TWI836382B - Polycarbonate polyol and its manufacturing method, composition and its manufacturing method, polyurethane resin and water-based polyurethane resin dispersion - Google Patents

Abstract

The polycarbonate polyol of the present invention is represented by the following formula (A-1): [In formula (A-1), ^R1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; ^R2 represents an alkanediyl group; n and m each represent an integer greater than 1; plural ^R2s may be the same or different.]

Description

Polycarbonate polyol and its manufacturing method, composition and its manufacturing method, polyurethane resin and water-based polyurethane resin dispersion

The present invention relates to a polycarbonate polyol and a method for producing the same, a composition and a method for producing the same, a polyurethane resin, and an aqueous polyurethane resin dispersion.

Polycarbonate polyols, like polyester polyols, polyether polyols, etc., can be effectively used as raw materials for producing polyurethane resins (also known as "polyurethane resins") by reacting with polyisocyanate compounds. It can be effectively used as a raw material for adhesives, coatings, etc.

Because polyester polyol has ester bonds, polyurethane resin obtained from polyester polyol has the disadvantage of poor hydrolysis resistance. In addition, because polyether polyol has ether bonds, the polyurethane resin obtained from polyether polyol has the disadvantage of poor weather resistance and heat resistance. In view of these, polyurethane resins obtained from polycarbonate polyols tend to be excellent in durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).

Polycarbonate polyols are generally produced by reacting carbonates and diols in the presence of an ester exchange catalyst (ester exchange reaction).

So far, polycarbonate polyols with various structures have been proposed to suit the purpose. For example, Patent Documents 1 and 2 propose polycarbonate polyols obtained by transesterification of polycarbonate diol and a triol compound and/or a tetraol compound. [Advanced technical documents] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 3-220233 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-184380

(The problem that the invention wants to solve)

An object of the present invention is to provide a novel polycarbonate polyol that can be effectively used as a raw material for polyurethane resin and the like, a method for producing the polycarbonate polyol, and a polyurethane resin using the polycarbonate polyol as a raw material. The present invention also aims to provide: a composition containing the polycarbonate polyol and a manufacturing method thereof, as well as a polyurethane resin using the composition as a raw material. The present invention also aims to provide a composition for forming a polyurethane resin that has good tensile strength, elongation and feel, and excellent durability. The present invention also aims to provide a composition for forming a polyurethane resin that has excellent workability, good elongation and feel, and excellent durability. The present invention also aims to provide an aqueous polyurethane resin dispersion containing the above-mentioned polyurethane resin with an acidic group. (Means to solve problems)

The present invention provides the following [1]~[23].

[1] A polycarbonate polyol represented by the following formula (A-1): [In formula (A-1), ^R1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; ^R2 represents an alkanediyl group; n and m each represent an integer greater than 1; plural ^R2s may be the same or different.]

[2] The polycarbonate polyol according to [1], wherein all R ² are linear alkanediyl groups.

[3] The polycarbonate polyol according to claim [1], wherein at least one of R ² is a branched alkane diyl group.

[4] The polycarbonate polyol according to any one of [1] to [3], wherein R ² contains two or more alkane diyl groups.

[5] A composition comprising: a polycarbonate polyol as described in any one of [1] to [4] and a polyol represented by the following formula (B); [Chemical 2] [In formula (B), R ¹ has the same meaning as above.]

[6] The composition according to [5], wherein, when the total molar number of the groups represented by the following formula (a-1) contained in the composition is _CA1 and the total molar number of the polyol contained in the composition is _CB , the molar ratio ( _CA1 / _CB ) is 0.1 to 150. [Chemical 3] [In formula (a-1), * represents a bonding base to the carbonate group.]

[7] The composition according to [5] or [6], further comprising: a compound (A-2) represented by the following formula (A-2) and a compound (A-3) represented by the following formula (A-3): [Chemical 4] [In formula (A-2), ^R1 and ^R2 are synonymous with the above; ⁿ² represents an integer greater than 1; when ⁿ² is greater than 2, the plural ^R2s may be the same or different from each other]; [Chemistry 5] [In formula (A-3), ^R1 and ^R2 have the same meanings as above; ⁿ³ , ^m3 and ^p3 each represent an integer greater than 1; plural ^R2 may be the same or different.]

[8] The composition according to any one of [5] to [7], wherein the total molar number of groups represented by the following formula (a-1) contained in the composition is C _A1 , When the total molar number of groups represented by the following formula (I) contained in the above composition is C _T , the molar ratio (C _A1 /C _T ) is 0.10 to 0.99. [Chemical 6] [In the formula (a-1), * represents the bonding base to the carbonate group. ] [Chemical 7] [In formula (I), R ¹ is synonymous with the above, and * represents a bonding base. ]

[9] The composition according to any one of [5] to [8], wherein the total molar number of the polyols contained in the composition is _CB , and the composition contains: When the total molar number of the base shown in the formula (I) is set to C _T , the molar ratio (C _B /C _T ) is 0.001~0.900; [Chemical 8] [In formula (I), R ¹ is synonymous with the above, and * represents a bonding base. ]

[10] The composition according to any one of [5] to [9], further containing: lithium acetate acetonate.

[11] A method for producing polycarbonate polyol by using a mixed liquid containing a polyol represented by the following formula (B), a diol represented by the following formula (D), a carbonate, and a transesterification catalyst. The polycarbonate polyol according to any one of [1] to [4] is obtained by performing a reflux reaction while removing the alcohol derived from the carbonate from the reaction system. [Chemical 9] [In formula (B), R ¹ is synonymous with the above. ] [Chemical 10] [In formula (D), R ² has the same meaning as above. ]

[12] A method for producing a composition, comprising heating a mixed solution containing a polyol represented by the following formula (B), a diol represented by the following formula (D), a carbonate, and an ester exchange catalyst, and performing a reflux reaction while removing the alcohol derived from the carbonate from the reaction system, thereby obtaining a composition described in any one of [5] to [10]. [Chemical 11] [In formula (B), R ¹ has the same meaning as above.] [Chemical 12] [In formula (D), ^R2 has the same meaning as above.]

[13] A production method as described in [11] or [12], wherein the heating of the mixed solution comprises: heating at a temperature T1 under a pressure of 101.325 kPa ± 20.000 kPa, and then heating at a temperature T2 under a reduced pressure of less than 10.000 kPa; the temperatures T1 and T2 satisfy the relationship of the following formulas (α) and (β), and the reflux reaction distills off the alcohol derived from the carbonate at a temperature below 120°C and removes it from the reaction system. 120°C ≦ T1 ≦ 155°C   ． ． ． (α) 140°C ≦ T2 ≦ 155°C   ． ． ． (β)

[14] The production method according to any one of [11] to [13], wherein the transesterification catalyst content in the mixed liquid is smaller than the polyol, the diol and the diol in the mixed liquid. The total amount of the above carbonate is 100 parts by mass, ranging from 0.001 to 0.050 parts by mass.

[15] The production method as described in any one of [11] to [14], wherein the above-mentioned ester exchange catalyst contains: lithium acetylacetonate.

[16] A polyurethane resin which is a polycondensate of a polyol component and a polyisocyanate component or a cross-linked product thereof, wherein the polyol component contains the polycarbonate polyol according to any one of [1] to [4].

[17] The polyurethane resin according to [16], wherein the polyol component further contains: a polyol represented by the following formula (B); [Chemical 13] [In formula (B), R ¹ is synonymous with the above. ]

[18] The polyurethane resin as described in [17], wherein, when the total molar number of the groups represented by the following formula (a-1) contained in the polyol component is _CA1 and the total molar number of the polyol contained in the polyol component is _CB , the molar ratio ( _CA1 / _CB ) is 0.1 to 150. [Chemical 14] [In formula (a-1), * represents a bonding base to the carbonate group.]

[19] The polyurethane resin according to [17] or [18], wherein the polyol component further comprises: a compound (A-2) represented by the following formula (A-2) and a compound (A-3) represented by the following formula (A-3); [Chemical 15] [In formula (A-2), ^R1 and ^R2 are synonymous with those above; ⁿ² represents an integer greater than or equal to 1; when ⁿ² is greater than or equal to 2, the plural ^R2s may be the same or different from each other.] [Chemistry 16] [In formula (A-3), ^R1 and ^R2 have the same meanings as above; ⁿ³ , ^m3 and ^p3 each represent an integer greater than 1; plural ^R2 may be the same or different.]

[20] The polyurethane resin according to any one of [17] to [19], wherein, when the total molar number of the groups represented by the following formula (a-1) contained in the above polyol component is set as _CA1 and the total molar number of the groups represented by the following formula (I) contained in the above polyol component is set as _CT , the molar ratio ( _CA1 / _CT ) is 0.10 to 0.99. [Chemical 17] [In formula (a-1), * represents a bonding base to the carbonate group.] [Chemical 18] [In formula (I), ^R1 has the same meaning as above, and * represents a bonding base.]

[21] The polyurethane resin according to any one of [17] to [20], wherein the total molar number of the polyols contained in the polyol component is C _B , and When the total molar number including the base represented by the following formula (I) is C _T , the molar ratio (C _B /C _T ) is 0.001 to 0.900. [Chemical 19] [In formula (I), R ¹ is synonymous with the above, and * represents a bonding base. ]

[22] The polyurethane resin according to any one of [16] to [21], wherein the polyol component further contains a polyol having an acidic group.

[23] An aqueous polyurethane resin dispersion comprising: an aqueous medium, and the polyurethane resin described in [22] or a neutralized product thereof dispersed in the aqueous medium. (Effect of the invention)

According to the present invention, there can be provided a novel polycarbonate polyol that can be effectively used as a raw material for polyurethane resin, a manufacturing method thereof, and a polyurethane resin using the polycarbonate polyol as a raw material. According to the present invention, there can also be provided: a composition containing the polycarbonate polyol and a manufacturing method thereof, as well as a polyurethane resin using the composition as a raw material. According to the present invention, it is also possible to provide a composition for forming a polyurethane resin that has good tensile strength, elongation, and feel, and has excellent durability. The present invention also aims to provide a composition for forming a polyurethane resin that has excellent workability, good elongation and feel, and excellent durability. According to the present invention, it is also possible to provide: an aqueous polyurethane resin dispersion containing the above-mentioned polyurethane resin having an acidic group.

The following is a detailed description of the embodiments of the present invention. In addition, in this specification, the numerical range represented by "~" indicates a range including the numerical values recorded before and after the "~" as the minimum value and the maximum value. The minimum value or maximum value of the numerical range represented by "~" can be arbitrarily combined with the maximum value or minimum value of other numerical ranges represented by "~". In addition, the upper limit value and the lower limit value recorded individually can also be arbitrarily combined.

<Polycarbonate polyol> A polycarbonate polyol in one embodiment is a compound represented by the following formula (A-1) (hereinafter also referred to as "compound (A-1)"): [Chemical 20] [In formula (A-1), ^R1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; ^R2 represents an alkanediyl group; n and m each represent an integer greater than 1; plural ^R2s may be the same or different.]

The alkyl group and hydroxyalkyl group represented by R ¹ may be linear or branched. The carbon number system of the alkyl group and the hydroxyalkyl group may be, for example, 1 to 5, 1 to 4, or 1 to 2. Specific examples of the alkyl group and hydroxyalkyl group include methyl, ethyl, propyl, butyl, pentyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, and the like. R ¹ is preferably an alkyl group or a hydroxyalkyl group, more preferably an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms.

The alkane diyl group represented by R ² may be linear or branched. When there are two or more R ² groups, all of them may be linear or branched, or some of them may be linear and the rest may be branched. The carbon number of the alkane diyl group is, for example, 2 to 10. Specific examples of the alkanediyl group include ethanediyl, 1,2-propylenediyl, 1,3-propylenediyl, 1,2-butylenediyl, 1,3-butylenediyl, 1,4-butylenediyl, 1,5-pentanediyl, 2,2-dimethyl-1,3-propylenediyl, 1,6-hexanediyl, 3-methyl-1,5-pentanediyl, 1,8-octanediyl, 2-ethyl-1,6-hexanediyl, 1,9-nonanediyl, 2-methyloctane-1,8-diyl, and 2-butyl-2-ethyl-1,3-propylenediyl.

n and m can be 1~65, 2~60 or 2~55 respectively.

The number average molecular weight of the compound (A-1) is, for example, 200 to 6000. Here, the number average molecular weight is the number average molecular weight calculated as bifunctional polyoxypropylene polyol as measured by GPC (Gel Permeation Chromatography).

The hydroxyl value of the compound (A-1) is, for example, 30 to 800 mgKOH/g. Here, the "hydroxyl value" refers to the number of milligrams (mg) of potassium hydroxide corresponding to the hydroxyl groups in 1 g of the compound (A-1), and is measured according to JIS K1557-1.

The property of the compound (A-1) is not particularly limited, but it may be a solid state at 25°C or a liquid state at 25°C. Compound (A-1) may also be in a liquid state at low temperature (for example, 5°C). The properties of compound (A-1) can be changed by using the type of alkanediyl group (number of carbon atoms, presence or absence of branches, etc.) of ^R2 contained in compound (A-1), and the hydroxyl value of compound (A-1), etc. . For example, when there are multiple types of alkane diradicals, when the alkane diradicals are branched, or when the hydroxyl value of compound (A-1) is high, compound (A-1) is likely to be liquid at 25°C.

