JP6229250B2 - Polycarbonate diol-containing composition and method for producing polycarbonate diol-containing composition - Google Patents

Description

  The present invention relates to a polycarbonate diol-containing composition having good color tone and excellent heat resistance with little color change due to heating, and a method for producing the same.

  Conventionally, raw materials for the main soft segment parts of polyurethane resins produced on an industrial scale include ether types typified by polytetramethylene glycol, ester types typified by adipate esters, and polylactones typified by polycaprolactone. Examples thereof include polycarbonate types represented by polycarbonate polyol (Non-patent Document 1).

  Among these, the polycarbonate type using polycarbonate diol is considered the best durability grade in heat resistance and hydrolysis resistance. It is durable film, artificial leather for automobiles and furniture, paint (especially water-based paint), coating agent, Widely used as an adhesive. Under such circumstances, a method of obtaining a polycarbonate polyol while using a special dihydroxy compound as a monomer component and distilling off a monohydroxy compound by-produced by transesterification with a carbonic acid diester under reduced pressure has been proposed (for example, Patent Documents). 1-5).

  Also disclosed is a method for producing a polycarbonate polyol by reacting a diaryl carbonate and a polyol (see, for example, Patent Document 6).

JP-A-5-51428 JP-A-2-289616 JP2012-072350A JP 2012-077280 A WO09 / 033934 Pamphlet Japanese Patent No. 4198940

"Basics and Applications of Polyurethane" pages 96-106, supervised by Katsuharu Matsunaga, CMC Publishing Co., Ltd., published in November 2006

  When polycarbonate diol is produced using a dihydroxy compound as a monomer component, these dihydroxy compounds have low polymerization reactivity, so that it is necessary to increase the polymerization reactivity, for example, by increasing the amount of catalyst or raising the temperature. Therefore, the polycarbonate diol produced under these conditions is colored or inferior in thermal stability.

  Further, when diaryl carbonate, which is a highly reactive carbonate source, is used, there is a problem of coloring due to the influence of a phenolic compound by-produced during the reaction.

Furthermore, when the polycarbonate diol having the above-mentioned problems is used as a raw material for the polycarbonate-based polyurethane, there is a risk of causing coloration during the polyurethane-forming reaction, deterioration of the thermal stability of the polyurethane, and color change due to heating. .
In order to solve these problems, a phosphorus compound is added during the polymerization reaction to reduce the coloration of the polycarbonate diol, or a phosphorus compound or a hindered phenol compound is used as a heat stabilizer in the polyurethane produced using the polycarbonate diol. Attempts have been made to add, but further improvements have been demanded.

  This invention is made | formed in view of the above-mentioned subject, The objective is to provide the polycarbonate diol containing composition excellent in heat resistance with little color change by heating, etc. with favorable color tone.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the number average molecular weight is 250 or more and 5000 or less, and the ratio of the hydroxyl group to the total end groups is 95 mol% or more and at least 1 The present inventors have found that the above-described problems can be solved by a polycarbonate diol-containing composition containing at least one phosphorus compound and at least one hindered phenol compound, and have reached the present invention.

（式（Ｄ）において、ｎは０又は１、Ｒ^１及びＲ^２はそれぞれ独立に炭素数１〜１５のアルキル基、アルケニル基、アルキニル基、及びアルコキシ基よりなる群から選ばれる基であり、これらの基はヘテロ原子を含有していてもよい。Ｘは、それぞれ独立にヘテロ原子を含有してもよい炭素数１〜１５の２価の基を表す。）

（式（Ｅ）において、上記式（Ｅ）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

（式（Ａ）において、Ｙは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｂ）において、Ｚは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｃ）において、Ｒ₁、Ｒ₂、Ｒ₃はそれぞれ独立に水素あるいは炭素数１〜９のアル
キル基を示す。） That is, the gist of the present invention resides in the following [1] to [9].
[1] (1) the following formula (D) represented by the structural units, and (2) has a moiety represented by the following formula (E), the structural unit derived from a no dihydroxy compound an aromatic ring structure among one of the structural units, and (3) (1), a (2) other than, having no aromatic ring structure, Lupo polycarbonate diol having a structural unit derived from a dihydroxy compound of an aliphatic hydrocarbon And a polycarbonate diol-containing composition containing a polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less and a hydroxyl group ratio of 95 mol% or more to all terminal groups, a phosphorus compound, and a hindered phenol compound. And the phosphorus compound is a compound represented by the following formula (A) and / or a compound represented by the following formula (B), and the content of the phosphorus compound is: It is 2 ppm or more and 50 ppm or less as a phosphorus atom with respect to the mass of the carbonate diol-containing composition, and the content of the hindered phenol compound is 50 ppm or more and 500 ppm or less with respect to the mass of the polycarbonate diol-containing composition. A polycarbonate diol-containing composition characterized by being.

(In Formula (D), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an alkynyl group, and an alkoxy group, These groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

(In the formula (E), the case where the site represented by the above formula (E) is a part of —CH ₂ —O—H is excluded.)

(In formula (A), Y represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (B), Z represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms.)

[ 2 ] The polycarbonate diol-containing composition according to [1 ], wherein the polycarbonate diol is a polycarbonate diol obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials.
[ 3 ] The polycarbonate diol-containing composition as described in [ 2 ], wherein the carbonic acid diester is diaryl carbonate .
[4 ] The structural unit represented by the formula (D) is derived from 2,2-dialkyl-1,3-propanediol, according to any one of [1] to [3] Polycarbonate diol-containing composition .
[5 ] The dihydroxy compound having a site represented by the formula (E) is at least one dihydroxy compound selected from the group consisting of isosorbide, isomannide, and isoidide . [4] The polycarbonate diol-containing composition according to any one of [4] .

（式（Ｄ）において、ｎは０又は１、Ｒ^１及びＲ^２はそれぞれ独立に炭素数１〜１５のアルキル基、アルケニル基、アルキニル基、及びアルコキシ基よりなる群から選ばれる基であり、これらの基はヘテロ原子を含有していてもよい。Ｘは、それぞれ独立にヘテロ原子を含有してもよい炭素数１〜１５の２価の基を表す。）

（式（Ｅ）において、上記式（Ｅ）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

（式（Ａ）において、Ｙは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｂ）において、Ｚは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｃ）において、Ｒ₁、Ｒ₂、Ｒ₃はそれぞれ独立に水素あるいは炭素数１〜９のアルキル基を示す。） [6] (1) the following formula (D) by the structure units of which are represented, and (2) has a moiety represented by the following formula (E), a structural unit derived from a no dihydroxy compound an aromatic ring structure one of the structural units of and, (3) (1), (2) other than, having no aromatic ring structure, Lupo polycarbonate diol having a structural unit derived from a dihydroxy compound of an aliphatic hydrocarbon And a polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less and a ratio of hydroxyl groups to all terminal groups of 95 mol% or more, a phosphorus compound, and a hindered phenol compound, Is a compound represented by the following formula (A) and / or a compound represented by the following formula (B), and the content of the phosphorus compound is based on the mass of the polycarbonate diol-containing composition. And the manufacturing method of the polycarbonate diol containing composition which is 2 ppm or more and 50 ppm or less as a phosphorus atom, and content of the said hindered phenol type compound is 50 ppm or more and 500 ppm or less with respect to the mass of the said polycarbonate diol containing composition. The polycarbonate diol-containing composition is obtained by transesterification using a dihydroxy compound and a carbonic acid diester as raw materials and in the presence of the phosphorus compound and the hindered phenol compound. The manufacturing method of a containing composition.

(In Formula (D), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an alkynyl group, and an alkoxy group, These groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

(In the formula (E), the case where the site represented by the above formula (E) is a part of —CH ₂ —O—H is excluded.)

(In formula (A), Y represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (B), Z represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms.)

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polycarbonate diol containing composition excellent in heat resistance with a favorable color tone, little coloring change by heating, etc.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

[1. Polycarbonate diol-containing composition]
The polycarbonate diol-containing composition of the present invention comprises a polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less, and a ratio of hydroxyl groups to all terminal groups of 95 mol% or more, a phosphorus compound, and a hindered phenol compound. It contains.
The polycarbonate diol-containing composition of the present invention is preferably obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials in the presence of a phosphorus compound and a hindered phenol compound.

  Hereinafter, the polycarbonate diol, the phosphorus compound, the hindered phenol compound, and the method for producing the polycarbonate diol-containing composition constituting the polycarbonate diol-containing composition of the present invention will be described in detail.

