得之胺基甲酸酯預聚物，且該胺基甲酸酯預聚物具有末端異氰酸酯基。 A coating composition comprising a urethane prepolymer obtained by reacting a polycarbonate diol composition according to any one of claims 1 to 12 with an organic polyisocyanate, and the urethane The ester prepolymer has a terminal isocyanate group. 一種塗佈組合物，其包含使如請求項1至12中任一項之聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯樹脂。 A coating composition comprising a polyurethane urethane resin obtained by reacting a polycarbonate diol composition according to any one of claims 1 to 12, an organic polyisocyanate, and a chain extender. 一種水系塗佈組合物，其包含使水、如請求項1至12中任一項之聚碳酸酯二醇組合物、有機聚異氰酸酯及鏈伸長劑反應而獲得之聚胺基甲酸酯。 An aqueous coating composition comprising a polyurethane obtained by reacting water, a polycarbonate diol composition according to any one of claims 1 to 12, an organic polyisocyanate, and a chain extender. 一種熱塑性聚胺基甲酸酯，其係使用如請求項1至12中任一項之聚碳酸酯二醇組合物與有機聚異氰酸酯而獲得。 A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of claims 1 to 12 together with an organic polyisocyanate.
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