Hereinafter, the compound (A-1) will be described in more detail by dividing into a plurality of embodiments (first to third embodiments).

(First embodiment) In the first embodiment, R ² of the compound (A-1) contains only linear alkane diyl groups. That is, all R ² are linear alkane diyl groups. Since R ² of the compound (A-1) contains only linear alkane diyl groups, it is easy to be solid at 25°C.

In the first embodiment, R ² of compound (A-1) preferably contains only one linear alkanediyl group. In this case, the tendency of compound (A-1) to be solid at 25°C is increased.

The carbon number of the linear alkane diyl group is preferably 2 to 10, more preferably 2 to 9, and particularly preferably 4 to 9. Preferred examples of the linear alkane diyl group include 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, and 1,9-nonanediyl.

The number average molecular weight of the compound (A-1) of the first embodiment may be 200-6000, 300-5000, or 500-4000.

The hydroxyl value of the compound (A-1) of the first embodiment is preferably 30 to 800 mgKOH/g, but may also be 40 to 700 mgKOH/g, or 50 to 600 mgKOH/g.

(Second Embodiment) In the second embodiment, R ² of the compound (A-1) contains two or more alkanediyl groups. Since R ² of compound (A-1) contains two or more kinds of alkanediyl groups, it is easy to become liquid at 25°C.

In the second embodiment, from the viewpoint of being able to easily form a polyurethane resin having good tensile strength, elongation, and hand feeling and excellent durability when used as a raw material for a polyurethane resin, ^R2 of the compound (A-1) preferably contains only a linear alkane diyl group. An example of a preferred combination of alkane diyl groups is a combination of two or more alkane diyl groups having 2 to 10 carbon atoms. A more preferred combination of alkane diyl groups is a combination of 1,6-hexanediol and at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,9-nonanediol.

In the second embodiment, when used as a raw material for polyurethane resin, 1,6-hexane in compound (A-1) can easily form a polyurethane resin with good tensile strength, elongation and feel, and excellent durability. The molar number of the radical, relative to the total molar number of the alkane diradicals contained in ^R2 , is preferably 0.30 or more (for example, 0.30~0.95), more preferably 0.40 or more (for example, 0.40~0.95), and still more preferably 0.50 or above (such as 0.50~0.90 or 0.50~0.80).

The number average molecular weight of the compound (A-1) of the second embodiment is preferably 200-6000, and may be 300-5000 or 500-4000.

The hydroxyl value of the compound (A-1) of the second embodiment may be 30 to 800 mgKOH/g, 40 to 700 mgKOH/g, or 50 to 600 mgKOH/g.

(Third Embodiment) In the third embodiment, R ² of the compound (A-1) contains a branched alkanediyl group. The compound (A-1) of the third embodiment has a branched alkanediyl group as ^R2 , and therefore is easily liquid at 25°C.

In the third embodiment, ^R2 of compound (A-1) may contain two or more alkane diyl groups. All of the two or more alkane diyl groups may be branched alkane diyl groups, but from the perspective of being able to easily form a polyurethane resin having excellent workability, good elongation and feel, and excellent durability when used as a raw material for a polyurethane resin, it is preferred that a portion of them be straight-chain alkane diyl groups. In this case, the ratio of the molar number of the branched alkane diyl groups of compound (A-1) to the total molar number of the alkane diyl groups contained in ^R2 is preferably 0.10 to 1, more preferably 0.20 to 0.90, and even more preferably 0.30 to 0.70.

The number of carbon atoms in the branched alkane diyl group is preferably 2 to 10, more preferably 2 to 9, and still more preferably 4 to 9. The number of carbon atoms in the main chain of the branched alkanediyl group (the straight chain with the largest number of carbon atoms) is preferably 2 to 9, more preferably 3 to 9, and still more preferably 4 to 8. Preferred examples of branched alkanediyl are 3-methylpentane-1,5-diyl and 2-methyl-1,8-octanediyl.

The carbon number of the linear alkane diyl group is preferably 2 to 10, more preferably 2 to 9, and particularly preferably 4 to 9. Preferred examples of linear alkanediyl are 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, and 1,9-nonanediyl.

In the third embodiment, from the viewpoint that when used as a raw material for a polyurethane resin, a polyurethane resin having excellent workability, good elongation and good hand feel, and excellent durability can be easily formed, the ratio of the molar number of 1,6-hexanediyl groups in the compound (A-1) to the total molar number of alkanediyl groups contained in ^R2 is preferably 0 or more (e.g., 0 to 0.95), more preferably 0.10 or more (e.g., 0.10 to 0.95), further preferably 0.3 or more (e.g., 0.3 to 0.90), and particularly preferably 0.50 or more (e.g., 0.50 to 0.80).

The number average molecular weight of the compound (A-1) of the third embodiment is preferably 200 to 6000, but may also be 300 to 5000 or 500 to 4000.

The hydroxyl value of the compound (A-1) of the third embodiment is preferably 30 to 800 mgKOH/g, and may be 40 to 700 mgKOH/g or 50 to 600 mgKOH/g.

The polycarbonate polyol (compound (A-1)) described above is, for example, a reaction product of a polyol represented by the following formula (B) (hereinafter also referred to as "polyol (B)"), a diol represented by the following formula (D) (hereinafter also referred to as "diol (D)"), and a carbonate, and is obtained by reacting two of the hydroxyl groups of the polyol (B) with a carbonate, or a reaction product of a carbonate and a diol (D). [Chemistry 21] [In formula (B), R ¹ has the same meaning as above.] [Chemical 22] [In formula (D), ^R2 has the same meaning as above.]

Specific examples of the polyol (B) include trihydroxymethylpropane, trihydroxymethylethane, and pentaerythritol, which may be used alone or in combination of two or more.

Specific examples of the diol (D) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. Diol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8- Octanediol, 2-ethyl-1,6-hexanediol, 1,9-nonanediol, 2-methyloctane-1,8-diol, and 2-butyl-2-ethyl- 1,3-propanediol. These systems may be used alone or two or more types may be used in combination.

Examples of the carbonate system include: dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethyl carbonate, trimethylene carbonate, 1 , 2-propyl carbonate, etc. These systems may be used alone or two or more types may be used in combination. From the viewpoint of ease of acquisition, ease of setting polymerization reaction conditions, etc., it is preferable to use one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethyl carbonate. At least 1 species.

At least one of the hydroxyl groups of the compound (A-1) is derived from, for example, the hydroxyl group of the polyol (B) (the unreacted hydroxyl group of the polyol (B)). This hydroxyl group is affected by steric hindrance and tends to have lower reactivity than the hydroxyl group derived from the diol (D). Furthermore, the length from the hydroxyl group derived from the polyol (B) to the branch (the carbon atom bonded to R ¹ ) is shorter than the length from the hydroxyl group derived from the diol (D) to the branch, so The polyurethane resin obtained by reacting compound (A-1) and an isocyanate compound tends to have higher rigidity. Compound (A-1) can be expected to be used in a variety of polyurethane resin raw materials by utilizing the reactivity of the hydroxyl group and the difference in length between the hydroxyl group and the branch.

(composition) A composition according to one embodiment contains the polycarbonate polyol (compound (A-1)) of the above embodiment and polyol (B).

The polyol (B) has the same meaning as above, and the alkane diyl group contained in R ² of the polyol (B) may be the same as the alkane diyl group contained in R ² of the compound (A-1). When R ² of the compound (A-1) contains two or more alkane diyl groups, the composition may contain two or more polyols (B). In this case, the combination of alkane diyl groups contained in R ² of the two or more polyols (B) may be the same as the combination of alkane diyl groups contained in R ² of the compound (A-1).

If the total mole number of the groups represented by the following formula (a-1) contained in the composition is C _A1 and the total mole number of the polyol (B) contained in the composition is C _B , then the mole number The preferred ear ratio (C _A1 /C _B ) is 0.1~150. If the molar ratio (C _A1 /C _B ) is within the above range, when the composition is used as a raw material for a polyurethane resin, it is easy to form a polyurethane resin with good elongation and feel and excellent durability. [Chemistry 23] [In the formula (a-1), * represents the bonding base to the carbonate group (-OC(O)O-). ] In addition, even if it has the same structure as the group represented by the above formula (a-1), when * is bonded to a group other than the carbonate group (such as a hydroxyl group (-OH), etc.), it is not included in the formula (a -1) in the base shown.

The molar ratio (C _A1 /C _B ) is measured from ¹ H-NMR of the composition using deuterated chloroform as the solvent and tetramethylsilane as the reference material, and the ¹ H-NMR mass spectrum signal obtained from the measurement. The integral value can be obtained. Specifically, for example, the integrated value Δ _S1 (2 mol parts of hydrogen atom) of the methylene signal (S1) adjacent to the hydroxyl group of the group represented by the formula (a-1) is similar to that of the hydroxyl group of the polyol (B). The molar ratio (C _A1 /C _B ) can be calculated from the integrated value Δ _S2 (6 mol points of hydrogen atoms) of the methylene signal (S2) at the adjacent position. In this case, the molar ratio (C _A1 /C _B ) can be expressed as three times the ratio of the signal (S1) integrated value Δ _S1 to the signal (S2) integrated value Δ _S2 (3×Δ _S1 /Δ _S2 ).

The composition may further contain at least one of a polycarbonate polyol represented by the following formula (A-2) (hereinafter referred to as "compound (A-2)") and a polycarbonate polyol represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)"). [In formula (A-2), ^R1 and ^R2 are synonymous with those above; ⁿ² represents an integer greater than or equal to 1; when ⁿ² is greater than or equal to 2, the plural ^R2s may be the same or different from each other.] [Chem. 25] [In formula (A-3), ^R1 and ^R2 have the same meanings as above; ⁿ³ , ^m3 and ^p3 each represent an integer greater than 1; plural ^R2 may be the same or different.]

The atom or group contained in R ¹ of compound (A-2) may be the same as the atom or group contained in R ¹ of compound (A-1). Likewise, the atom or group contained in R ¹ of compound (A-3) is preferably the same as the atom or group contained in R ¹ of compound (A-1).

The alkanediyl group contained in ^R2 of compound (A-2) may be the same as the ^alkanediyl group contained in R2 of compound (A-1). Similarly, the alkanediyl group contained in ^R2 of compound (A-3) may be the same as the ^alkanediyl group contained in R2 of compound (A-1). When R ² of compound (A-1) contains two or more types of alkanediyl groups, it is preferred that R ² of both compound (A-2) and compound (A-3) contain two or more types of alkanediyl groups. In this case, the combination of alkanediyl groups contained in ^R2 of compound (A-2) and compound (A-3) may be the same as the combination of alkanediyl groups contained in ^R2 of compound (A-1).

n ² , n ³ , m ³ and p ³ can be 1 to 65, 2 to 60 or 3 to 50 respectively.

If the total mole number of the groups represented by the above formula (a-1) contained in the composition is set to C _A1 , and the total mole number of the above-mentioned polyol contained in the composition is set to _CB , the composition contains the following When the total mole number of the base shown in formula (I) is set to C _T , the mole ratio (C _A1 /C _T ) can be 0.10~0.99, and the mole ratio (C _B /C _T ) can be 0.001~0.900 . If the molar ratio (C _A1 /C _T ) and the molar ratio (C _B /C _T ) are respectively within the above ranges, when the composition is used as a raw material for polyurethane resin, it will be easy to form a polyurethane resin with good elongation and feel, and Polyurethane resin with excellent durability. [Chemical 26] [In formula (I), R ¹ is synonymous with the above, and * represents a bonding base. ]

The molar ratio ( _CA1 /C _T ) and the molar ratio ( _CB /C _T ) can be determined, for example, from ^1H -NMR measurement of the composition and the integrated value of the ^1H -NMR mass spectrum signal obtained by using deuterated chloroform as a solvent and tetramethylsilane as a standard substance, similarly to the molar ratio ( _CA1 /C _B ). Specifically, for example, when ^R1 in formula (I) is an alkyl group, the molar ratio ( ^CA1 /CT) can be calculated from the ratio of the integral value _ΔS1 (2 mol parts of hydrogen atoms) of the signal (S1) and the integral value _ΔS3 (3 mol parts of hydrogen atoms) of the terminal methyl signal (S3) of R1 (alkyl group) in formula (I), and the molar ratio ( _CB / _CT ) can be calculated from the ratio of the integral value _ΔS2 (6 mol parts of hydrogen atoms) of the signal (S2) and the integral value _ΔS3 (3 mol parts of hydrogen atoms) of the signal ( _{S3 )} . In this case, the Moire ratio ( _CA1 / _CT ) can be expressed as 1.5 times (1.5× _ΔS1 / _ΔS3 ) the ratio of the integral value _ΔS1 of the signal (S1) to the integral value _ΔS3 of the signal (S3), and the Moire ratio ( _CB / _CT ) can be expressed as 0.5 times (0.5× _ΔS2 / _ΔS3 ) the ratio of the integral value _ΔS2 of the signal (S2) to the integral value _ΔS3 of the signal (S3).