[2. Polycarbonate diol]
<2-1. Polycarbonate diol>
The polycarbonate diol-containing composition of the present invention has a number average molecular weight of 250 or more and 5000 or less, and the ratio of hydroxyl groups to all terminal groups is 95 mol% or more (hereinafter also referred to as “polycarbonate diol used in the present invention”). Containing.
The polycarbonate diol used in the present invention is preferably obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials. The transesterification reaction is more preferably performed in the presence of a transesterification catalyst.

(Molecular weight distribution)
The lower limit of the number average molecular weight (Mn) of the polycarbonate diol used in the present invention is usually 250, preferably 500, more preferably 600, and particularly preferably 800. On the other hand, the upper limit is usually 5,000, preferably 4,000, and more preferably 3,000. When the number average molecular weight of the polycarbonate diol is less than the lower limit, the characteristic properties of the polycarbonate diol derived from the raw material dihydroxy compound component such as flexibility and hardness may not be sufficiently obtained. On the other hand, when the above upper limit is exceeded, the viscosity increases, which may affect handling during polyurethane formation.

  The molecular weight distribution (Mw / Mn) of the polycarbonate diol used in the present invention is not particularly limited, but the lower limit is usually 1.5, preferably 2.0. The upper limit is usually 3.5, preferably 3.0.

When the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this polycarbonate diol tend to become hard at low temperatures, the elongation tends to be small, and when trying to produce a polycarbonate diol having a molecular weight distribution less than the above range, Sophisticated purification operations such as removing oligomers may be required.

Here, Mw is a weight average molecular weight, and Mn is a number average molecular weight, which can be usually determined by measurement by gel permeation chromatography (GPC). Alternatively, ¹ H-NMR is measured, and the number average molecular weight can be determined from the integrated value by a terminal group quantification method.

(Terminal structure of molecular chain)
The polycarbonate diol used in the present invention basically has a hydroxyl group as the terminal structure of the molecular chain.
In the present invention, the proportion of the structure in which the molecular chain terminal contained in the polycarbonate diol is a hydroxyl group is usually 95 mol% or more, preferably 97 mol% or more, more preferably 97 mol% or more of the total number of terminal groups. Is preferably 98 mol% or more. The upper limit of the ratio of the number of molecular chain terminals to the hydroxyl group is not particularly limited, and is usually 99.9 mol%, preferably 99.99 mol%, and most preferably 99.999 mol%. When the ratio of the hydroxyl group is smaller than the above lower limit, the degree of polymerization may not increase when the polyurethane-forming reaction is performed using the polycarbonate diol-containing composition of the present invention as a raw material. On the other hand, if it is larger than the upper limit, the polymerization rate may not be controlled during the polyurethane reaction.

  In the polycarbonate diol used in the present invention, the terminal structure of the polymer is basically a hydroxyl group, but in the product of the polycarbonate diol obtained by the reaction of a dihydroxy compound and a carbonic acid diester, some polymer terminals are not hydroxyl groups as impurities. There may be a structure. As specific examples of the structure, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many are structures derived from a carbonic acid diester.

For example, when diphenyl carbonate is used as the carbonic acid diester, phenoxy group (PhO-) is used as the aryloxy group, methoxy group (MeO-) is used as the alkyloxy group when dimethyl carbonate is used, and ethoxy group is used when diethyl carbonate is used. When (EtO-), ethylene carbonate is used, a hydroxyethoxy group (HOCH ₂ CH ₂ O-) may remain as a terminal group (where Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group).

  In the present invention, the proportion of the structure in which the molecular chain terminal contained in the polycarbonate diol is an alkyloxy group or an aryloxy group is usually 5 mol% or less of the total number of terminal groups, preferably 5 mol% or less. Is preferably 3 mol% or less, more preferably 1 mol% or less. The lower limit of the ratio of the number of the molecular chain terminal at the end of the alkyloxy group or aryloxy group is not particularly limited, and is usually 0.01 mol%, preferably 0.001 mol%, most preferably 0 mol%. . If the proportion of alkyloxy group or aryloxy group is large, the degree of polymerization may not increase during the polyurethane reaction.

  As described above, the polycarbonate diol used in the present invention has a structure in which the ratio of the number of molecular chain ends to a hydroxyl group is usually 95% or more, and the hydroxyl group can react with an isocyanate during the polyurethane reaction.

The hydroxyl value of the polycarbonate diol according to the first aspect of the present invention is not particularly limited, but the lower limit is usually 20 mg-KOH / g, preferably 30 mg-KOH / g, more preferably 40 mg-KOH / g. The upper limit is usually 230 mg-KOH / g, preferably 1
90 mg-KOH / g, more preferably 140 mg-KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high, and handling during polyurethane formation may be difficult. If the upper limit is exceeded, strength and hardness may be insufficient when polyurethane is used.

<2-2. Dihydroxy Compound>
The polycarbonate diol used in the present invention is preferably obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing a first dihydroxy compound and / or a second dihydroxy compound described later and a carbonic acid diester as raw materials. Hereinafter, the first dihydroxy compound and the second dihydroxy compound are collectively referred to as “the dihydroxy compound of the present invention”.
A dihydroxy compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(First dihydroxy compound)
The polycarbonate diol used in the present invention preferably has a structural unit represented by the following formula (D) as part of its structure. The polycarbonate diol used in the present invention has a structure derived from a dihydroxy compound having a site represented by the following formula (F) in a part of the structure (hereinafter sometimes referred to as “first dihydroxy compound”). It is preferable to include at least a unit (first structural unit). That is, the first dihydroxy compound according to the present invention is preferably a raw material compound that gives a structure of the following formula (D) when polycarbonate diol is used, and further includes two hydroxyl groups and a structure of the following formula (F). Preferably it contains at least units. In addition, the polycarbonate diol used in the present invention preferably has a structure derived from the first dihydroxy compound and represented by the following formula (D).

（式（Ｄ）において、ｎは０又は１、Ｒ^１及びＲ^２はそれぞれ独立に炭素数１〜１５のアルキル基、アリール基、アルケニル基、アルキニル基、及びアルコキシ基よりなる群から選ばれる基であり、これらの基はヘテロ原子を含有していてもよい。Ｘは、それぞれ独立にヘテロ原子を含有してもよい炭素数１〜１５の２価の基を表す。）

(In formula (D), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an aryl group, an alkenyl group, an alkynyl group, and an alkoxy group. And these groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

（式（Ｆ）において、ｎは０又は１、Ｒ^１及びＲ^２はそれぞれ独立に炭素数１〜１５のアルキル基、アリール基、アルケニル基、アルキニル基、及びアルコキシ基よりなる群から選ばれる基であり、これらの基はヘテロ原子を含有していてもよい。Ｘは、それぞれ独立にヘテロ原子を含有してもよい炭素数１〜１５の２価の基を表す。）

(In Formula (F), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an aryl group, an alkenyl group, an alkynyl group, and an alkoxy group. And these groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

R ¹ and R ^{2 in} formulas (D) and (F) are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an aryl group, an alkenyl group, an alkynyl group, and an alkoxy group, These groups may contain a hetero atom. Preferably it is a C1-C15 alkyl group.
X in the formulas (D) and (F) each independently represents a C 1-15 divalent group that may contain a hetero atom. X may contain a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

  The first dihydroxy compound according to the present invention is not particularly limited as long as it has a site represented by the above formula (F) in a part of its structure. For example, 2,2-dimethyl- 1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-pentyl-2-propyl-1 2,2-dialkyl-substituted 1,3-propanediols such as 1,3-propanediol (hereinafter also referred to as “2,2-dialkyl-1,3-propanediols”, provided that the alkyl group has 15 or less carbon atoms. Such as 2,2,4,4-tetramethyl-1,5-pentanediol, and 2,2,9,9-tetramethyl-1,10-decanediol. Alkyl substituted alkylenediols, and the like.

  Among these dihydroxy compounds, 2,2-dimethyl-1,3-, from the viewpoint of easy availability, easy handling, reactivity during polymerization, and hue of the resulting polycarbonate diol and polycarbonate diol-containing composition. 2, such as propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-pentyl-2-propyl-1,3-propanediol 2-dialkyl substituted 1,3-propanediol is preferred.

(Second dihydroxy compound)
The polycarbonate diol used in the present invention is a structural unit derived from a dihydroxy compound having a site represented by the following formula (E) in a part of its structure (hereinafter sometimes referred to as “second dihydroxy compound”) ( It is preferable to include at least a second structural unit. That is, the second dihydroxy compound according to the present invention is preferably a raw material compound that gives a structure of the following formula (D) when polycarbonate diol is used, and further has two hydroxyl groups and a structure of the following formula (E). Preferably it contains at least units.

（但し、式（Ｅ）において、上記式（Ｅ）で表される部位が−ＣＨ_２−Ｏ−Ｈの一部である場合を除く。）

(However, in the formula (E), the part represented by the formula (E) is a part of —CH ₂ —O—H).