The composition may further contain, for example, the above-mentioned diol (D), the above-mentioned carbonate, or a polycarbonate diol which is a reaction product of the above-mentioned diol (D) and the above-mentioned carbonate. However, it is preferable that the composition mainly contains a compound having a group represented by the above formula (I) (compounds (A-1) to (A-3), polyol (B), etc.). The "main component" here refers to the component (component group) with the highest mass fraction. The glycol (D) content is based on the total mass of the composition and can be 20 to 60 mass%. The carbonate content is based on the total mass of the composition and can be 20 to 60 mass%. The polycarbonate diol content is based on the total mass of the composition and can be 20 to 80 mass%.

The polycarbonate diol system that the composition can contain is represented by the following formula (E): [Chemical 27] [In formula (E), R ² has the same meaning as above, and q represents an integer of 1 or more (for example, 1 to 60). ]

When polycarbonate diol represented by the above formula (E) (hereinafter referred to as "polycarbonate diol (E)") is contained, the q value indicating the degree of polymerization is smaller than the total amount of polycarbonate diol (E). The greater the proportion of large compounds, the better the hand properties tend to be. This tendency is due to the greater the proportion of 1,6-hexanediyl among the 1,4-butanediyl, 1,5-pentadiyl and 1,6-hexanediyl contained in R ² , and the polycarbonate diol ( The larger the number average molecular weight of E) is, the more obvious it is. The above ratio can be confirmed by comparing peaks corresponding to each component in an LC mass spectrum obtained by performing LC-MS measurement using a reverse phase chromatography analyzer, for example. For example, among the peaks observed in the LC mass spectrum, if the maximum intensity of the peak corresponding to polycarbonate diol (E) with q 3 is set to P3, and the peak intensity corresponding to polycarbonate diol (E) with q 4 When the maximum intensity is set to P4 and the maximum intensity of the peak corresponding to polycarbonate diol (E) with q=5 is set to P5, the ratio of P3 to the sum of P3, P4 and P5 (P3/[P3+P4+P5] ), the best series is 0.1~0.75, the better series is 0.15~0.50, and the particularly good series is 0.20~0.40. The ratio of P5 to the sum of P3, P4 and P5 (P5/[P3+P4+P5]) is preferably 0.1~0.70, more preferably 0.15~0.50, and further preferably 0.2~0.40. If P3/(P3+P4+P5) and P5/(P3+P4+P5) are within the above range, when the composition is used as a raw material for polyurethane resin, there is a tendency to easily form a polyurethane resin with good feel. Furthermore, if P5/(P3+P4+P5) is 0.70 or less, when the polyurethane resin is torn from the release paper on which the decorative shape has been applied, the decoration tends to be easily retained. In addition, the LC-MS measurement system uses a gradient method. Furthermore, by using the intensity of the blank sample (without sample) to reduce the intensity of the sample sample, the baseline can be kept constant. In this way, the intensity of each peak can be calculated correctly. In order to accurately compare the peak intensities, the maximum value of the peak intensity in P3 to P5 was set to 1, and the peak intensities other than the maximum intensity were calculated. The correspondence between peaks and compounds can be confirmed by, for example, performing individual MS measurements of each peak (device: Bruker Daltonics microTOF, ion source: APCI, measurement mode: positive mode) and analyzing the main peak of the obtained mass spectrum.

The composition may be a reaction mixture of polyol (B), diol (D), and carbonate. The above reaction is usually carried out in the presence of a transesterification catalyst, so the composition may further contain a transesterification catalyst. The preferred transesterification catalyst is lithium acetate acetonate. The transesterification catalyst content is based on the total mass of the composition, and is preferably 0.0001~0.100% by mass.

The properties of the composition are not particularly limited, and may be solid at 25°C or liquid at 25°C. The composition may also be liquid at a low temperature (e.g., 5°C). The properties of the composition may be changed by the types and content ratios of the components (e.g., compounds (A-1) to (A-3) and polyol (B)).

The number average molecular weight of the composition is, for example, 200 to 6000. Here, the number average molecular weight of the composition is the number average molecular weight converted into bifunctional polyoxypropylene polyol by measuring the entire composition using GPC (Gel Permeation Chromatography).

The hydroxyl value of the composition is, for example, 30 to 800 mgKOH/g. Here, the hydroxyl value of the composition refers to the number of milligrams (mg) of potassium hydroxide corresponding to the hydroxyl groups in 1 g of the composition, and is measured according to JIS K1557-1.

Hereinafter, the above-mentioned composition will be described in more detail by dividing the plurality of embodiments (first to third embodiments).

(First Embodiment) The compound (A-1) of the composition of the first embodiment contains the compound (A-1) of the first embodiment. The molar ratio (C _A1 /C _B ) in the first embodiment is, for example, 0.2 to 150. The composition of the first embodiment having such characteristics easily becomes solid at 25°C.

In the first embodiment, when deuterated chloroform is used as the solvent and tetramethylsilane is used as the standard substance, when ¹ H-NMR measurement of the composition is performed, for example, the signal (S1) is observed in the range of 3.430 ppm to less than 3.550 ppm of the ¹ H-NMR mass spectrum, and the signal (S2) is observed in the range of 3.725 ppm to 3.800 ppm (or 3.725 ppm to less than 3.800 ppm) of the ¹ H-NMR mass spectrum. Furthermore, when R ¹ of formula (I) is ethyl, the signal (S3) is observed in the range of 0.700 ppm to 1.000 ppm, and when R ¹ of formula (I) is methyl, the signal (S3) is observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in the first embodiment, the Moire ratio ( _CA1 /C _B ), the Moire ratio ( _CA1 /C _T ), and the Moire ratio (C _B /C _T ) can be obtained from the ratios of the signal integrated values.

The molar ratio (C _A1 /C _B ) of the composition of the first embodiment is preferably 0.500 or more, more preferably 3.000 or more, and further preferably 5.000 or more. The molar ratio (C _A1 /C _B ) is preferably 120 or less, more preferably 90 or less, and further preferably 60 or less. If the molar ratio (C _A1 /C _B ) is within the above range, when the composition is used as a raw material for polyurethane resin, it will be possible to easily form a polyurethane resin with good tensile strength, elongation and feel, and excellent durability. tendency.

The molar ratio (C _A1 /C _T ) of the composition of the first embodiment is, for example, 0.12 to 0.99. The molar ratio (C _A1 /C _T ) may be 0.150 or more or 0.200 or more, or 0.800 or less or 0.500 or less. When the molar ratio (C _A1 /C _T ) is within the above range, when the composition is used as a raw material for a polyurethane resin, it tends to be easy to form a polyurethane resin having good tensile strength, elongation, and hand feel, and excellent durability.

The molar ratio (C _B /C _T ) of the composition of the first embodiment is, for example, 0.001 to 0.900. The molar ratio (C _B /C _T ) may be 0.003 or more or 0.005 or more, and may be 0.300 or less or 0.100 or less. If the molar ratio (C _B /C _T ) is within the above range, when the composition is used as a raw material for polyurethane resin, it will be possible to easily form a polyurethane resin with good tensile strength, elongation and feel, and excellent durability. tendency.

In the first embodiment, the ratio of the integrated value Δ _S1 of the signal (S1) to the integrated value Δ _S2 of the signal (S2) (Δ _S1 /Δ _S2 ) is, for example, 0.067 to 50. The above ratio (Δ _S1 /Δ _S2 ) may be 0.500 or more, 1.000 or more or 2.000 or more, and may be 40 or less, 30 or less or 20 or less.

In the first embodiment, the ratio (Δ _S1 / Δ _S3 ) of the integral value Δ _S1 of the signal (S1) to the integral value Δ _S3 of the signal (S3) is, for example, 0.08 to 0.66. The above ratio (Δ _S1 / Δ _S3 ) may be greater than or equal to 0.100 or greater than or equal to 0.133, or less than or equal to 0.533 or less than or equal to 0.333.

In the first embodiment, the ratio (Δ _S2 /Δ S3 ) of the integrated value Δ _S2 of the signal (S2) to the integrated value Δ _S3 of the signal ( _S3 ) is, for example, 0.002 to 1.8. The ratio (Δ _S2 /Δ _S3 ) may be 0.006 or more or 0.010 or more, and may be 0.600 or less or 0.200 or less.

(Second embodiment) The compound (A-1) of the second embodiment composition contains the compound (A-1) of the second embodiment. In the second embodiment, the molar ratio ( _CA1 /C _B ) is, for example, 0.1 to 150. The second embodiment composition having such characteristics is easily in liquid form at 25°C.

In the second embodiment, when deuterated chloroform is used as the solvent and tetramethylsilane is used as the reference material, and ¹ H-NMR measurement of the composition is performed, for example, the above-mentioned signal (S1) will be 3.430 ppm or more in the ¹ H-NMR mass spectrum and The above signal (S2) is observed in the range of 3.720ppm and below 3.800ppm (or 3.720ppm and below 3.800ppm) of the ¹ H-NMR mass spectrum. In addition, when R ¹ of the formula (I) is an ethyl group, the above signal (S3) is observed in the range of 0.700 ppm or more and 1.000 ppm or less. When R ¹ of the formula (I) is a methyl group, the above signal (S3) is observed in the range of 0.700 ppm or more and 1.000 ppm or less. Signal (S3) will be observed in the range above 0.700ppm and below 1.130ppm. Therefore, in the second embodiment, from the ratio of the integrated values of these signals, the molar ratio (C _A1 /C _B ), the molar ratio (C _A1 /C _T ) and the molar ratio (C _B /C _T ).

The molar ratio ( _CA1 / _CB ) of the second embodiment composition is preferably 0.100 or more, more preferably 3.000 or more, and further preferably 5.000 or more. The molar ratio ( _CA1 / _CB ) is preferably 150 or less, more preferably 90 or less, and further preferably 60 or less. When the molar ratio ( _CA1 / _CB ) is within the above range, when the composition is used as a raw material for a polyurethane resin, it tends to be easy to form a polyurethane resin having good tensile strength, elongation, and hand feel, and excellent durability.

The molar ratio (C _A1 /C _T ) of the composition of the second embodiment is, for example, 0.10 to 0.99. The molar ratio (C _A1 /C _T ) may be 0.200 or more or 0.300 or more, and may be 0.800 or less or 0.600 or less. If the molar ratio (C _A1 /C _T ) is within the above range, when the composition is used as a raw material for polyurethane resin, it will be possible to easily form a polyurethane resin with good tensile strength, elongation and feel, and excellent durability. tendency.

The molar ratio ( _CB / _CT ) of the composition of the second embodiment is, for example, 0.001 to 0.900. The molar ratio ( _CB / _CT ) may be 0.005 or more or 0.010 or more, or 0.300 or less or 0.100 or less. When the molar ratio ( _CB / _CT ) is within the above range, when the composition is used as a raw material for a polyurethane resin, it tends to be easy to form a polyurethane resin having good tensile strength, elongation, and hand feel, and excellent durability.

In the second embodiment, the ratio (Δ _S1 / Δ _S2 ) of the integral value Δ _S1 of the signal (S1) to the integral value Δ _S2 of the signal (S2) is, for example, 0.030 to 50. The above ratio (Δ _S1 / Δ _S2 ) may be greater than 0.500, greater than 1.000, or greater than 2.000, or less than 40, less than 30, or less than 20.

In the second embodiment, the ratio (Δ _S1 / Δ _S3 ) of the integral value Δ _S1 of the signal (S1) to the integral value Δ _S3 of the signal (S3) is, for example, 0.067 to 0.66. The above ratio (Δ _S1 / Δ _S3 ) may be greater than or equal to 0.133 or greater than or equal to 0.200, or less than or equal to 0.533 or less than or equal to 0.400.

In the second embodiment, the ratio (Δ _S2 /Δ S3 ) of the integrated value Δ _S2 of the signal (S2) to the integrated value Δ _S3 of the signal ( _S3 ) is, for example, 0.002 to 1.800. The above ratio (Δ _S2 /Δ _S3 ) may be 0.010 or more or 0.020 or more, and may be 0.6 or less or 0.2 or less.

(Third Embodiment) The compound (A-1) of the composition of the third embodiment contains the compound (A-1) of the above-mentioned third embodiment. In the third embodiment, the molar ratio (C _A1 /C _B ) is, for example, 0.1 to 150. The composition of the third embodiment having such characteristics is easily liquid at 25°C.

In the third embodiment, when deuterated chloroform is used as the solvent and tetramethylsilane is used as the reference material, and ¹ H-NMR measurement of the composition is performed, for example, the above-mentioned signal (S1) will be 3.450 ppm or more in the ¹ H-NMR mass spectrum. And the above-mentioned signal (S2) is observed in the range of 3.720ppm and below 3.800ppm (or 3.720ppm and less than 3.800ppm) of the ¹ H-NMR mass spectrum. Therefore, in the third embodiment, the molar ratio (C _A1 /C _B ) can be obtained from the ratio of the integrated values of these signals.

The molar ratio ( _CA1 / _CB ) of the composition of the third embodiment is preferably 0.100 or more, more preferably 1.000 or more, and further preferably 2.000 or more. The molar ratio ( _CA1 / _CB ) is preferably 120 or less, more preferably 90 or less, and further preferably 60 or less. When the molar ratio ( _CA1 / _CB ) is within the above range, when the composition is used as a raw material for a polyurethane resin, it tends to be easy to form a polyurethane resin having excellent workability, good elongation and feel, and excellent durability.