  When the ratio of the structural unit derived from the dihydroxy compound having the site represented by the above formula (E) is too large, the reaction in producing the polyurethane may be difficult to control.

  The second dihydroxy compound according to the present invention is not particularly limited as long as it has a site represented by the above formula (E) in a part of its structure. For example, diethylene glycol, triethylene glycol, Oxyalkylene glycols such as tetraethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9 , 9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- ( -Hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 , 5-Dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2) , 2-dimethylpropoxy) phenyl) fluorinated fluorene such as fluorene, etc., a compound having an aromatic group in the side chain and an ether group bonded to the aromatic group in the main chain, represented by the following formula (H) Examples thereof include a dihydroxy compound and a compound having a cyclic ether structure such as spiroglycol represented by the following formula (I) and the following formula (J).

Among these dihydroxy compounds, oxyalkylene glycols such as diethylene glycol and triethylene glycol are available from the viewpoint of easy availability, easy handling, reactivity during polymerization, and hue of the resulting polycarbonate diol and polycarbonate diol-containing composition. And compounds having a cyclic ether structure are preferred, and among the compounds having a cyclic ether structure, those having a plurality of ring structures are preferred.
Among these, from the viewpoint of heat resistance, compounds having a cyclic ether structure, represented by dihydroxy compounds represented by the following formulas (H), (I), and (J), are preferable, and the cyclic ether structure is Of these compounds, those having a plurality of ring structures are preferable. Furthermore, anhydrous sugar alcohols represented by dihydroxy compounds represented by the following formula (H) are preferred.

  These may be used alone or in combination of two or more depending on the required performance of the polycarbonate diol and the polycarbonate diol-containing composition to be obtained.

Examples of the dihydroxy compound represented by the above formula (H) include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
Among these dihydroxy compounds, it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of light resistance of the polycarbonate diol and the polycarbonate diol-containing composition, and among them, it is abundant as a plant-derived resource and can be easily obtained. Isosorbide obtained by dehydrating and condensing sorbitol produced from various starches is most preferable from the viewpoints of availability, light resistance, optical properties, moldability, heat resistance, and carbon neutrality.

(Other dihydroxy compounds)
The polycarbonate diol used in the present invention contains a structural unit derived from a dihydroxy compound other than the first dihydroxy compound or the second dihydroxy compound (hereinafter sometimes referred to as “other dihydroxy compound”). Other dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-decanediol, 1,2 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclo Xanthodimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2, Dihydroxy compounds of aliphatic hydrocarbons such as 5-norbornane dimethanol and 1,3-adamantane dimethanol, 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4 -Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, , 2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4 -Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone, Bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 9,9-bis (4- (2-hydroxyethoxy-2-methyl) Phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluor And aromatic bisphenols such as 9,9-bis (4-hydroxy-2-methylphenyl) fluorene. Among the aliphatic hydroxy dihydroxy compounds, 1,2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, Dihydroxy compounds of alicyclic hydrocarbons such as 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol are preferred.

  Among these, from the viewpoint of light resistance of the polycarbonate diol and the polycarbonate diol-containing composition, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, a dihydroxy compound of an aliphatic hydrocarbon is preferable. Examples of the aliphatic hydrocarbon dihydroxy compound include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and tricyclodecanedi. Methanol is preferable, and 1,4-butanediol and 1,6-hexanediol are particularly preferable.

<2-3. Carbonic acid diester>
The polycarbonate diol used in the present invention is preferably obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the first dihydroxy compound and / or the second dihydroxy compound and a carbonic acid diester as raw materials.

Examples of the carbonic acid diester used in the present invention include diaryl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. Examples include alkylene carbonate.
Among these, diaryl carbonate is preferable, and diphenyl carbonate is particularly preferable.
These carbonic acid diesters may be used alone or in combination of two or more.

  Carbonic acid diesters may contain impurities such as chloride ions, which may inhibit the polymerization reaction and may affect the hue of the resulting polycarbonate diol and polycarbonate diol-containing composition. Accordingly, it is preferable to use a product purified by distillation or the like.

<2-4. Transesterification Catalyst>
The polycarbonate diol used in the present invention is produced by transesterifying the dihydroxy compound containing the first dihydroxy compound and / or the second dihydroxy compound and the carbonic acid diester as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

As the transesterification catalyst, any compound that is generally considered to have transesterification ability can be used without limitation.
Examples of transesterification catalysts include lithium, sodium, potassium, rubidium, cesium and other periodic table group 1 metal compounds; magnesium, calcium, strontium, barium and other periodic table group 2 metal compounds; titanium, zirconium Periodic Table Group 4 metal compounds such as Hafnium; Periodic Table Group 5 metal compounds such as hafnium; Periodic Table Group 9 metal compounds such as cobalt; Periodic Table Group 12 metal compounds such as zinc; Periodic table Group 13 metal compounds; Germanium, tin, lead and other periodic table group 14 metal compounds; Antimony, bismuth and other periodic table Group 15 metal compounds; Lanthanum, cerium, europium, ytterbium and other lanthanide metals And the like. Among these, from the viewpoint of increasing the transesterification reaction rate, compounds of Group 1 metal of the periodic table, compounds of Group 2 metal of the periodic table, compounds of Group 4 metal of the periodic table, compounds of Group 5 metal of the periodic table, Periodic table Group 9 metal compound, Periodic table Group 12 metal compound, Periodic table Group 13 metal compound, Periodic table Group 14 metal compound, Periodic table Group 1 metal compound, Periodic table 2 Group metal compounds are more preferred, and periodic table Group 2 metal compounds are more preferred. Among the compounds of Group 1 metals of the periodic table, lithium, potassium, and sodium compounds are preferable, lithium and sodium compounds are more preferable, and sodium compounds are more preferable. Among the compounds of Group 2 metals of the periodic table, magnesium, calcium and barium compounds are preferred, calcium and magnesium compounds are more preferred, and magnesium compounds are more preferred. These metal compounds may be used as hydroxides or salts. Examples of salts when used as a salt include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonic acid, toluenesulfonic acid and trifluoro Examples thereof include sulfonates such as romethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates, and dihydrogen phosphates; acetylacetonate salts. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

  Among these, Preferably, periodic table group 1 metal, periodic table group 2 metal, periodic table group 4 metal, periodic table group 5 metal, periodic table group 9 metal, periodic table group 12 metal, periodic table An acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, or alkoxide of at least one metal selected from the group consisting of Group 13 metals and Group 14 metals is used. More preferably, an acetate, carbonate or hydroxide of a Group 2 metal of the periodic table is used, more preferably a Group 2 metal compound of the periodic table such as magnesium or calcium, particularly preferably an acetate of the metal. Most preferably, magnesium acetate is used.

These metal compounds may be used individually by 1 type, and may use 2 or more types together.
Specific examples of compounds using Group 1 metals in the periodic table of the transesterification catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, carbonic acid Lithium, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, benzoic acid Cesium, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate; disodium salt of bisphenol A, dipotassium salt, dicesium salt, dilithium salt; phenol Sodium salt, potassium salt, cesium salt, a lithium salt; and the like are.

  Examples of compounds using Group 2 metals of the periodic table include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, Examples include calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenyl phosphate.

  Examples of compounds using Group 4 metal, Group 12 metal, and Group 14 metal of the periodic table include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate; titanium such as titanium tetrachloride Halides: Zinc salts such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate; tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin Tin compounds such as oxide and dibutyltin dimethoxide; zirconium compounds such as zirconium acetylacetonate, zirconium oxyacetate and zirconium tetrabutoxide; lead compounds such as lead (II) acetate, lead (IV) acetate and lead (IV) chloride Can be mentioned.

When the transesterification catalyst is used in the production of the polycarbonate polyol according to the present invention, the amount used is preferably an amount that does not affect the performance even if it remains in the obtained polycarbonate polyol, and the weight of the dihydroxy compound The upper limit is preferably 500 ppm, more preferably 100 ppm, and still more preferably 50 ppm as a weight ratio in terms of metal to the weight. On the other hand, the lower limit is an amount that provides sufficient polymerization activity, and is preferably 0.01 ppm, more preferably 0.1 ppm, and even more preferably 1 ppm.
When a group 2 metal compound of the periodic table is used as a catalyst, the total amount of all metal atoms is preferably 5 μmol or more, more preferably 7 μmol or more, and even more preferably 10 μmol per 1 mol of all dihydroxy compounds used as raw materials. As mentioned above, Preferably it is 500 micromol or less, More preferably, it is 300 micromol or less, More preferably, it is 100 micromol or less.