In the third embodiment, the ratio ( _ΔS1 /ΔS2) of the integrated value _ΔS1 of the signal (S1) to the integrated value _ΔS2 of the signal ( _S2 ) is, for example, 0.033~50. The above ratio ( _ΔS1 / _ΔS2 ) may be 0.500 or more, 1.000 or more or 2.000 or more, and may be 40 or less, 30 or less or 20 or less.

<Production method of polycarbonate polyol and composition>

The method for producing the compound (A-1) according to the above embodiment is to heat a mixed liquid containing a polyol (B), a diol (D), a carbonate, and a transesterification catalyst while removing carbonic acid derived from the reaction system. While carrying out a reflux reaction (ester exchange reaction) with the alcohol of the ester, compound (A-1) is obtained.

In the above method, the reaction mixture containing compound (A-1) can also obtain the above-mentioned embodiment of the composition. Therefore, the above method can also be regarded as a method for producing the above-mentioned embodiment of the composition.

The details of the polyol (B), diol (D) and carbonate are as described above, and the preferred examples (preferred ^R1 and ^R2 examples, and preferred combination examples) are the same as the preferred examples and preferred combination examples of ^R1 and ^R2 possessed by compound (A-1). From the viewpoint of easily obtaining the desired compound (A-1), lithium acetylacetonate is preferably used as the transesterification catalyst.

When two or more diols (D) are used, from the perspective of being able to easily form a polyurethane resin having good tensile strength, elongation, good hand feel, and excellent durability when used as a raw material for a polyurethane resin, the ratio of the molar number of 1,6-hexanediol to the total molar number of diols (D) is preferably 0.30 or more (e.g. 0.30 to 0.95), more preferably 0.40 or more (e.g. 0.40 to 0.95), and further preferably 0.50 or more (e.g. 0.50 to 0.90 or 0.50 to 0.80).

The mixing ratio of polyol (B) and diol (D) [diol (D) content in the mixed liquid/polyol (B) content in the mixed liquid], preferably 1/100~5 in terms of molar ratio /1, preferably 1/80~3/1. By setting the mixing ratio of diol and polyol to the above range, compound (A-1) can be obtained efficiently. The above mixing ratio may also be 1/5~60/1 or 1/1~40/1 in terms of molar ratio.

Mixing ratio of carbonate, polyol (B) and diol (D) [carbonate content in the mixed liquid/total content of polyol (B) and diol (D) in the mixed liquid], emol The better system is 1/3~3/1, and the better system is 1/2.5~2.5/1. By setting the mixing ratio of carbonate, polyol (B), and diol (D) within the above range, compound (A-1) can be obtained efficiently.

The content of the ester exchange catalyst in the mixed solution can be 0.0001-0.1 parts by mass, or 0.0005-0.01 parts by mass, relative to 100 parts by mass of the total amount of the polyol, diol and carbonate in the mixed solution, from the viewpoint of being able to easily and appropriately control the reaction temperature and suppress the increase in the color number of the reaction product. The content of the ester exchange catalyst is preferably as small as possible from the viewpoint of being able to easily control the reactivity of the polyurethane reaction. If the content of the ester exchange catalyst increases, the reactivity of the polyurethane reaction is easily improved. The content of the ester exchange catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and further preferably 0.003 parts by mass or more, relative to 100 parts by mass of the total amount of the polyol, diol and carbonate in the mixed solution, from the viewpoint of being easy to control the polyurethane reaction. From the viewpoint of suppressing the increase in the color number of the reaction product, the content of the transesterification catalyst in the mixed solution is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and further preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyol, diol and carbonate in the mixed solution. From these viewpoints, the content of the transesterification catalyst in the mixed solution is preferably 0.001-0.050 parts by mass, more preferably 0.002-0.040 parts by mass, and further preferably 0.003-0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyol, diol and carbonate in the mixed solution.

The heating temperature (reaction temperature) of the mixed liquid is, for example, 80 to 250°C, or 100 to 220°C. If the reaction temperature is 80° C. or higher, the transesterification reaction proceeds easily, and the desired compound (A-1) can be easily obtained. If the reaction temperature is 250° C. or lower, the color number of the obtained compound (A-1) and the composition polyol can be suppressed. In addition, the transesterification reaction can be carried out while maintaining the temperature at a constant state, or the reaction can be carried out while increasing the temperature in a stepwise or continuous manner according to the progress of the reaction. From the viewpoint of easily obtaining the desired compound (A-1), it is preferable to heat at a temperature T1 that satisfies the relationship of the following formula (α), and then to heat at a temperature T2 that satisfies the relationship of the following formula (β). In addition, the temperature T1 and the temperature T2 preferably satisfy the relationship of the following formula (γ). In addition, the average temperature T1 _m of the first heating temperature and the average temperature T2 _m of the second heating temperature preferably satisfy the relationship of the following formula (δ). Thus, the progress of the reaction can also be estimated from the amount of distillate. 120℃≦T1≦155℃． ． ． (α) 140℃≦T2≦155℃． ． ． (β) T1<T2. ． ． (γ) T1 _m <T2 _m . ． ． (δ)

The mixed solution can be heated under normal pressure, but in the second half of the reaction, it can also be carried out under reduced pressure (e.g., 101~0.1 kPa). This can speed up the distillation rate of the generated distillate and accelerate the progress of the reaction. In addition, the so-called "normal pressure" in this specification refers to a pressure of 101.325 kPa±20.000 kPa. From the viewpoint of easily obtaining the desired compound (A-1), the heating of the mixed solution preferably includes: first heating at a pressure of 101.325 kPa ± 20.000 kPa (first heating), and then heating at a reduced pressure of less than 10.000 kPa (second heating). More preferably, the temperature of the first heating is a temperature T1 satisfying the relationship of the above formula (α), and the temperature of the second heating is a temperature T2 satisfying the relationship of the above formula (β). More preferably, the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula (γ). In addition, from the viewpoint of easily obtaining the compound (A-1), it is preferred to distill off the alcohol derived from the carbonate at a temperature below 120°C and remove it from the reaction system.

The above-mentioned production method may also perform post-processing such as distillation and drying on the reaction mixture obtained. Moreover, in the above-mentioned production method, after obtaining compound (A-1) or a composition containing the same, components such as polyol (B) are added to prepare the composition of the above-mentioned embodiment (for example, satisfying the above-mentioned molar ratio (C _A1 / C _B ), molar ratio (C _A1 /C _T ) and molar ratio (C _B /C _T )).

＜Polyurethane resin and its manufacturing method＞ Polyurethane resin is a polycondensate of a polyol component and a polyisocyanate component or a cross-linked product thereof. The "cross-linked product" here refers to one in which condensation polymers are cross-linked using a chain extension agent or the like.

(Polyol component) The polyol component contains the above-mentioned compound (A-1). The polyol component may also contain a polyol other than compound (A-1) (a compound having two or more terminal hydroxyl groups). The polyol component may further contain, for example, a polyol that can be contained in the above-mentioned composition (compound (A-2), compound (A-3), polyol (B), diol (D), polycarbonate diol, etc.). The content ratio of these polyols may also be the same as the polyol content ratio of the above-mentioned composition [for example, molar ratio ( _CA1 / _CB ), molar ratio ( _CA1 / _CT ) and molar ratio ( _CB / _CT )]. In other words, the polyol component may also contain a polyol mixture in which compounds other than the polyol are removed from the above-mentioned composition.

The polyol component may further contain a polyol having an acidic group. In this case, the polyurethane resin contains acidic groups. Polyurethane resins with acidic groups are suitable for water-based polyurethane resin dispersions. Related water-based polyurethane resin dispersions will be described later.

The acidic group is, for example, a functional group (hydrophilic group) that imparts hydrophilicity to an isocyanate group-terminated prepolymer obtained by reaction with isocyanate. Examples of the polyol system having such an acidic group include dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), dimethylol valeric acid, dimethylol nonanoic acid and the like. Alkanoic acid.

(Polyisocyanate) Examples of the polyisocyanate system include aromatic polyisocyanate, aromatic aliphatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Moreover, modified polyisocyanate which is one of these modified bodies can also be used. Modified polyisocyanate systems include, for example: isocyanate-modified polyisocyanate (isocyanate trimer), allophanate-modified polyisocyanate, uretdione-modified polyisocyanate, and polyurethane-modified polyisocyanate. , Biuret modified polyisocyanate, uretonimine modified polyisocyanate, urea modified polyisocyanate, etc. These systems may be used alone or two or more types may be used in combination.

Examples of aromatic isocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate/2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'- Diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc.

Examples of aromatic aliphatic isocyanates include 1,3-diisocyanatophenylene dimethyl ester, 1,4-diisocyanatophenylene dimethyl ester, and mixtures thereof; 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, and mixtures thereof; ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

Examples of aliphatic isocyanates include: hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, Lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-Trimethylhexane diisocyanate, decamethylene diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethyl Hexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl yl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)carbonate (Isocyanatoethyl) ether, 1,4-butanediol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2 , 6-diisocyanatocaproate, 2-isocyanatopropyl-2,6-diisocyanatocaproate, etc.

Examples of the alicyclic isocyanate include isophorone diisocyanate, cyclohexyl diisocyanate, di(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, diisocyanatomethylcyclohexylmethane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, di(4-isocyanato-n-butylene)neopentatriol, hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatomethyl)cyclohexane, diisocyanatomethyl-3-(2-isocyanatomethyl)cyclohexane, diisocyanatomethyl-2 ... 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(isocyanatomethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2-(isocyanatomethyl)-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)bicyclo[2.2.1]heptane, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, and the like.

(Polyol component/polyisocyanate component blending ratio) The blending ratio of the polyol component to the polyisocyanate component is preferably 9:1~1:9, and more preferably 6:4~4:6, based on the molar ratio of the active hydrogen in the polyol component to the isocyanate group in the polyisocyanate component. If the blending ratio is within this range, the polyurethane resin tends to have better performance.

(Chain extender) The chain extender can be appropriately selected according to the purpose and application. Examples of chain extenders include water; ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, styrene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]propane [0043] The invention relates to low molecular weight polyols such as [(4-(2-hydroxyethoxy)phenyl)sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, etc.; high molecular weight polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyetherester polyols, polycarbonate polyols, polyolefin polyols, etc.; polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. The amount of the chain extender (the proportion of the structure derived from the chain extender contained in the polyurethane resin) can be 0.1 to 50 parts by weight relative to 100 parts by weight of the total amount of the polyol component and the polyisocyanate component. In addition, when the chain extender is a polyol, the content of the polyol is calculated including both the chain extender and the polyol component.

The above-mentioned polyurethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and an optional chain extension agent (polyurethanization reaction). The polyurethanization reaction can be carried out at room temperature (for example, 25°C) or under heating (for example, 40 to 150°C).

During the polyurethanation reaction, a catalyst (polyurethanation catalyst) can also be added for the purpose of shortening the reaction time, increasing the reaction rate, etc. Examples of the catalyst system include: tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexanediamine; and stannous octoate, Tin-based catalysts such as stannous oleate and dibutyltin dilaurate and other metal catalysts. These systems may be used alone or two or more types may be used in combination. Among these, dibutyltin dilaurate is preferably used. The usage amount of the catalyst may be 0.001 to 100 parts by mass relative to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.

When a catalyst is used in the polyurethanization reaction, it is preferable to use a phosphorus compound for handling the catalyst. 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 diphenyl phosphate. Phosphate triesters such as cresyl ester; methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate , 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol acid phosphate, methacrylic acid -2-Hydroxyethyl acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl)phosphate and other acidic phosphates; triphenyl phosphite, phosphite Nonyl phenyl ester, tricresyl phosphite, triethyl phosphite, ginseng phosphite (2-ethylhexyl), tridecyl phosphite, trilauryl phosphite, ginseng phosphite (tridecyl ester) ), trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl monodecyl phosphite, trilauryl phosphite, hydrogen phosphite Diethyl ester, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis( Decyl) neopentyl erythritol diphosphite, tristearyl phosphite, distearyl neopentyl erythritol diphosphite, phosphite (2,4-di-tert-butylphenyl ester), etc. Phosphate esters; phosphoric acid, phosphorous acid, hypophosphorous acid, etc. These systems may be used alone or two or more types may be used in combination. Among these, acidic phosphate is preferred, and 2-ethylhexyl acidic phosphate is more preferred. The usage amount of the phosphorus compound may be 10 to 2000 parts by mass relative to 100 parts by mass of the catalyst.

The polyurethane reaction can be carried out in the presence of a solvent. Examples of the solvent include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.

The polyurethane resin system described above has good elongation and feel, excellent durability, and may have good tensile strength depending on the situation. Therefore, the above-mentioned polyurethane resin is suitable for synthetic leather, artificial leather, coated materials, etc.

<Aqueous polyurethane resin dispersion> Aqueous polyurethane resin dispersion contains: an aqueous medium, and a polyurethane resin dispersed in the aqueous medium or a neutralized product thereof. The polyurethane resin is a polyurethane resin containing an acidic group (the polyol component contained is a polyol having an acidic group).

The aqueous medium may be a solution containing an emulsifier, a dispersant, etc. in addition to water. The aqueous medium preferably contains water, and more preferably consists only of water.

When the aqueous polyurethane resin dispersion contains a neutralized product of the polyurethane resin, the acidic group of the polyurethane resin can be neutralized by a neutralizer. Examples of the neutralizer include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, iodine, N-methyliodine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified iodine; alkali metals such as lithium, potassium, and sodium; and inorganic bases such as sodium hydroxide and potassium hydroxide. From the perspective of improving the durability and smoothness of the coating, it is preferred to use a highly volatile neutralizer such as ammonia, trimethylamine, triethylamine, etc., which can be easily dissociated by heating. These neutralizers can be used alone or in combination of two or more.

When producing aqueous polyurethane resin dispersions, compounds containing anionic polar groups can also be used. The compound containing an anionic polar group may be composed of, for example, an organic acid having one or more active hydrogens and a neutralizing agent. Examples of organic acids include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, thiosulfonates, and the like. The anionic polar groups contained in the organic acid can be introduced alone, or they can be combined with metal ions like chelates.

When producing aqueous polyurethane resin dispersions, compounds containing cationic polar groups can also be used. The compound containing a cationic polar group is composed of, for example, one selected from the group consisting of a tertiary amine having one or more active hydrogens, a neutralizer for inorganic acids, a neutralizer for organic acids, and a quaternary agent. . Furthermore, as the compound containing a cationic polar group, cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts can also be used.

Examples of tertiary amines having one or more active hydrogen atoms include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, triisopropanolamine, N-methyl-bis-(3-aminopropyl)-amine, and N-methyl-bis-(2-aminopropyl)-amine. Furthermore, what is obtained by adding alkylene oxide to a primary amine such as ammonia or methylamine, or a secondary amine such as dimethylamine, can also be used.

Examples of inorganic acids and organic acids include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.

Examples of the quaternary agent include dimethyl sulfate, chlorotoluene, bromoacetamide, chloroacetamide, and the like. Furthermore, halogenated alkyl groups such as ethyl bromide, propyl bromide and butyl bromide can also be used.

The water-based polyurethane resin dispersion system can be produced, for example, by sequentially performing the following steps: reacting a polyol component containing a polyol with an acidic group and a polyisocyanate component in the presence of a solvent (or in the absence of a solvent) to form The steps of making a polyurethane prepolymer; neutralizing the acidic groups in the prepolymer with a neutralizing agent; dispersing the neutralized prepolymer in an aqueous medium; and dispersing the neutralized prepolymer in the aqueous medium. The step of reacting the prepolymer with the chain extension agent. In addition, in each step, by using a catalyst as necessary, the reaction can be promoted and the amount of by-products can be controlled.

A film formed from the aqueous polyurethane resin dispersion described above (for example, a film formed by coating the aqueous polyurethane resin dispersion on a base material) has excellent adhesion, flexibility, touch, and the like. Therefore, the above-mentioned water-based polyurethane resin dispersion can be applied to artificial leather, synthetic leather and coated materials.

＜Two liquid composition set＞ The two-liquid composition set of the polyol component and the polyisocyanate component for forming the polyurethane resin can be stored and transported in separate containers. The two-liquid composition contains a first liquid containing at least the polyol component and a second liquid containing at least the polyisocyanate component. When chain extension agents, catalysts, solvents, etc. are used, these may be contained in the first liquid and/or the second liquid, or may be blended in the first liquid and the second liquid respectively. The above-mentioned two-liquid composition system can be applied to, for example, coating materials, and can also be applied to the production of artificial leather, synthetic leather, etc. When the above-mentioned two-liquid composition set is used as a coating material, for example, the first liquid and the second liquid are mixed, and then the obtained mixed liquid is applied to the base material, and optionally heated to form a coating film ( For example, a cured film containing polyurethane resin). [Example]

The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

<First Embodiment> (Example 1A) In a 1L double-port glass reactor equipped with a mixer, thermometer, heating device and cooler, mix: 35.2g trimethylolpropane, 354.2g 1,4-butanediol, 510.7g diethyl carbonate, and lithium acetate acetonate 0.045g. The obtained mixture was heated at 130 to 150°C (initial 130°C and final 150°C) under normal pressure to react for 8 hours while removing low-boiling components (carbonate-derived alcohol, etc.). The distillate temperature is set to be 77°C or more and less than 79°C. Then, the pressure in the flask was reduced to 1 kPa at a reaction temperature of 150° C., and the reaction was further carried out for 8 hours to obtain a composition (PCP-1A) containing polycarbonate polyol represented by the above formula (A-1).

(Example 2A) Except for using a mixed liquid obtained by mixing 31.3g of trimethylolpropane, 413.8g of 1,6-hexanediol, 454.9g of diethyl carbonate, and 0.045g of lithium acetate acetonate, the rest was the same as in Example 1A. A composition (PCP-2A) containing polycarbonate polyol represented by the above formula (A-1) was obtained.

(Example 3A) Except for using a mixed solution obtained by mixing 83.0 g of trihydroxymethylpropane, 334.6 g of 1,4-butanediol, 482.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate, the rest was the same as Example 1A to obtain a composition (PCP-3A) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 4A) Except for using a 1L double-necked glass reactor equipped with a stirrer, a thermometer, a heater and a cooler, 74.4 g of trihydroxymethylpropane, 393.2 g of 1,6-hexanediol, 432.4 g of diethyl carbonate and 0.045 g of lithium acetylacetonate to obtain a mixed solution, the rest was the same as in Example 1A to obtain a composition (PCP-4A) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 5A) 900 g of the composition (PCP-2A) obtained in Example 2A was mixed with 100 g of trimethylolpropane at 80°C to obtain a composition (PCP) containing the polycarbonate polyol represented by the above formula (A-1). -5A).

(Example 6A) In addition to being used in a 1L double-port glass reactor equipped with a mixer, thermometer, heating device and cooler, mix: 33.6g trimethylolethane, 198.3g 1,6-hexanediol, diethyl carbonate The composition (PCP-6A) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1A except for the mixture obtained by adding 218.1 g of lithium acetate acetonate and 0.025 g of lithium acetate acetonate. ).

(Example 7A) In addition to being used in a 1L double-port glass reactor equipped with a mixer, thermometer, heating device and cooler, mix: 37.7g of neopentylerythritol, 196.4g of 1,6-hexanediol, and 215.9g of diethyl carbonate. , and 0.025 g of lithium acetate acetonate, and the composition (PCP-7A) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1A except for the obtained mixed liquid.

(Example 8A) Except that the distillate temperature was set to be above 80°C and below 83°C, the rest was the same as Example 4A to obtain a composition (PCP-8A) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 9A) Except that the amount of lithium acetylacetonate blended was changed to 0.135 g and the distillate temperature was set to 84°C or higher and less than 108°C, the rest was the same as Example 4A to obtain a composition (PCP-9A) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 1A) 800 g of the composition (PCP-2A) obtained in Example 2A and 200 g of trihydroxymethylpropane were mixed at 80°C to obtain a composition (PCP-10A) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 2A) The mixed solution obtained in the same manner as in Example 4A was heated at 150°C (150°C at the beginning and 150°C at the end) under normal pressure, and the reaction was carried out for 8 hours while removing low-boiling components (such as alcohols derived from carbonates). The distillate temperature was set to be higher than 120°C. Furthermore, at a reaction temperature of 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was carried out for another 8 hours to obtain a composition (PCP-11A) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 3A) Except that the pressure in the flask was rapidly reduced to 1 kPa at a reaction temperature of 150°C, the same procedures as in Reference Example 2A were followed to obtain a composition (PCP-12A) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 4A) Except that the heating temperature under normal pressure was set to 140-150°C (140°C at the initial stage and 150°C at the final stage), the rest was the same as Reference Example 2A to obtain a composition (PCP-13A) containing a polycarbonate polyol represented by the above formula (A-1).

(Comparative Example 1A) 450 g of Nipporan 980R and 450 g of trihydroxymethylpropane were mixed at 80°C to obtain a polycarbonate diol-containing composition (PCD-1A).

(Comparative Example 2A) Except for using a mixed solution obtained by mixing 74.4 g of trihydroxymethylpropane, 393.2 g of 1,6-hexanediol, 432.4 g of diethyl carbonate, and 0.09 g of tetrabutyl titanium, the rest was the same as in Example 1A to obtain a polycarbonate polyol-containing composition (PCP-14A).

(Analysis and evaluation) [Determination of number average molecular weight] GPC analysis of the composition obtained above was performed under the following conditions, and the number average molecular weight of the composition was measured. The results are shown in Table 2 and Table 3. - condition - (1) Measuring device: HLC-8420 (manufactured by Tosoh Corporation) (2) Pipe string: TSKgel (manufactured by Tosoh Corporation) ． G3000H-XL ． G3000H-XL ． G2000H-XL ． G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (accessory to HLC-8420) (5)Temperature: 40℃ (6)Flow rate: 1.000ml/min (7) Calibration line: Use the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industry Co., Ltd.) to obtain a calibration line. ． "SANNIX PP-200" (number average molecular weight = 200, average number of functional groups: 2) ． "SANNIX PP-400" (number average molecular weight = 400, average number of functional groups: 2) ． "SANNIX PP-1000" (number average molecular weight = 1000, average number of functional groups: 2) ． "SANNIX PP-2000" (number average molecular weight = 2000, average number of functional groups: 2) ． "SANNIX PP-3000" (number average molecular weight = 3200, average number of functional groups: 2) ． "SANNIX PP-4000" (number average molecular weight = 4160, average number of functional groups: 2) (8) Approximate formula of calibration curve: cubic formula (9) Sample solution concentration: 0.5 mass% THF solution

[Hydroxyl value determination] The hydroxyl value of the composition obtained above was determined according to the method using an acetylation reagent in accordance with JIS K1557-1. The results are shown in Tables 2 and 3.

[Evaluation of properties] The above-obtained composition was set as a sample, and the sample was heated at 80°C for 1 hour and then placed at 5°C and 25°C for 3 days. The state of the sample after placement was visually confirmed. If it showed only slight fluidity at the above temperature, it was evaluated as liquid, and if it had no fluidity, it was evaluated as solid. The results are shown in Tables 2 and 3.

[Composition analysis (1)] The composition analysis of the composition was performed in the following order.

First, the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) to obtain a solution. Tetramethylsilane (TMS) used as a chemical shift reference was added to this solution to obtain a test solution. For the obtained test liquid, ¹ H-NMR was measured using JNM-ECX400 manufactured by JEOL Ltd., the TMS signal was set to 0 ppm, and a ¹ H-NMR mass spectrum was obtained. For reference, the ¹ H-NMR mass spectrum of the composition obtained in Example 2A is shown in Figures 1 to 3. In addition, the measurement was performed under the following conditions. - condition- . Resonance frequency: 400MHz. Pulse width: 45degree． Waiting time: 5 seconds. Number of points: 64. Sample solution concentration (heavy chloroform containing TMS): 3 mass vol%

Next, from the ¹ H-NMR mass spectrum obtained as described above, the integral value Δ _S1 of the methylene signal (S1) at the hydroxyl adjacent position of the group represented by the above formula (a-1) and the integral value Δ _S2 of the methylene signal (S2) at the hydroxyl adjacent position of the polyol (B) are obtained. In addition, when R ¹ of the group represented by the formula (I) is a methyl group or an ethyl group, the integral value of the signal of the terminal methyl group is obtained and set as the integral value Δ _S3 of the signal (S3). Specifically, a signal of 3.430 ppm or more and less than 3.550 ppm is set as a signal (S1), a signal of 3.725 ppm or more and 3.800 ppm or less is set as a signal (S2), a signal of 0.700 ppm or more and 1.130 ppm or less is set as a signal (S3) when R ¹ of the group represented by formula (I) is a methyl group (when the polyol (B) is trihydroxymethylethane), and a signal of 0.700 ppm or more and 1.000 ppm or less is set as a signal (S3) when R ¹ of the group represented by formula (I) is an ethyl group (when the polyol (B) is trihydroxymethylpropane). In addition, the baseline for determining the relevant integral value is a line drawn horizontally based on the lower mass spectrum intensity by comparing the mass spectrum intensities at both ends of the specified mass spectrum range.

From the obtained integral values, the molar ratio ( _CA1 /C _B ), molar ratio ( _CA1 /C _T ) and molar ratio (C _B /C _T ) were calculated. The results are shown in Tables 2 and 3. In addition, PCP-1A~13A showed the presence of compound (A-1) by the presence of signal (S1). On the other hand, PCD-1A and PCP-14A did not confirm the signal (S1). Moreover, PCP-1A~13A showed the presence of compound (A-2) by the presence of signal (S4) above 3.550ppm and below 3.62ppm. In addition, if one of the three bonding bases in formula (I) is a bonding base for carbonate groups, and the other two are bonding bases for hydroxyl groups, the total molar number of which is set as C _A2 , then the integral value of the above signal (S4) is related to C _A2 . Moreover, if the total molar number of the three bonding bases in formula (I) is all bonding bases for carbonate groups, then _CT is consistent with the sum of C _A1 , C _A2 , C _A3 and _CB . PCP-1A~6A and PCP-8A~14A confirm that the value of _CT minus C _A1 , C _A2 and _CB is positive _by the integral value of the above signals (S1)~(S4), indicating the presence of compound (A-3).