  If the amount of the catalyst is too small, the polymerization rate becomes slow. As a result, when trying to obtain a polycarbonate diol having a desired molecular weight, the polymerization temperature has to be increased, and the resulting polycarbonate diol and the polycarbonate diol-containing composition are obtained. There is a possibility that the hue may be affected, or the unreacted raw material may volatilize during the polymerization and the molar ratio of the dihydroxy compound and the carbonic acid diester may collapse, resulting in an increase in molecular weight. On the other hand, when the amount of the polymerization catalyst used is too large, not only the hue of the resulting polycarbonate diol and the polycarbonate diol-containing composition is affected, but also the reaction rate in the urethanization reaction may be affected.

Further, Group 1 metals of the periodic table, especially lithium, sodium, potassium, cesium, particularly sodium, potassium, cesium, may have a bad influence on the hue when contained in a polycarbonate diol-containing composition, May be mixed not only from the catalyst used but also from the raw materials and the reactor, so that the total amount of these in the polycarbonate diol-containing composition is usually 1 mass ppm or less, preferably 0.8 mass as the metal amount. ppm or less, more preferably 0.7 mass ppm or less.
The amount of metal in the polycarbonate diol and the polycarbonate diol-containing composition can be measured by recovering the metal in the polycarbonate diol-containing composition by a method such as wet ashing, and then using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP). Can be measured using.

  Further, when a polycarbonate diol used in the present invention is produced using diaryl carbonate such as diphenyl carbonate as the carbonic acid diester, phenol and substituted phenol are by-produced and remain in the polycarbonate diol, in the polycarbonate diol-containing composition. In addition, phenol and substituted phenols also have an aromatic ring, which may cause coloring, and may cause odors, or may act as a terminal terminator during polyurethane formation and have a degree of polymerization. It may not go up. The polycarbonate diol contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 mass ppm or more after a normal batch reaction, but a horizontal reactor or thin film having excellent devolatilization performance. Using an evaporator, the aromatic monohydroxy compound in the polycarbonate diol is 500 ppm by mass or less, preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by mass.

  These aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

[3. Phosphorus compound]
The polycarbonate diol-containing composition of the present invention contains a phosphorus compound.
The phosphorus compound is a compound having a phosphorus atom in the molecule, and the phosphorus compound used in the present invention is represented by the compound represented by the following formula (A) and / or the following formula (B). A compound is preferred.

（式（Ａ）において、Ｙは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｂ）において、Ｚは炭素数５〜１８のアルキル基、もしくは下記式（Ｃ）で表される芳香族基を示す。）

（式（Ｃ）において、Ｒ₁、Ｒ₂、Ｒ₃はそれぞれ独立に水素あるいは炭素数１〜９のアルキル基を示す。）

(In formula (A), Y represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (B), Z represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms.)

Y in the formula (A) represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the above formula (C).
In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms. R ₁ , R ₂ and R ₃ preferably have 3 or more carbon atoms, particularly preferably 4 or more, more preferably 8 or less, and particularly preferably 6 or less. Of these, a tert-butyl group is particularly preferred.

In the polycarbonate diol-containing composition of the present invention, the phosphorus compound content is preferably 2 ppm or more, more preferably 5 ppm or more, more preferably 10 ppm, based on the mass of the polycarbonate diol-containing composition as phosphorus atoms. It is above, and it is preferable that it is 100 ppm or less, More preferably, it is 50 ppm or less, More preferably, it is 25 ppm or less.
When the content of the phosphorus compound is within the above range, it is possible to obtain a polycarbonate diol-containing composition having good color tone and little color change or composition change due to heating.

Examples of the compound represented by the formula (A) include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis ( 2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
Among these, bis (nonylphenyl) pentaerythritol diphosphite and distearyl pentaerythritol diphosphite are preferably used.
The compound represented by the formula (A) may be used alone or in combination of two or more.

Examples of the compound represented by the formula (B) include triphenyl phosphite, tris (2-isobutylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris. (2-t-pentylphenyl) phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di-t-butylphenyl) Examples thereof include phosphite, tris (2-t-butyl-6-methylphenyl) phosphite, diphenyloctyl phosphite, diphenyldecyl phosphite, and trioctyl phosphite.
Among these, triphenyl phosphite, tris (2-t-butyl-6-methylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite Preferably used.
The compound represented by Formula (B) may use together 1 type (s) or 2 or more types.

  The molecular weight of the compound represented by formula (A) or formula (B) is not particularly limited, but usually 300 or more is used, preferably 400 or more, particularly preferably 500 or more, and usually 1200 or less, preferably Is 1000 or less, particularly preferably 700 or less.

  The polycarbonate diol-containing composition of the present invention contains a phosphorus compound. When the polycarbonate diol is produced by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials, the polycarbonate diol in the polycondensation reaction is produced. From the viewpoint of preventing deterioration, for example, it is preferable to perform a transesterification reaction in the presence of a phosphorus compound by putting a phosphorus compound together with a raw material monomer into a reactor.

[4. Hindered phenolic compounds]
The polycarbonate diol-containing composition of the present invention contains a hindered phenol compound.

  In the polycarbonate diol-containing composition of the present invention, the content of the hindered phenol-based compound is 50 ppm or more from the viewpoint of the effect of suppressing coloring and heat resistance with respect to the mass of the polycarbonate diol-containing composition. More preferably, it is 100 ppm or more, more preferably 200 ppm or more, and is preferably 2000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less from the viewpoint of urethanization reaction or urethane physical properties. It is.

  When the content of the hindered phenol compound is within the above range, it is possible to obtain a polycarbonate diol-containing composition having good color tone and little color change, composition change, and the like due to heating.

  Examples of the hindered phenol compound include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnama ), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphine Acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] Ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 4 or more carbon atoms is preferable. Specifically, triethylene glycol-bis [3- (3-tert-butyl-5- Methyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate}, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5 -Methyl-4-hydroxyphenyl) propionate] is more preferred.
One or more hindered phenol compounds may be used in combination.

  The polycarbonate diol-containing composition of the present invention contains a hindered phenol-based compound. When the polycarbonate diol is produced by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials, the polycarbonate undergoing a polycondensation reaction. From the viewpoint of preventing deterioration of the diol, for example, it is preferable to perform a transesterification reaction in the presence of the hindered phenol compound by putting the hindered phenol compound together with the raw material monomer into the reactor.

[5. Method for producing polycarbonate diol-containing composition]
The polycarbonate diol-containing composition of the present invention uses a dihydroxy compound and a carbonic acid diester as raw materials, and in the presence of a phosphorus compound and a hindered phenol compound, if necessary, by means of a transesterification reaction using the above-described transesterification catalyst. Can be manufactured. That is, the method for producing a polycarbonate diol-containing composition of the present invention (hereinafter also referred to as the production method of the present invention) comprises adding a phosphorus compound and a hindered phenol compound in the polycarbonate diol production process, and performing internal polymerization. It is characterized by doing.

<5-1. Raw material>
In the method for producing a polycarbonate diol-containing composition of the present invention, as a dihydroxy compound, a dihydroxy compound having a moiety represented by the above formula (F) and / or a dihydroxy compound having a moiety represented by the above formula (E). Is preferably used. Moreover, it is preferable to use the above-mentioned carbonic acid diester as the carbonic acid diester. Moreover, it is preferable to use the compound represented by the above formula (A) and / or the compound represented by the above formula (B) as the phosphorus compound. Moreover, it is preferable to use the above-mentioned hindered phenol type compound as a hindered phenol type compound.

  The polycarbonate diol used in the present invention can be obtained by polycondensation of a dihydroxy compound and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound, carbonic acid diester, phosphorus compound, and hindered phenol compound are It is preferable to mix uniformly before the transesterification reaction and perform the transesterification reaction in the presence of the phosphorus compound and the hindered phenol compound to obtain the polycarbonate diol-containing composition of the present invention. The phosphorus compound and the hindered phenol compound can be mixed into the reaction system at any timing during the transesterification reaction before the transesterification reaction, but are raw materials from the viewpoint of suppressing thermal degradation of the dihydroxy compound. Most preferably, the dihydroxy compound and the carbonic acid diester are mixed at the same time. In addition, phosphorus compounds and hindered phenol compounds are mixed with solid raw materials of carbonic acid diesters and dihydroxy compounds, which are raw materials, and charged into a mixing tank, or dissolved or dispersed in liquid raw materials, and reactions other than raw materials. It can be added by a method such as uniformly dissolving or dispersing in a solvent that does not contribute to the above.

<5-2. Reaction conditions>
In the method for producing a polycarbonate diol-containing composition of the present invention, the mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, particularly preferably 100 ° C. or higher. The upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 120 ° C. or lower. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, and this may often affect solidification and the like. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a change in the hue of the polycarbonate diol and the polycarbonate diol-containing composition obtained, which may affect the light resistance.

  The operation of mixing the dihydroxy compound which is the raw material of the polycarbonate diol used in the present invention and the carbonic acid diester is usually an oxygen concentration of 0.0001% by volume or more, usually 10% by volume or less, preferably 5% by volume or less, particularly preferably 1 It is preferable to carry out in an atmosphere of volume% or less from the viewpoint of influence on the hue.

In order to obtain the polycarbonate diol used in the present invention, the carbonic acid diester is preferably used in a molar ratio of usually 0.50 or more, preferably 0.60 or more, based on the dihydroxy compound used in the reaction. It is preferably used in a molar ratio of 00 or less, preferably 0.98 or less.
If this molar ratio is excessively small, the desired molecular weight of the produced polycarbonate diol may not be reached, or the residual monomer may increase, and the desired physical properties may not be obtained when a polyurethane is obtained.

  On the other hand, when the molar ratio is excessively large, the molecular weight of the polycarbonate diol produced is excessively high, handling becomes difficult, a desired hydroxyl value cannot be obtained, or an alkyloxy group or aryloxy group at the terminal is obtained. There is a possibility that the degree of polymerization does not increase when the ratio of the groups becomes large and the polyurethane-forming reaction is carried out.

  The polycondensation reaction is carried out while measuring the molecular weight of the polycarbonate diol produced, and is terminated when the target molecular weight is reached. The reaction time required for polycondensation varies greatly depending on the dihydroxy compound, carbonic acid diester used, the presence / absence of a catalyst, and the type, so it cannot be specified unconditionally, but the reaction time required to reach a predetermined molecular weight is usually 50 hours or less, preferably 20 hours or less, more preferably 10 hours or less.

  In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type. In the initial stage of the polycondensation reaction, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum. From the viewpoint of hue, it is important to appropriately select the jacket temperature and the internal temperature, and the pressure in the reaction system. For example, if either the temperature or the pressure is changed too quickly before the polycondensation reaction reaches a predetermined value, the unreacted monomer will be distilled off, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a polycondensation rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser in the reactor for performing polycondensation in order to suppress the amount of the monomer to be distilled off, and the effect is particularly effective in a reactor in the early stage of polycondensation having many unreacted monomer components. large. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected depending on the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 ° C. or more at the inlet of the reflux condenser. Preferably it is 80 degreeC or more, Most preferably, it is 100 degreeC or more, Usually, 180 degreeC or less, Preferably it is 150 degreeC or less, Most preferably, it is 130 degreeC or less. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

In order to maintain the polycondensation rate appropriately and suppress the distillation of the monomer, while maintaining the hue, thermal stability, light resistance, etc. of the final polycarbonate diol-containing composition, Selection of type and quantity is important.
The polycarbonate diol used in the present invention is preferably produced by polycondensation in multiple stages using a plurality of reactors using a catalyst. The reason for carrying out polycondensation in a plurality of reactors is the polycondensation reaction. In the initial stage, since there are many monomers in the reaction solution, it is important to suppress the volatilization of the monomer while maintaining the necessary polycondensation reaction rate. This is because it is important to sufficiently distill off the by-produced monohydroxy compound for shifting to the side. Thus, in order to set different polycondensation reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polycondensation reactors arranged in series.

As described above, the number of reactors used in the method for producing the polycarbonate diol used in the present invention may be at least two, but from the viewpoint of production efficiency, preferably three or more, more preferably 3 ~ 5.
In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

  In the present invention, the catalyst used for polycondensation can be mixed in the raw material preparation tank and the raw material storage tank, or can be directly mixed in the polycondensation reaction tank, but from the viewpoint of supply stability and control of the polycondensation reaction. Is provided with a catalyst supply line in the middle of the raw material line before being supplied to the polycondensation reaction tank, and preferably supplied as an aqueous solution.

  If the temperature of the polycondensation reaction is too low, the productivity will decrease and the thermal history of the product will increase.If the temperature is too high, not only will the monomer be volatilized, but the polycarbonate diol and the polycarbonate diol-containing composition will be decomposed and colored. There is a possibility to encourage.

  Specifically, the maximum internal temperature of the polycondensation reactor is usually 70 ° C. or higher, preferably 100 ° C. or higher, more preferably 130 ° C. or higher, usually 250 ° C. or lower, preferably 230 ° C. or lower, more preferably 180 ° C. or lower.

  Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the production system by distilling off the light-boiling components produced out of the system. Therefore, it is usually preferable to carry out the reaction in the latter half of the reaction while employing a reduced pressure condition while distilling off the light boiling component. Alternatively, the reaction can be carried out while efficiently distilling off the light-boiling components produced by gradually lowering the pressure as the reaction proceeds.

In particular, it is preferable to increase the degree of vacuum at the end of the reaction because monohydroxy compounds such as phenol, cyclic carbonate, and the like, which are by-produced, can be distilled off.
The reaction pressure at the end of the reaction is not particularly limited, but the upper limit is usually 10 kPa, preferably 5 kPa, more preferably 1 kPa. In order to effectively distill these light-boiling components, the reaction can be carried out while passing a small amount of an inert gas such as nitrogen, argon or helium through the reaction system.

<5-3. Purification>
After the reaction, the terminal structure in the polycarbonate diol product contained in the polycarbonate diol-containing composition obtained by the above reaction is an impurity having an alkyloxy group, an impurity having an aryloxy group, a phenol, a raw material diol or carbonic acid. Purification can be performed for the purpose of removing the ester, the by-product cyclic carbonate, and the added catalyst. In the purification at that time, a method of distilling off a light boiling compound by distillation can be employed. As a specific method of distillation, there is no particular limitation on the form such as vacuum distillation, steam distillation, thin film distillation, etc., and any method can be adopted. Further, in order to remove water-soluble impurities, it may be washed with water, alkaline water, acidic water, a chelating agent solution or the like. In that case, the compound dissolved in water can be selected arbitrarily.

[6. Other ingredients]
In the polycarbonate diol-containing composition of the present invention, the above-mentioned phosphorus compound and hindered phenol compound are mixed with the raw material dihydroxy compound and carbonic acid diester, and an ester exchange catalyst is added if necessary. May be included as other components.

(Acidic compounds)
The polycarbonate diol-containing composition of the present invention may further contain an acidic compound.
The compounding amount of the acidic compound is preferably 0.00001 parts by mass or more, more preferably 0.0001 parts by mass or more, particularly preferably 0.001 parts by mass or more with respect to 100 parts by mass of the polycarbonate diol-containing composition. 0002 parts by mass or more, on the other hand, preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and particularly preferably 0.001 parts by mass or less.
If the blending amount of the acidic compound is excessively small, coloring of the polycarbonate diol-containing composition may not be sufficiently suppressed. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of a polycarbonate diol containing composition may fall remarkably.

  Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.

These acidic compounds can be mixed in the manufacturing process of a polycarbonate diol containing composition as a compound which neutralizes the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate diol containing composition mentioned above.
The polycarbonate diol-containing composition of the present invention may contain a bluing agent, an antistatic agent, an inorganic filler and the like as desired.

[7. Properties of polycarbonate diol-containing composition]
<APHA value>
The color of the polycarbonate diol-containing composition of the present invention is preferably in a range that does not affect the color of the resulting polyurethane when used in the production of polyurethane, and the degree of coloring is determined by the Hazen color number (APHA value; The value (hereinafter also referred to as “APHA value”) expressed in JIS-K0071-1: 1998) is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.

<Application>
The polycarbonate diol-containing composition of the present invention is excellent in light resistance, transparency, hue, heat resistance, and thermal stability. The polycarbonate diol-containing composition of the present invention is suitably used as a raw material for polycarbonate-based polyurethane.

[8. Polyurethane]
Polyurethane can be produced using the above-described polycarbonate diol of the present invention. Hereinafter, the polyurethane obtained by using the polycarbonate diol of the present invention may be referred to as “the polyurethane of the present invention”.
The polyurethane of the present invention is obtained using the above-mentioned polycarbonate diol-containing composition of the present invention as a raw material.

In the method for producing a polyurethane using the polycarbonate diol-containing composition of the present invention, known polyurethane reaction conditions for producing a polyurethane are usually used.
For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol-containing composition of the present invention with a polyisocyanate and a chain extender in the range of room temperature to 200 ° C.
Further, the polycarbonate diol-containing composition of the present invention and excess polyisocyanate are first reacted to produce a prepolymer of terminal isocyanate, and a polyurethane can be produced by increasing the degree of polymerization using a chain extender.

<8-1. Reaction reagents>
(Polyisocyanate)
Examples of the polyisocyanate used for producing the polyurethane using the polycarbonate diol-containing composition of the present invention include various known polyisocyanate compounds such as aliphatic, alicyclic or aromatic.