[Composition analysis (2)] The above-obtained composition was subjected to LC-MS measurement under the following conditions to obtain: the maximum intensity of the peak corresponding to the polycarbonate diol with q of 3 in formula (E), the maximum intensity of the peak corresponding to the polycarbonate diol with q of 4 in formula (E), and the maximum intensity of the peak corresponding to the polycarbonate diol with q of 5 in formula (E), and the ratio of P3 to the sum of P3, P4 and P5 (P3/[P3+P4+P5]), and the ratio of P5 to the sum of P3, P4 and P5 (P5/[P3+P4+P5]). The results are shown in Tables 2 and 3. - Conditions - (1) Analyzer: Agilent 1290 Infinity II series (manufactured by Agilent Technologies) (2) Column: TSKgel (manufactured by Tosoh Corporation) TSKgel ODS-100V (4.6 mmID×15 cm) (3) Mobile phase: Solution A: Water/methanol = 5/5 (vol/vol%) Solution B: Tetrahydrofuran (THF) Water: Purified water THF: FUJIFILM Wako Pure Chemical Industries, Ltd. for HPLC Methanol: FUJIFILM Wako Pure Chemical Industries, Ltd. for HPLC (4) Pretreatment Weigh the sample (composition), add the specified mobile phase (solution B), and stand overnight at room temperature to dissolve. The obtained sample solution is gently shaken to mix, and then filtered using a 0.45μm PTFE cartridge filter. (5) Gradient conditions [Table 1] Time(min.) Liquid A (v/v%) Solution B (v/v%) 0 90 10 5 90 10 10 60 40 55 0 100 62 0 100 62.1 90 10 (6) Detector: Volatile light scattering detector (ELSD) G4260B (manufactured by Agilemt Technologies) (7) Temperature: 40°C (8) Flow rate: 0.40 ml/min (9) Injection volume: 15 μL (10) Sample solution concentration (THF): 1.0 mg/L In addition, the molecular structure of each peak was identified by performing MS measurement on each peak individually (device: Bruker Daltonics microTOF, ion source: APCI, measurement mode: positive mode).

[Table 2] Example 1A Example 2A Example 3A Example 4A Example 5A Example 6A Example 7A Example 8A Example 9A Composition PCP-1A PCP-2A PCP-3A PCP-4A PCP-5A PCP-6A PCP-7A PCP-8A PCP-9A composition Diol(D) 1,4-butanediol 354.2 - 334.6 - - - - - - 1,6-Hexanediol - 413.8 - 393.2 - 198.3 196.4 393.2 393.2 Polyol(B) trimethylolpropane 35.2 31.3 83.0 74.4 100.0 - - 74.4 74.4 Trihydroxymethylethane - - - - - 33.6 - - - neopentylerythritol - - - - - - 37.7 - - Carbonate diethyl carbonate 510.7 454.9 482.4 432.4 - 218.1 215.9 432.4 432.4 catalyst Lithium acetate acetonate 0.045 0.045 0.045 0.045 - 0.025 0.025 0.045 0.135 Composition PCP-2A - - - - 900.0 - - - - Analysis and evaluation Number average molecular weight (g/mol) 1390 1820 650 1060 640 1150 980 706 415 Hydroxyl value (mgKOH/g) 94 79 225 163 189 150 220 233 408 Traits 5℃ solid state solid state solid state solid state solid state solid state solid state solid state liquid 25℃ solid state solid state solid state solid state solid state solid state solid state solid state liquid Composition analysis (1) ¹ H-NMR measurement C _A1 /C _B 35.000 40.200 9.429 9.577 0.206 13.050 1.420 3.833 0.755 C _A1 /C _T 0.350 0.335 0.440 0.415 0.135 0.435 - 0.345 0.190 C _B /C _T 0.010 0.008 0.047 0.043 0.657 0.033 - 0.090 0.252 Composition analysis (2) LC-MS determination P3/[P3+P4+P5] - 0.25 - 0.35 - - - 0.40 0.50 P5/[P3+P4+P5] - 0.37 - 0.26 - - - 0.22 0.14

[table 3] Reference example 1A Reference example 2A Reference example 3A Reference Example 4A Comparative example 1A Comparative example 2A Composition PCP-10A PCP-11A PCP-12A PCP-13A PCD-1A PCP-14A composition Diol(D) 1,6-Hexanediol - 393.2 393.2 393.2 - 393.2 Polyol(B) trimethylolpropane 200.0 74.4 74.4 74.4 450.0 74.4 Carbonate diethyl carbonate - 432.4 432.4 432.4 - 432.4 catalyst Lithium acetate acetonate - 0.045 0.045 0.045 - - Tetrabutyl titanate - - - - - 0.09 Composition Nipporan 980R - - - - 450.0 - PCP-2A 800.0 - - - - - Analysis and evaluation Number average molecular weight (g/mol) 370 246 249 276 210 265 Hydroxyl value (mgKOH/g) 308 703 686 623 656 855 Traits 5℃ solid state liquid liquid liquid solid state liquid 25℃ solid state liquid liquid liquid solid state liquid Composition analysis (1) ¹ H-NMR measurement C _A1 /C _B 0.061 0.106 0.192 0.195 - - C _A1 /C _T 0.080 0.065 0.115 0.100 - - C _B /C _T 1.310 0.615 0.598 0.512 0.998 0.905 Composition analysis (2) LC-MS determination P3/[P3+P4+P5] - 0.85 0.84 0.75 - 1.00 P5/[P3+P4+P5] - 0.01 0.01 0.04 - 0.00

In Table 2 and Table 3, the "composition" (unit: g) of Examples 1A to 4A and 6A to 9A, Reference Examples 2A to 4A, and Comparative Example 2A represents the reaction raw materials. Example 5A, Reference Example 1A, and Comparative Example The "composition" (unit: g) in Example 1A represents the blended ingredients.

(physical property evaluation) A polyurethane cured film (film) was produced according to the following method, and the obtained film was used as a sample, and the physical properties (tensile properties, moisture and heat resistance properties, and feel properties) were evaluated.

[Production of polyurethane hardened coating] First, the composition obtained above, the polyisocyanate component (C-2612), the polyurethanization catalyst, the phosphorus compound (JP508), and the diluting solvent were prepared according to the formulas (unit: g) described in Tables 4 and 5. Mix in a 200mL glass bottle. Immediately after mixing, the mixture is poured onto the release paper and cast into a 200μm thick film using a rod coater. Next, the cast film was heated and hardened under conditions of 25°C for 30 minutes, 50°C for 30 minutes, 80°C for 30 minutes, 120°C for 1 hour, and 50°C for 18 hours, to obtain a polyurethane cured film. (film).

[Evaluation of tensile properties and hand feel properties] The tensile properties and hand feel properties of the obtained film were measured according to JIS K6251 under the following conditions. The results are shown in Tables 4 and 5. - Conditions - . Test equipment: Tensile machine UTA-500 (manufactured by A&D Co., Ltd.) . Measurement conditions: 25℃×50%RH . Chuck speed: 200mm/min . Dumbbell No. 4 If the tensile strength is 10MPa or more and the elongation at break is 200% or more, the tensile properties are evaluated as good, and if the 100% modulus is 5MPa or less, the hand feel properties are evaluated as good. In addition, if the tensile strength is 3MPa or more, there will be no practical problem.

[Evaluation of moisture and heat resistance] The obtained film was placed in a moisture and heat dryer at 80°C × 95% RH for 28 days and used as a test body. Then, the tensile strength of each test body was measured in the same way as the tensile properties described above. The tensile strength retention rate was calculated according to the following formula (1) and used as an index of the moisture and heat resistance of the polyurethane resin. The test device used was ESPEC CORP (manufactured by ESPEC). The results are shown in Tables 4 and 5. Tensile strength retention rate (%) = C/D × 100 (1) C: Tensile strength after moisture and heat resistance test (MPa) D: Tensile strength before moisture and heat resistance test (MPa) If the tensile strength retention rate is 80% or more, the moisture and heat resistance is evaluated as good.

[Table 4] Example 1A Example 2A Example 3A Example 4A Example 5A Example 6A Example 7A Example 8A Example 9A Composition type PCP-1A PCP-2A PCP-3A PCP-4A PCP-5A PCP-6A PCP-7A PCP-8A PCP-9A formula Composition 28.2 29.6 20 23.2 21.7 twenty four 20.2 19.7 14.2 Polyisocyanate ingredients C-2612 11.8 10.4 20 16.8 18.3 16 19.8 20.3 25.8 Polyurethanization catalyst DOTDL 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Phosphorus compounds JP508 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 dilution solvent Methyl ethyl ketone 42 42 42 42 42 42 42 42 42 Toluene 18 18 18 18 18 18 18 18 18 Mol ratio (isocyanate group/hydroxyl group) 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 physical properties 100% modulus (MPa) 2.2 2.1 1.4 2.6 4.7 2.4 3.1 2.8 2.2 Tensile strength(MPa) 14 26 28 25 twenty three 26 31 18 13 Stretch rate(%) 380 390 400 370 300 350 300 350 310 Tensile strength retention rate (%) 101 102 85 81 105 86 91 90 70

[table 5] Reference Example 1A Reference Example 2A Reference Example 3A Reference Example 4A Comparative Example 1A Comparative Example 2A Composition type PCP-10A PCP-11A PCP-12A PCP-13A PCD-1A PCP-14A formula Composition 16.9 9.7 9.9 10.6 10.2 8.3 Polyisocyanate ingredients C-2612 23.1 30.3 30.1 29.4 29.8 31.7 Polyurethane Catalyst DOTDL 0.01 0.01 0.01 0.01 0.01 0.01 Phosphorus compounds JP508 0.01 0.01 0.01 0.01 0.01 0.01 Diluent Methyl Ethyl Ketone 42 42 42 42 42 42 Toluene 18 18 18 18 18 18 Molar ratio (isocyanate/hydroxyl) 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 Physical properties 100% modulus (MPa) 19.2 29.3 28.5 20.3 30.3 38.2 Tensile strength(MPa) 65 35 31 32 36 42 Elongation(%) 200 80 90 120 130 50 Tensile strength retention rate (%) 100 100 102 103 99 101

The details of the materials used in the first embodiment are as follows: ． 1,4-Butanediol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． 1,6-hexanediol: manufactured by BASF-JAPAN ． Trimethylolpropane: manufactured by Sigma-Aldrich Company ． Trimethylolethane: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Neopenterythritol: manufactured by FUJIFILM Wako Pure Pharmaceuticals Co., Ltd. ． Diethyl carbonate: manufactured by Sigma-Aldrich Company ． Dimethyl carbonate: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Lithium acetate acetonate: manufactured by Sigma-Aldrich ． Lithium hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. ． Tetrabutyl titanate: manufactured by Tokyo Chemical Industry Co., Ltd. ． Nipporan 980R: Trade name, 1,6-hexanediol polycarbonate diol, hydroxyl value = 56KOHmg/g, f = 2, manufactured by Tosoh Corporation ． JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Seongbuk Chemical Industry Co., Ltd. ． C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation ． DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. ． Methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd. ． Toluene: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

<Example 2> (Example 1B) In a 1L double-necked glass reactor equipped with a stirrer, a thermometer, a heater and a cooler, 35.2g of trihydroxymethylpropane, 298.5g of 1,6-hexanediol, 97.5g of 1,4-butanediol, 468.8g of diethyl carbonate, and 0.045g of lithium acetylacetonate were mixed. The obtained mixed solution was heated at 130-150°C (130°C at the initial stage and 150°C at the final stage) under normal pressure, and the reaction was carried out for 8 hours while removing low-boiling components (such as alcohols derived from carbonates). The distillate temperature was set to be above 77°C and below 79°C. Then, at a reaction temperature of 150°C, the pressure in the flask was reduced to 1 kPa, and the reaction was continued for 8 hours to obtain a composition (PCP-1B) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 2B) Except for using a mixed liquid obtained by mixing 34.6g of trimethylolpropane, 218.4g of 1,6-hexanediol, 166.6g of 1,4-butanediol, 480.4g of diethyl carbonate, and 0.045g of lithium acetate acetonate. Except for this, a composition (PCP-2B) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B.

(Example 3B) Except for using a mixed solution obtained by mixing 75.6 g of trihydroxymethylpropane, 358.2 g of 1,6-hexanediol, 30.4 g of 1,4-butanediol, 426.1 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate, the rest was the same as in Example 1B to obtain a composition (PCP-3B) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 4B) Except for using a mixed liquid obtained by mixing 37.3g of trimethylolpropane, 273.7g of 1,6-hexanediol, 159.1g of 1,9-nonanediol, 432.8g of diethyl carbonate, and 0.045g of lithium acetate acetonate. Except for this, a composition (PCP-4B) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B.

(Example 5B) 900 g of the composition (PCP-1B) obtained in Example 1B and 100 g of trihydroxymethylpropane were mixed at 80°C to obtain a composition (PCP-5B) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 6B) Except for using a mixture obtained by mixing 31.4g of trimethylolethane, 299.8g of 1,6-hexanediol, 98.0g of 1,4-butanediol, 470.8g of diethyl carbonate, and 0.045g of lithium acetate acetonate. The composition (PCP-6B) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except for the liquid.