  For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimerized isocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group Aliphatic diisocyanates; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,3-bis (Isocyanatomethyl) cycloaliphatic diisocyanates such as cyclohexane; xylylene diisocyanate, 4,4'-diphenyldi Cyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4 ' -Dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethyl A typical example is aromatic diisocyanate such as xylylene diisocyanate. These may be used alone or in combination of two or more.

  Among these, preferred organic diisocyanates are 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate from the viewpoint that the physical properties of the resulting polyurethane are balanced and that a large amount can be obtained industrially at low cost.

(Chain extender)
The chain extender used in producing the polyurethane of the present invention is a low molecular weight compound having at least two active hydrogens that react with an isocyanate group, and usually includes polyols and polyamines.

Specific examples thereof include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4-heptanediol, 1,8- Linear diols such as octanediol, 1,4-dimethylolhexane, 1,9-nonanediol, 1,12-dodecanediol, dimer diol; 2-methyl-1,3-propanediol, 2,2-dimethyl -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl- Diols having a branched chain such as 1,3-propanediol; Diols having a cyclic group such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, xylylene glycol, 1 Diols having aromatic groups such as 1,4-dihydroxyethylbenzene and 4,4′-methylenebis (hydroxyethylbenzene); Polyols such as glycerin, trimethylolpropane and pentaerythritol; N-methylethanolamine, N-ethylethanolamine Hydroxyamines such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2-hydro Xylethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis (o-chloroaniline) ), Xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, polyamines such as N, N′-diaminopiperazine; and water.
These chain extenders can be used alone or in combination of two or more.

  Among these, preferred chain extenders are preferably 1,4-butanediol, 1,5-pentanediol, 1,5-butanediol, and the like because the balance of physical properties of the obtained polyurethane is preferable, and a large amount can be obtained industrially at low cost. 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-aminopropane and the like.

(Chain terminator)
In producing the polyurethane of the present invention, a chain terminator having one active hydrogen group can be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane.
Examples of these chain terminators include aliphatic monools such as ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having an amino group. Is done.
These may be used alone or in combination of two or more.

(catalyst)
In the polyurethane formation reaction in producing the polyurethane of the present invention, tin compounds such as amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine or tin catalysts such as trimethyltin laurate and dibutyltin dilaurate, Can also use known urethane polymerization catalysts represented by organic metal salts such as titanium compounds. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

(Other polyols)
When producing the polyurethane of the present invention, in addition to the polycarbonate diol-containing composition of the present invention, other known polyols can be used in combination as required. Examples of known polyols that can be used at that time include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol (PTMG); bisphenol A, ethylene oxide adducts of glycerin, propylene oxide adducts, etc. Polyalkylene alkylene oxide adducts; polyester polyol, polycaprolactone polyol, polycarbonate polyol and the like.

  Examples of polyester polyols include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, maleic acid, succinic acid, fumaric acid, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, Examples thereof include those obtained from glycols such as 1,5-pentanediol, 1,6-hexanediol, and trimethylolpropane.

  Examples of the polycarbonate polyol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, homopolycarbonate diol produced from 2-methylpropanediol, and copolymerized polycarbonate diol. Is an example of what can be used.

  When these other polyols are used, the ratio of the polycarbonate diol-containing composition of the present invention in the total polyol is not particularly limited in order to sufficiently obtain the effect of using the polycarbonate diol-containing composition of the present invention. In general, it is preferably used in an amount of 30% by weight or more, particularly 50% by weight or more.

(solvent)
The polyurethane formation reaction in producing the polyurethane of the present invention may be performed using a solvent.
Preferred solvents include amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ether solvents such as tetrahydrofuran and dioxane; methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and the like. Examples include ketone solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents can be used alone or as a mixed solvent of two or more.

  Among these, preferred organic solvents are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.

  Moreover, the polyurethane resin of an aqueous dispersion can also be manufactured from the polyurethane resin composition with which the polycarbonate diol containing composition of this invention, polydiisocyanate, and the said chain extender were mix | blended.

<8-2. Manufacturing method>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagent, all production methods generally used experimentally or industrially can be used.

  Examples thereof include a method in which a polyol, a polyisocyanate, and a chain extender containing the polycarbonate diol-containing composition of the present invention are mixed and reacted (hereinafter referred to as “one-step method”), or the polycarbonate diol of the present invention is first contained. There is a method of reacting a polyol containing the composition with a polyisocyanate to prepare a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with a chain extender (hereinafter referred to as “two-stage method”).

  In the two-stage method, a polyol containing the polycarbonate diol-containing composition of the present invention is preliminarily reacted with 1 equivalent or more of an organic polyisocyanate to prepare a part of both-end isocyanate intermediate corresponding to the soft segment of polyurethane. It is going to be. In this way, once the prepolymer is prepared and reacted with the chain extender, it may be easy to adjust the molecular weight of the soft segment part, and when it is necessary to ensure phase separation of the soft segment and the hard segment. Is useful.

(One-step method)
The one-stage method is also called a one-shot method, and is a method in which a reaction is carried out by collectively charging a polyol, a polyisocyanate, and a chain extender containing the polycarbonate diol-containing composition of the present invention.

The amount of polyisocyanate used in the one-stage method is not particularly limited, but when the total number of hydroxyl groups of the polyol containing the polycarbonate diol-containing composition of the present invention and the number of hydroxyl groups and amino groups of the chain extender is 1 equivalent, the lower limit Is usually 0.7 equivalents, preferably 0.8 equivalents, more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is usually 3.0 equivalents, preferably 2.0 equivalents, more Preferably it is 1.5 equivalent, More preferably, it is 1.1 equivalent.
If the amount of polyisocyanate used is too large, the unreacted isocyanate group will cause a side reaction, which tends to make it difficult to obtain the desired physical properties. If it is too small, the molecular weight of the polyurethane will not be sufficiently increased, and the desired performance Tend not to be expressed.

  The amount of the chain extender is not particularly limited, but when the number obtained by subtracting the number of isocyanate groups of the polyisocyanate from the number of hydroxyl groups of the polyol containing the polycarbonate diol-containing composition of the present invention is 1 equivalent, the lower limit is usually 0.7 equivalents, preferably 0.8 equivalents, more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is 3.0 equivalents, preferably 2.0 equivalents, more preferably 1.5 equivalents. Equivalent, particularly preferably 1.1 equivalent. If the amount of chain extender used is too large, the resulting polyurethane tends to be difficult to dissolve in the solvent and difficult to process. If too small, the resulting polyurethane is too soft and has sufficient strength, hardness, elastic recovery performance and elasticity. The holding performance may not be obtained or the high temperature characteristics may be deteriorated.

(Two-stage method)
The two-stage method is also called a prepolymer method, in which a polyisocyanate and a polyol containing the polycarbonate diol-containing composition of the present invention are reacted in advance at a polyisocyanate / polyol reaction equivalent ratio of 1.0 to 10.00, and the terminal is isocyanate. This is a method for producing a polyurethane by producing a prepolymer as a base, and then adding a chain extender having active hydrogen such as a polyhydric alcohol or an amine compound to this.

The two-stage method can be carried out without a solvent or in the presence of a solvent.
The polyurethane production by the two-stage method can be carried out by any of the methods (1) to (3) described below.
(1) Without using a solvent, first a polyisocyanate and a polyol containing a polycarbonate diol are directly reacted to synthesize a prepolymer and used as it is in the subsequent chain extension reaction.
(2) A prepolymer is synthesized by the method of (1) and then dissolved in a solvent and used in the subsequent chain extension reaction.
(3) A polyisocyanate and a polyol containing polycarbonate diol are reacted from the beginning using a solvent, and then a chain extension reaction is performed in the solvent.

  In the case of the method (1), when the chain extender is allowed to act, the polyurethane coexists with the solvent by dissolving the chain extender in the solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is important to get in shape.

The amount of polyisocyanate used in the two-stage method is not particularly limited, but the lower limit is usually 1.0, preferably 1., as the number of isocyanate groups when the number of hydroxyl groups of the polyol containing polycarbonate diol is 1 equivalent. The upper limit is usually 10.0, preferably 5.0, and more preferably 3.0.
If the amount of isocyanate used is too large, excess isocyanate groups may cause a side reaction, and if it is too small, the molecular weight of the resulting polyurethane does not increase sufficiently, and there is a tendency to cause problems in strength and thermal stability.

The amount of chain extender used is not particularly limited, but the lower limit is usually 0.1, preferably 0.5, more preferably 0.8 relative to the equivalent of the isocyanate group contained in the prepolymer. Is usually in the range of 5.0, preferably 3.0, and more preferably 2.0.
When performing the chain extension reaction, a monofunctional organic amine or alcohol may be present together for the purpose of adjusting the molecular weight.

  In the chain extension reaction, each component is usually reacted at 0 to 250 ° C., but this temperature varies depending on the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, etc., and is not particularly limited. If the temperature is too low, the progress of the reaction may be too slow, the productivity of the raw material and the polymer may be low, and the productivity may be deteriorated. If the temperature is too high, side reactions and decomposition of the resulting polyurethane may occur. . The chain extension reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added to chain extension reaction as needed.
Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid and the like. Examples of the stabilizer include 2, One type or two or more types such as 6-dibutyl-4-methylphenol, distearylthiodipropionate, di-betanaphthylphenylenediamine, and tri (dinonylphenyl) phosphite can be used. However, when the chain extender is highly reactive, such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.

<8-3. Additives>
The polyurethane of the present invention produced using the polycarbonate diol-containing composition of the present invention has a heat stabilizer, a light stabilizer, a colorant, a filler, a stabilizer, an ultraviolet absorber, an antioxidant, an anti-tacking agent, Various additives such as a flame retardant, an anti-aging agent and an inorganic filler can be added and mixed within a range not impairing the properties of the polyurethane of the present invention.

  Compounds that can be used as heat stabilizers include phosphoric acid, phosphorous acid aliphatic, aromatic or alkyl group-substituted aromatic esters and hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkyl Phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, thiodipropionic acid esters, etc. Compounds containing sulfur; tin compounds such as tin malate and dibutyltin monoxide can be used.

Specific examples of the hindered phenol compound include Irganox 1010 (trade name: manufactured by Ciba Geigy) and Irganox 1520 (trade name: manufactured by Ciba Geigy).
Examples of the phosphorus compound include PEP-36, PEP-24G, and HP-10 (all trade names: manufactured by Asahi Denka Co., Ltd.) Irgafos 168 (trade name: manufactured by Ciba-Gigi Co., Ltd.).
Specific examples of the compound containing sulfur include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).

  Examples of light stabilizers include benzotriazole and benzophenone compounds. Specifically, “TINUVIN 622LD”, “TINUVIN 765” (manufactured by Ciba Specialty Chemicals), “SANOL LS-2626”. “SANOL LS-765” (manufactured by Sankyo Co., Ltd.) or the like can be used.

  Examples of the ultraviolet absorber include “TINUVIN 328” and “TINUVIN 234” (manufactured by Ciba Specialty Chemicals).

  Examples of colorants include direct dyes, acid dyes, basic dyes, metal complex dyes, and the like; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide, and mica; and coupling azo series, condensed azo series, And organic pigments such as anthraquinone, thioindigo, dioxazone, and phthalocyanine.

  Examples of the inorganic filler include short glass fiber, carbon fiber, alumina, talc, graphite, melamine, and clay.

  Examples of the flame retardant include addition of phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, and reactive flame retardants.

  These additives may be used alone or in combination of two or more in any combination and ratio.

  The additive amount of these additives is preferably 0.01% by weight, more preferably 0.05% by weight, still more preferably 0.1% by weight, and the upper limit is preferably 10% by weight with respect to the polyurethane. More preferably, it is 5% by weight, still more preferably 1% by weight. If the amount of the additive added is too small, the effect of the addition cannot be sufficiently obtained, and if it is too large, it may precipitate in the polyurethane or generate turbidity.

<8-4. Physical properties>
(Molecular weight)
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited. However, the number average molecular weight (Mn) in terms of polystyrene measured by GPC is 50,000 to 500,000, particularly 100,000 to 300,000. It is preferable that If the molecular weight is smaller than the lower limit, sufficient strength and hardness may not be obtained. If the molecular weight is larger than the upper limit, it may be necessary to adjust the processing conditions.

<8-5. Application>
The polyurethane of the present invention has the best durability grade in heat resistance and hydrolysis resistance, and is widely used as a durable film, artificial leather for automobiles and furniture, paints (particularly water-based paints), coating agents, and adhesives. can do.

[9. Effects of the present invention]
ADVANTAGE OF THE INVENTION According to this invention, the polycarbonate diol containing composition excellent in heat resistance with favorable color tone and few coloring changes by heating can be provided.

  The polycarbonate diol-containing composition of the present invention contains a polycarbonate diol, a phosphorus compound, and a hindered phenol compound. In the polycarbonate diol-containing composition of the present invention, it is presumed that the above-described effects are exhibited by the phosphorus compound and the hindered phenol compound functioning as an antioxidant.

  In the method for producing a polycarbonate diol-containing composition of the present invention, the polycarbonate diol-containing composition was obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials in the presence of a phosphorus compound and a hindered phenol compound. Is. According to the method for producing a polycarbonate diol-containing composition of the present invention, by performing internal addition polymerization using a phosphorus compound and a hindered phenol compound in combination, the monomer raw material and the polycarbonate diol are thermally decomposed during the transesterification reaction. Is suppressed, and it is estimated that the above-mentioned effect is produced when the phosphorus compound and the hindered phenol compound function as an antioxidant.

  The polycarbonate diol-containing composition of the present invention can be suitably used as a raw material for polyurethane. According to the polyurethane using the polycarbonate diol-containing composition of the present invention as a raw material, the heat resistance, weather resistance, water resistance, chemical resistance, and oleic acid resistance, which are characteristics as a polyurethane derived from a conventional polycarbonate diol, are maintained. It is possible to provide a polyurethane having a good color tone and excellent heat resistance with little color change due to heating.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

The abbreviations of the compounds used in the description of the following examples are as follows.
16HD: 1,6-hexanediol (manufactured by BASF)
ISB: Isosorbide (Rocket Fleure, trade name POLYSORB)
NPG: Neopentyl glycol (Mitsubishi Gas Chemical Co., Ltd.)
DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
IRGANOX245: Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan)
IRGAFOS 168: Tris (2,4-di-t-butylphenyl) phosphite (BA
SF Japan)
PEP-4C: Bis (nonylphenyl) pentaerythritol diphosphite (manufactured by ADEKA)
In the following examples, the physical properties and characteristics of polycarbonate diol and polycarbonate diol-containing compositions were evaluated by the following methods.

<Measurement of number average molecular weight>
The number average molecular weight (Mn) was calculated from the integral value obtained by dissolving the product in CDCl ₃ and measuring ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) at 400 MHz. Each integral value was calculated according to the following chemical shift. Note that the chemical shift value may vary slightly depending on the composition. In this case, the method of taking the integral value may be changed as appropriate.

[Composition analysis (ISB / 16HD)]
The integrated value of the chemical shift value was taken by the ¹ H-NMR.
Integral value of δ 5.207 to 4.973 ppm = a
Integral value of δ 4.697 to 4.599 ppm = b
Integral value of δ4.599 to 4.464 ppm = c
Integral value of δ 3.686 to 3.501 ppm = d
Integral value of δ2.764-2.717 ppm = e
Integral value of δ 1.493 to 1.295 ppm = f
There are two types of structures of chain ends derived from ISB, which are referred to as “ISB end 1” and “ISB end 2”, respectively. Further, the ISB-derived structure part in the polycarbonate diol other than the terminal is defined as “in ISB”. Similarly, regarding 16HD, “16HD end” and “16HD medium” are set. Considering the number of each proton, calculate the number according to the following formula.
(ISB) Terminal 1 = be
(ISB) middle = c- (ISB) terminal 1
(ISB) terminal 2 = a- (ISB) terminal 1- (ISB) medium × 2
(16HD) terminal = (d-e- (ISB) terminal 1) / 2
(16HD) medium = (f− (16HD) terminal × 4) ÷ 4

[Composition analysis (NPG / 16HD)]
The integrated value of the chemical shift value was taken by the ¹ H-NMR.
Integral value of δ 4.25 to 4.05 ppm = g
Integral value of δ 4.05 to 3.87 ppm = h
Integral value of δ 3.70 to 3.57 ppm = i
Integral value of δ3.41-3.30 ppm = j
Integral value of δ 1.15 to 1.12 ppm = k
The terminal derived from NPG is referred to as “NPG terminal”. Further, the NPG-derived structure part in the polycarbonate polyol other than the terminal is referred to as “in NPG”. Similarly, regarding 16HD, “16HD end” and “16HD medium” are set. Considering the number of each proton, calculate the number according to the following formula.
NPG end = j ÷ 2
In NPG = (h−j) ÷ 4
16HD end = i ÷ 2
16HD medium = (g-16HD end × 2-k ÷ 6 × 4) ÷ 4

<Measurement of amount of hindered phenolic compound in polycarbonate diol>
The content of the polycarbonate diol-containing composition was calculated from the integral value of the hindered phenol compound by the ¹ H-NMR.