(Example 7B) In addition to using a mixed liquid obtained by mixing 35.8g of neopenterythritol, 298.3g of 1,6-hexanediol, 97.5g of 1,4-butanediol, 468.5g of diethyl carbonate, and 0.045g of lithium acetate acetonate. Except for this, the composition (PCP-7B) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B.

(Example 8B) Except for using a mixed solution obtained by mixing 35.8 g of trihydroxymethylpropane, 374.7 g of 1,6-hexanediol, 31.7 g of 1,4-butanediol, 453.0 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate, the rest was the same as Example 1B to obtain a composition (PCP-8B) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 1B) 800 g of the composition (PCP-1B) obtained in Example 1B and 200 g of trihydroxymethylpropane were mixed at 80°C to obtain a composition (PCP-9B) containing the polycarbonate polyol represented by the above formula (A-1).

(Comparative Example 1B) Except for using a mixed solution obtained by mixing 196g of 1,6-hexanediol, 172.8g of 1,5-pentanediol, 431.2g of diethyl carbonate, and 0.045g of lithium acetylacetonate, the rest was the same as in Example 1B to obtain a polycarbonate diol-containing composition (PCD-1B).

(Comparative Example 2B) 450 g of the composition (PCD-1B) obtained in Comparative Example 1B and 450 g of trimethylolpropane were mixed at 80° C. to obtain a polycarbonate diol-containing composition (PCD-2B).

(Analysis and Evaluation) The number average molecular weight and hydroxyl value of the composition obtained above were measured in the same manner as in Example 1, and property evaluation and composition analysis (1) were performed. In the composition analysis (1), a signal of 3.430 ppm or more and 3.530 ppm or less was set as signal (S1), a signal of 3.720 ppm or more and 3.800 ppm or less was set as signal (S2), a signal of 0.700 ppm or more and 1.130 ppm or less was set as signal (S3) when R ¹ of the group represented by formula (I) was methyl (when the polyol (B) was trihydroxymethylethane), and a signal of 0.700 ppm or more and 1.000 ppm or less was set as signal (S3) when R ¹ of the group represented by formula (I) was ethyl (when the polyol (B) was trihydroxymethylpropane). The results are shown in Tables 6 and 7. For reference, the ¹ H-NMR mass spectra of the composition obtained in Example 1B are shown in Figures 4 to 6. In addition, as a result of the composition analysis (1), PCP-1B to 9B indicate the presence of compound (A-1) by the presence of signal (S1). On the other hand, PCD-1B to 2B did not confirm signal (S1). PCP-1B to 9B indicate the presence of compound (A-2) by the presence of signal (S4) above 3.550 ppm and below 3.620 ppm. PCP-1B to 6B and PCP-8B to 9B indicate the presence of compound (A-3) by the positive value of the integral value of the above signals (S1) to (S4) minus _CA1 , _CA2 and _CB from _CT .

[Table 6] Embodiment 1B Example 2B Example 3B Example 4B Example 5B Example 6B Example 7B Composition PCP-1B PCP-2B PCP-3B PCP-4B PCP-5B PCP-6B PCP-7B Composition Diol (D) 1,4-Butanediol 97.5 166.6 30.4 - - 98.0 97.5 1,6-Hexanediol 298.5 218.4 358.2 273.7 - 299.8 298.3 1,9-Nonanediol - - - 159.1 - - - Polyol (B) Trihydroxymethylpropane 35.2 34.6 75.6 37.3 100.0 - - Trihydroxymethylethane - - - - - 31.4 - Pentaerythritol - - - - - - 35.8 Carbonate Diethyl carbonate 468.8 480.4 426.1 432.8 - 470.8 468.5 Catalyst Lithium acetylacetonate 0.045 0.045 0.045 0.045 - 0.045 0.045 Composition PCP-1B - - - - 900.0 - - Analysis and evaluation Number average molecular weight (g/mol) 2190 1610 1020 2080 640 1720 1650 Hydroxyl value (mgKOH/g) 78 85 182 81 198 81 83 Characteristics 5℃ Liquid Liquid Liquid Liquid Liquid Liquid Liquid 25℃ Liquid Liquid Liquid Liquid Liquid Liquid Liquid Composition analysis (1) ¹ H-NMR measurement C _A1 /C _B 26.407 25.602 8.100 31.854 0.141 25.750 4.520 C _A1 /C _T 0.430 0.425 0.405 0.420 0.105 0.412 - _CB / _CT 0.016 0.017 0.050 0.013 0.747 0.016 -

[Table 7] Example 8B Reference example 1B Comparative example 1B Comparative example 2B Composition PCP-8B PCP-9B PCD-1B PCD-2B composition Diol(D) 1,4-butanediol 31.7 - - - 1,5-Pentanediol - - 172.8 - 1,6-Hexanediol 374.7 - 196.0 - Polyol(B) trimethylolpropane 35.8 200.0 - 450.0 Carbonate diethyl carbonate 453.0 - 431.2 - catalyst Lithium acetate acetonate 0.045 - 0.045 - Composition PCD-1B - - - 450.0 PCP-1B - 800.0 - - Analysis and evaluation Number average molecular weight (g/mol) 2470 370 1710 210 Hydroxyl value (mgKOH/g) 68 316 55.9 650 Traits 5℃ solid state solid state liquid solid state 25℃ solid state solid state liquid solid state Composition analysis (1) ¹ H-NMR measurement C _A1 /C _B 34.791 0.097 - - C _A1 /C _T 0.435 0.080 - - C _B /C _T 0.013 0.825 - 0.998

In Tables 6 and 7, the "composition" (unit: g) of Examples 1B to 4B and 6B to 8B, and Comparative Example 1B represents the reaction raw materials, and the "composition" (unit: g) of Example 5A, Reference Example 1A, and Comparative Example 1A represents the blending components.

(Physical property evaluation) Except for mixing the above-obtained composition, polyisocyanate component (C-2612), polyurethane catalyst, phosphate ester (JP508), and diluent according to the formula (unit: g) listed in Tables 8 and 9, the rest is the same as in Example 1 to obtain a polyurethane cured film (film). Then, the obtained film is set as a sample, and the physical properties (tensile properties, moisture and heat resistance properties, feel properties) are evaluated in the same way as in Example 1. The results are shown in Tables 8 and 9. In addition, the physical property evaluation of Comparative Example 1B was not implemented.

[Table 8] Example 1B Example 2B Example 3B Example 4B Example 5B Example 6B Example 7B Composition type PCP-1B PCP-2B PCP-3B PCP-4B PCP-5B PCP-6B PCP-7B formula Composition 29.7 29 22.1 29.4 21.3 29.4 29.2 Polyisocyanate ingredients C-2612 10.3 11 17.9 10.6 18.7 10.6 10.8 Polyurethanation catalyst DOTDL 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Phosphorus compounds JP508 0.01 0.01 0.01 0.01 0.01 0.01 0.01 dilution solvent Methyl ethyl ketone 42 42 42 42 42 42 42 Toluene 18 18 18 18 18 18 18 Mol ratio (isocyanate group/hydroxyl group) 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 physical properties 100% modulus (MPa) 2.0 2.2 2.7 2.7 3.3 2.1 2.5 Tensile strength(MPa) 17.5 15.3 27.0 30.0 31.4 17.3 18.9 Stretch rate(%) 400 400 300 300 300 400 300 Tensile strength retention rate (%) 102 106 88 91 98 101 100

[Table 9] Embodiment 8B Reference Example 1B Comparative Example 2B Composition type PCP-8B PCP-9B PCD-2B formula Composition 30.7 16.6 10.2 Polyisocyanate ingredients C-2612 9.3 23.4 29.8 Polyurethane Catalyst DOTDL 0.01 0.01 0.01 Phosphorus compounds JP508 0.01 0.01 0.01 Diluent Methyl Ethyl Ketone 42 42 42 Toluene 18 18 18 Molar ratio (isocyanate/hydroxyl) 1.02/1.0 1.02/1.0 1.02/1.0 Physical properties 100% modulus (MPa) 1.9 10.0 35.2 Tensile strength(MPa) 28.5 34.5 40 Elongation(%) 400 230 100 Tensile strength retention rate (%) 99 98 102

Details of the materials used in the second embodiment are as follows: ． 1,4-Butanediol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． 1,5-pentanediol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． 1,6-hexanediol: manufactured by BASF-JAPAN ． 1,9-Nonanediol: manufactured by KURARAY Co., Ltd. ． Trimethylolpropane: manufactured by Sigma-Aldrich Company ． Trimethylolethane: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Neopenterythritol: manufactured by FUJIFILM Wako Pure Pharmaceuticals Co., Ltd. ． Lithium hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. ． Tetrabutyl titanate: manufactured by Tokyo Chemical Industry Co., Ltd. ． Diethyl carbonate: manufactured by Sigma-Aldrich Company ． Dimethyl carbonate: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Lithium acetate acetonate: manufactured by Sigma-Aldrich ． JP-508: Trade name, 2-ethylhexyl acid phosphate, manufactured by Seongbuk Chemical Industry Co., Ltd. ． C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition-modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation ． DOTDL: Dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. ． Methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd. ． Toluene: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

<Third Embodiment> (Example 1C) In a 1L double-port glass reactor equipped with a mixer, thermometer, heating device and cooler, fill: 36.1g of trimethylolpropane, 288g of 1,6-hexanediol, and 3-methyl-1 , 123.4g of 5-pentanediol, 452.4g of diethyl carbonate, and 0.045g of lithium acetyl acetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial 130°C and final 150°C) under normal pressure to react for 8 hours while removing low-boiling components (carbonate-derived alcohol, etc.). The distillate temperature is set to be 77°C or more and less than 79°C. Then, the pressure in the flask was reduced to 1 kPa at a reaction temperature of 150° C., and the reaction was further performed for 8 hours to obtain a composition (PCP-1C) containing polycarbonate polyol represented by the above formula (A-1).

(Example 2C) In addition to using filling materials such as: 36.2g trimethylolpropane, 205.7g 1,6-hexanediol, 205.7g 3-methyl-1,5-pentanediol, 452.3g diethyl carbonate, and lithium acetate acetonate Except for the mixed liquid obtained by mixing 0.045 g, the composition (PCP-2C) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C.

(Example 3C) In addition to using, add: 36.2g of trimethylolpropane, 411.5g of 3-methyl-1,5-pentanediol, 452.3g of diethyl carbonate, and 0.045g of lithium acetate acetonate. The mixture obtained by mixing The composition (PCP-3C) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except for the liquid.

(Example 4C) In addition to using, add: 74.3g trimethylolpropane, 353.9g 1,6-hexanediol, 39.3g 3-methyl-1,5-pentanediol, 432.4g diethyl carbonate, and acetyl acetone The composition (PCP-4C) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except for the mixed liquid obtained by mixing 0.045 g of lithium.

(Example 5C) Except for using a mixed solution obtained by mixing 60.4 g of trihydroxymethylpropane, 865.4 g of ND-15, 701.7 g of diethyl carbonate, and 0.06 g of lithium acetylacetonate, the rest was the same as Example 1C to obtain a composition (PCP-5C) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 6C) 900 g of the composition (PCP-1C) obtained in Example 1C and 100 g of trihydroxymethylpropane were mixed at 80°C to obtain a composition (PCP-6C) containing the polycarbonate polyol represented by the above formula (A-1).

(Example 7C) Except for using a mixed solution obtained by mixing 32.2 g of trihydroxymethylethane, 289.3 g of 1,6-hexanediol, 124.0 g of 3-methyl-1,5-pentanediol, 454.5 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate, the rest was the same as Example 1C to obtain a composition (PCP-7C) containing a polycarbonate polyol represented by the above formula (A-1).

(Example 8C) Except for use, add: 36.6g of neopentyl erythritol, 287.8g of 1,6-hexanediol, 123.4g of 3-methyl-1,5-pentanediol, 452.1g of diethyl carbonate, and lithium acetyl acetonate. Except for the mixed liquid obtained by mixing 0.045 g, the composition (PCP-8C) containing the polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C.

(Example 9C) Except for using a mixed solution obtained by mixing 36.1 g of trihydroxymethylpropane, 370.3 g of 1,6-hexanediol, 41.1 g of 3-methyl-1,5-pentanediol, 452.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate, the rest was the same as Example 1C to obtain a composition (PCP-9C) containing a polycarbonate polyol represented by the above formula (A-1).

(Reference Example 1C) 800 g of the composition (PCP-1C) obtained in Example 1C and 200 g of trihydroxymethylpropane were mixed at 80°C to obtain a composition (PCP-10C) containing the polycarbonate polyol represented by the above formula (A-1).

(Analytical Evaluation) The number average molecular weight and hydroxyl value of the composition obtained above were measured in the same manner as in Example 1, and property evaluation and composition analysis (1) were performed. In the composition analysis (1), a signal of 3.450 ppm or more and 3.530 ppm or less is regarded as signal (S1), and a signal of 3.720 ppm or more and 3.800 ppm or less is regarded as signal (S2). The results are shown in Table 10. In addition, for reference, the ¹ H-NMR mass spectrum of the composition obtained in Example 1C is shown in Figures 7 to 9. The results of the composition analysis (1) show that PCP-1C~10C indicates the presence of the compound (A-1) by the presence of the signal (S1), and the presence of the signal (S4) of 3.550 ppm or more and 3.620 ppm or less, And the presence of compound (A-2) is taught.