<Measurement of phosphorus atomic weight of phosphorus compound in polycarbonate diol>
About 1 g of polycarbonate diol was precisely weighed, 10 mL of 89% sulfuric acid was added, and heating was performed from 200 ° C. to 400 ° C. on a high temperature hot plate. After cooling to room temperature, 1 mL of 69% nitric acid was added, and heating was again performed from 200 ° C. to 400 ° C. on a high temperature hot plate. The operation of adding nitric acid and heating was repeated until the decomposition solution became transparent. After cooling to room temperature, it was quantified with ICP-OES Vista-Pro (manufactured by Agilent) using the liquid obtained above.

<Measurement of APHA value>
In accordance with JIS K0071-1 (1998), the measurement was made in comparison with a standard solution placed in a colorimetric tube. As a reagent, a chromaticity standard solution of 1000 degrees (1 mg Pt / mL) (Kishida Chemical) was used.

[Example 1]
16 HD: 404.3 g, ISB: 500.1 g, DPC: 1095.6 g, magnesium acetate tetrahydrate aqueous solution: 8.7 mL in a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure controller. (Concentration: 8.4 g / L, magnesium acetate tetrahydrate: 73 mg), IRGANOX 245: 0.208 g, PEP-4C: 0.208 g were added, and the nitrogen gas was replaced. First, the internal temperature was raised to 130 ° C., and the contents were dissolved by heating. When the temperature was raised and dissolved, the pressure was lowered to 5.33 kPa over 5 minutes, and the reaction was carried out at 130 ° C. and 5.33 kPa for 180 minutes. Then, after reducing the pressure to 0.40 kPa over 120 minutes, the reaction is carried out while distilling off and removing phenol and unreacted diol while raising the temperature to 160 ° C. over 70 minutes to obtain a polycarbonate diol intermediate. It was.

Further, the obtained polycarbonate diol intermediate was subjected to thin film distillation (jacket oil temperature: 180 ° C., pressure: 0.027 kPa) at a flow rate of 20 g / min to obtain a polycarbonate diol. The number average molecular weight (Mn), APHA value, hindered phenol heat stabilizer content, and phosphorus atom content of the polycarbonate diol were measured. The results are shown in Table 1.

[Example 2]
A polycarbonate diol was obtained in the same manner as in Example 1 except that PEP-4C in Example 1 was changed to IRGAFOS168, and the number average molecular weight (Mn), APHA value, hindered phenol heat stabilizer content, phosphorus content of each product were obtained. The atomic content was measured. The results are shown in Table 1.

[Comparative Example 1]
Except not using IRGANOX245 of Example 1 and PEP-4C, polycarbonate diol was obtained like Example 1, and the number average molecular weight (Mn) and APHA value of each product were measured. The results are shown in Table 1.

[Comparative Example 2]
Except not using PEP-4C of Example 1 and using IRGANOX245: 1.038 g, polycarbonate diol was obtained in the same manner as in Example 1, and the number average molecular weight (Mn), APHA value, hindered phenol of each product was obtained. The system heat stabilizer content was measured. The results are shown in Table 1.

[Comparative Example 3]
Except not using IRGANOX245 of Example 1 and using PEP-4C: 1.038 g, a polycarbonate diol was obtained in the same manner as in Example 1, and the number average molecular weight (Mn), APHA value, and phosphorus atom content of each product were obtained. The amount was measured. The results are shown in Table 1.

[Example 3]
In a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator, 16HD: 424.4 g, NPG: 374.0 g, DPC: 1201.6 g, magnesium acetate tetrahydrate aqueous solution: 4.6 mL (Concentration: 8.4 g / L, magnesium acetate tetrahydrate: 39 mg), IRGANOX245: 0.189 g, PEP-4C: 0.189 g were added, and the nitrogen gas was replaced. First, the internal temperature was raised to 130 ° C., and the contents were dissolved by heating. When the temperature was raised and dissolved, the pressure was reduced to 6.00 kPa over 5 minutes, and the reaction was performed at 130 ° C. and 6.00 kPa for 330 minutes. Then, after reducing the pressure to 0.40 kPa over 180 minutes, the reaction is performed while distilling off and removing phenol and unreacted diol while raising the temperature to 160 ° C. over 90 minutes to obtain a polycarbonate diol intermediate. It was.

Further, the obtained polycarbonate diol intermediate was subjected to thin film distillation (jacket oil temperature: 160 ° C., pressure: 0.027 kPa) at a flow rate of 20 g / min to obtain a polycarbonate diol after thin film distillation. The number average molecular weight (Mn), APHA value, hindered phenol heat stabilizer content, and phosphorus atom content of the polycarbonate diol product after thin film distillation were measured. The results are shown in Table 1.

[Comparative Example 4]
Except not using IRGANOX245 and PEP-4C of Example 3, polycarbonate diol was obtained like Example 3, and the number average molecular weight (Mn) and APHA value of each product were measured. The results are shown in Table 1.

  As is clear from the results in Table 1, the polycarbonate diol-containing compositions of Examples 1 to 3 are compared with the polycarbonate diol-containing composition of the comparative example by containing specific amounts of phosphorus compounds and hindered phenol compounds. It can be seen that the APHA value is low and the color change due to heating is prevented.

Claims (6)

(1) the following formula (D) by the structure units of which are represented, and (2) has a moiety represented by the following formula (E), any of the structural unit derived from a no dihydroxy compound an aromatic ring structure Kano structural units, and, (3) (1), (2) other than, having no aromatic ring structure, a reportage polycarbonate diol having a structural unit derived from a dihydroxy compound of an aliphatic hydrocarbon Polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less, and a ratio of hydroxyl groups to all terminal groups of 95 mol% or more,
A polycarbonate diol-containing composition containing a phosphorus compound and a hindered phenol compound,
The phosphorus compound is a compound represented by the following formula (A) and / or a compound represented by the following formula (B), and the content of the phosphorus compound is the mass of the polycarbonate diol-containing composition. In contrast, the phosphorus atom is 2 ppm or more and 50 ppm or less,
Content of the said hindered phenol type compound is 50 ppm or more and 500 ppm or less with respect to the mass of the said polycarbonate diol containing composition, The polycarbonate diol containing composition characterized by the above-mentioned.

(In Formula (D), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an alkynyl group, and an alkoxy group, These groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

(In the formula (E), the case where the site represented by the above formula (E) is a part of —CH ₂ —O—H is excluded.)

(In formula (A), Y represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (B), Z represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms.)   The polycarbonate diol-containing composition according to claim 1, wherein the polycarbonate diol is a polycarbonate diol obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials.   The polycarbonate diol-containing composition according to claim 2, wherein the carbonic acid diester is diaryl carbonate.   The polycarbonate diol-containing composition according to any one of claims 1 to 3, wherein the structural unit represented by the formula (D) is derived from 2,2-dialkyl-1,3-propanediol. . The dihydroxy compound having a site represented by the formula (E) is at least one dihydroxy compound selected from the group consisting of isosorbide, isomannide, and isoidide. 2. A polycarbonate diol-containing composition according to item 1. Any one of (1) a structural unit represented by the following formula (D) and (2) a structural unit derived from a dihydroxy compound having a site represented by the following formula (E) and having no aromatic ring structure structural units, and, (3) (1), (2) other than, having no aromatic ring structure, a reportage polycarbonate diol having a structural unit derived from a dihydroxy compound of aliphatic hydrocarbons, A polycarbonate diol having a number average molecular weight of 250 or more and 5000 or less, and a ratio of hydroxyl groups to all terminal groups of 95 mol% or more, a phosphorus compound, and a hindered phenol compound, wherein the phosphorus compound is represented by the following formula ( The compound represented by A) and / or the compound represented by the following formula (B), and the content of the phosphorus compound is relative to the mass of the polycarbonate diol-containing composition A method for producing a polycarbonate diol-containing composition having 2 ppm or more and 50 ppm or less as a phosphorus atom, and wherein the content of the hindered phenol compound is 50 ppm or more and 500 ppm or less with respect to the mass of the polycarbonate diol-containing composition. ,
A polycarbonate diol-containing composition characterized in that the polycarbonate diol-containing composition is obtained by a transesterification reaction using a dihydroxy compound and a carbonic acid diester as raw materials in the presence of the phosphorus compound and the hindered phenol compound. Production method.

(In Formula (D), n is 0 or 1, R ¹ and R ² are each independently a group selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an alkynyl group, and an alkoxy group, These groups may contain a hetero atom, and each X independently represents a divalent group having 1 to 15 carbon atoms which may contain a hetero atom.

(In the formula (E), the case where the site represented by the above formula (E) is a part of —CH ₂ —O—H is excluded.)

(In formula (A), Y represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (B), Z represents an alkyl group having 5 to 18 carbon atoms or an aromatic group represented by the following formula (C).)

(In the formula (C), R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms.)