[Table 10] Embodiment 1C Embodiment 2C Embodiment 3C Embodiment 4C Example 5C Example 6C Example 7C Example 8C Embodiment 9C Reference Example 1C Composition PCP-1C PCP-2C PCP-3C PCP-4C PCP-5C PCP-6C PCP-7C PCP-8C PCP-9C PCP-10C Composition Diol (D) 3-Methyl-1,5-pentanediol 123.4 205.7 411.5 39.3 - - 124 123.4 41.1 - 1,6-Hexanediol 288 205.7 - 353.9 - - 289.3 287.8 370.3 - ND-15 - - - - 865.4 - - - - - Polyol (B) Trihydroxymethylpropane 36.1 36.2 36.2 74.3 60.4 100 - - 36.1 200 Trihydroxymethylethane - - - - - - 32.2 - - - Pentaerythritol - - - - - - - 36.6 - - Carbonate Diethyl carbonate 452.4 452.3 452.3 432.4 701.7 - 454.5 452.1 452.4 - Catalyst Lithium acetylacetonate 0.045 0.045 0.045 0.045 0.06 - 0.045 0.045 0.045 - Composition PCP-1C - - - - - 900 - - - 800 Analysis and evaluation Number average molecular weight (g/mol) 2120 2230 2310 1340 3030 620 2150 2270 2370 380 Hydroxyl value (mgKOH/g) 79 73 73 156 54 198 78 75 71 316 Characteristics 5℃ Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Solid Solid 25℃ Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Solid Solid Composition analysis (1) ¹ H-NMR measurement C _A1 /C _B 8.434 6.725 2.712 9.706 46.053 0.234 7.083 4.952 12.500 0.091

In Table 10, the "composition" (unit: g) of Examples 1C to 5C and 7C to 9C indicates the reaction raw materials, and the "composition" (unit: g) of Example 6C and Reference Example 1C indicates the blending components.

(Physical property evaluation) Except for mixing the above-obtained composition, polyisocyanate component (C-2612), polyurethane catalyst, phosphate ester (JP508), and diluent according to the formula (unit: g) recorded in Table 11, the rest is the same as in Example 1 to obtain a polyurethane cured film (film). Then, the obtained film is set as a sample, and the physical properties (tensile properties, moisture and heat resistance properties, feel properties) are evaluated in the same way as in Example 1. The results are shown in Table 11.

[Table 11] Example 1C Example 2C Example 3C Example 4C Example 5C Example 6C Example 7C Example 8C Example 9C Reference example 1C Composition type PCP-1C PCP-2C PCP-3C PCP-4C PCP-5C PCP-6C PCP-7C PCP-8C PCP-9C PCP-10C formula Composition 29.6 30.2 30.2 23.6 32.3 21.3 29.7 30 30.4 16.6 Polyisocyanate ingredients C-2612 10.4 9.8 9.8 16.4 7.7 18.7 10.3 10 9.6 23.4 Polyurethanation catalyst DOTDL 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Phosphorus compounds JP508 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 dilution solvent Methyl ethyl ketone 42 42 42 42 42 42 42 42 42 42 Toluene 18 18 18 18 18 18 18 18 18 18 Mol ratio (isocyanate group/hydroxyl group) 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 1.02/1.0 physical properties 100% modulus (MPa) 2.0 2.1 1.9 2.4 1.5 3.6 2 2.5 2.0 11.2 Tensile strength(MPa) 7.3 6.1 4.0 3.8 25.0 27.1 3 27.4 20.5 32.8 Stretch rate(%) 300 300 500 300 400 300 300 250 300 200 Tensile strength retention rate (%) 102 100 105 87 100 103 105 101 98 100

Details of the materials used in the third embodiment are as follows: ． 3-Methyl-1,5-pentanediol: manufactured by KURARAY Co., Ltd. ． 1,5-Pentanediol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． 1,6-Hexanediol: manufactured by BASF-JAPAN Co., Ltd. ． ND-15: 1,9-nonanediol/2-methyl-1,8-octanediol mixture, manufactured by KURARAY Co., Ltd., trade name ． Trihydroxymethylpropane: manufactured by Sigma-Aldrich Co., Ltd. ． Trihydroxymethylethane: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Neopentylthritol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. ． Lithium hydroxide: manufactured by Tokyo Chemical Industry Co., Ltd. ． Tetrabutyl titanium: manufactured by Tokyo Chemical Industry Co., Ltd. ． Diethyl carbonate: manufactured by Sigma-Aldrich Co., Ltd. ． Dimethyl carbonate: manufactured by FUJIFILM Wako Jun Chemical Co., Ltd. ． Lithium acetylacetonate: manufactured by Sigma-Aldrich Co., Ltd. ． JP-508: 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd., trade name ． C-2612: CORONATE 2612 (trade name), hexamethylene diisocyanate addition modified polyisocyanate, isocyanate content = 17.2%, manufactured by Tosoh Corporation ． DOTDL: dioctyl tin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd. ． Methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd. ． Toluene: manufactured by FUJIFILM Wako Jun Chemical Co., Ltd.

without

FIG. 1 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 2A; FIG. 2 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 2A, in which a portion of 3.430 ppm or more and less than 3.550 ppm is enlarged; FIG. 3 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 2A, in which a portion of 3.725 ppm or more and less than 3.800 ppm is enlarged; FIG. 4 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1B; FIG. 5 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1B, in which a portion of 3.430 ppm or more and less than 3.530 ppm is enlarged; FIG6 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1B, in which the portion above 3.720 ppm and below 3.800 ppm is enlarged; FIG7 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1C; FIG8 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1C, in which the portion above 3.450 ppm and below 3.530 ppm is enlarged; and FIG9 is a ¹ H-NMR mass spectrum of a composition containing a polycarbonate polyol obtained in Example 1C, in which the portion above 3.720 ppm and below 3.800 ppm is enlarged.

Claims (23)

A polycarbonate polyol is represented by the following formula (A-1):

[In formula (A-1), R ¹ represents a hydrogen atom or an alkyl group; R ² represents an alkanediyl group; n and m each represent an integer greater than 1; plural R ² groups may be the same or different from each other]. The polycarbonate polyol according to claim 1, wherein all R ² are linear alkane diyl groups. The polycarbonate polyol according to claim 1, wherein at least one of R ² is a branched alkane diyl group. The polycarbonate polyol according to any one of claims 1 to 3, wherein ^R2 contains two or more kinds of alkanediyl groups. A composition containing: the polycarbonate polyol described in any one of claims 1 to 4, and the polyol represented by the following formula (B);

[In formula (B), R ¹ is synonymous with the above]. The composition according to claim 5, wherein the total molar number of groups represented by the following formula (a-1) contained in the above composition is set to C _A1 , and the molar number of the above polyol contained in the above composition is When the total mole number is set to C _B , the mole ratio (C _A1 /C _B ) is 0.1~150;

[In the formula (a-1), * represents the bonding base to the carbonate group]. The composition as described in claim 5, further comprising: a compound (A-2) represented by the following formula (A-2), and a compound (A-3) represented by the following formula (A-3):

[In formula (A-2), ^R1 and ^R2 are synonymous with the above; ⁿ² represents an integer greater than or equal to 1; when ⁿ² is greater than or equal to 2, the plural ^R2s may be the same or different from each other];

[In formula (A-3), R ¹ and R ² have the same meanings as above; n ³ , m ³ and p ³ each represent an integer greater than 1; plural R ² may be the same or different from each other]. The composition according to claim 5, wherein the total molar number of groups represented by the following formula (a-1) contained in the above composition is set to C _A1 , and the following formula (a-1) contained in the above composition is When the total molar number of the base shown in I) is set to C _T , the molar ratio (C _A1 /C _T ) is 0.10~0.99; [Chemical 6]

[In formula (a-1), * represents the bonding base to the carbonate group];

[In the formula (I), R ¹ is synonymous with the above, and * represents a bonding base]. The composition as claimed in claim 5, wherein, when the total molar number of the polyol contained in the composition is _CB and the total molar number of the group represented by the following formula (I) contained in the composition is _CT , the molar ratio ( _CB / _CT ) is 0.001-0.900;

[In formula (I), R ¹ has the same meaning as above, and * represents a bonding base]. A composition comprising a polycarbonate polyol represented by the following formula (A-1), a polyol represented by the following formula (B), and lithium acetylacetonate:

[In formula (A-1), R ¹ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R ² represents an alkanediyl group; n and m each represent an integer greater than 1; plural R ² groups may be the same or different];

[In formula (B), R ¹ has the same meaning as above]. A method for producing polycarbonate polyol, which involves heating a mixed liquid containing a polyol represented by the following formula (B), a diol represented by the following formula (D), a carbonate, and a transesterification catalyst. The alcohol derived from the above carbonate is removed from the reaction system while performing a reflux reaction to obtain a polycarbonate polyol represented by the following formula (A-1);

[In the formula (A-1), R ¹ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R ² represents an alkane diyl group; n and m each represent an integer of 1 or more; plural R ² systems are mutually exclusive It can be the same or different]

[In formula (B), R ¹ is synonymous with the above]; [Chemical 13] HO-R ² -OH (D) [In formula (D), R ² is synonymous with the above]. A method for producing a composition, which includes heating a mixed liquid containing a polyol represented by the following formula (B), a diol represented by the following formula (D), a carbonate, and a transesterification catalyst, while removing the liquid from the reaction system. The alcohol derived from the above-mentioned carbonate is removed while performing a reflux reaction to obtain the composition as described in any one of claims 5 to 9;

[In formula (B), R ¹ is synonymous with the above]; [Chemical 15] HO-R ² -OH (D) [In formula (D), R ² is synonymous with the above]. The manufacturing method as described in claim 11, wherein the heating system of the above mixed liquid includes: heating at a temperature T1 under a pressure of 101.325kPa±20.000kPa, and then heating at a temperature T2 under a reduced pressure of less than 10.000kPa. Heating is performed; the above-mentioned temperatures T1 and T2 satisfy the relationship of the following formulas (α) and (β). The above-mentioned reflux reaction system removes the alcohol derived from the above-mentioned carbonate from the reaction system by distilling it below 120°C; 120°C ≦T1≦155℃． ． ． (α) 140℃≦T2≦155℃． ． ． (β). The manufacturing method as described in claim 11, wherein the content of the transesterification catalyst in the mixed solution is 0.001-0.050 parts by mass relative to 100 parts by mass of the total amount of the polyol, the diol and the carbonate in the mixed solution. The manufacturing method according to any one of claims 11 to 14, wherein the transesterification catalyst contains: lithium acetate acetonate. A polyurethane resin is a condensation polymer or a cross-linked product of a polyol component and a polyisocyanate component, and the polyol component contains the polycarbonate polyol as described in any one of claims 1 to 4. The polyurethane resin according to claim 16, wherein the polyol component further contains: a polyol represented by the following formula (B);

[In formula (B), R ¹ is synonymous with the above]. The polyurethane resin as claimed in claim 17, wherein, when the total molar number of the groups represented by the following formula (a-1) contained in the polyol component is set as _CA1 and the total molar number of the polyol contained in the polyol component is set as _CB , the molar ratio ( _CA1 / _CB ) is 0.1 to 150;

[In formula (a-1), * represents a bonding base to the carbonate group]. The polyurethane resin as claimed in claim 17, wherein the polyol component further comprises: a compound (A-2) represented by the following formula (A-2), and a compound (A-3) represented by the following formula (A-3);

[In formula (A-2), ^R1 and ^R2 are synonymous with the above; ⁿ² represents an integer greater than 1; when ⁿ² is greater than 2, the plural ^R2s may be the same or different from each other]; [Chem. 19]

[In formula (A-3), R ¹ and R ² have the same meanings as above; n ³ , m ³ and p ³ each represent an integer greater than 1; plural R ² may be the same or different from each other]. The polyurethane resin as claimed in claim 17, wherein, when the total molar number of the groups represented by the following formula (a-1) contained in the above-mentioned polyol component is set as C _A1 and the total molar number of the groups represented by the following formula (I) contained in the above-mentioned polyol component is set as C _T , the molar ratio (C _A1 /C _T ) is 0.10-0.99;

[In formula (a-1), * represents a bonding base to the carbonate group];

[In formula (I), R ¹ has the same meaning as above, and * represents a bonding base]. The polyurethane resin as claimed in claim 17, wherein, when the total molar number of the polyol contained in the polyol component is _CB and the total molar number of the groups represented by the following formula (I) contained in the polyol component is _CT , the molar ratio ( _CB / _CT ) is 0.001-0.900;

[In formula (I), R ¹ has the same meaning as above, and * represents a bonding base]. A polyurethane resin is a condensate or crosslinked product of a polyol component and a polyisocyanate component, wherein the polyol component comprises a polycarbonate polyol represented by the following formula (A-1), wherein the polyol component further comprises: a polyol having an acidic group,

[In formula (A-1), R ¹ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R ² represents an alkanediyl group; n and m each represent an integer greater than 1; plural R ² groups may be the same or different from each other]. A water-based polyurethane resin dispersion comprises: an aqueous medium, and a polyurethane resin as described in claim 22 or a neutralized product thereof dispersed in the aqueous medium.

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