JP2017222854A - Polycarbonate diol-containing composition, polyurethane using polycarbonate diol-containing composition, and method for producing polycarbonate diol-containing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polycarbonate diol which has good handleability while being a solid at normal temperature, provides polyurethane to which excellent strength, hardness, heat resistance and abrasion resistance are imparted, and enhances processability.SOLUTION: A polycarbonate diol-containing composition contains polycarbonate diol obtained by a polymerization reaction of diaryl carbonate, diol represented by formula (A) and diol represented by formula (B) in the presence of a metallic compound catalyst, where a glass transition temperature of the polycarbonate diol-containing composition is -20°C or higher. In formula (A), Rand Rrepresent an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an alkoxy group having 1 to 15 carbon atoms, and may have an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom or a substituent containing them while having 1 to 15 carbon atoms. In formula (B), Rrepresents an aliphatic or alicyclic hydrocarbon group which has 1 to 15 carbon atoms and may have a hetero atom.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate diol-containing composition useful for producing a polycarbonate-based polyurethane, a production method thereof, and a polyurethane using the polycarbonate diol-containing composition.

Polycarbonate diol is used as a raw material for soft segment parts of polyurethane and thermoplastic elastomers, paints, adhesives, etc., and has the heat resistance, weather resistance, hydrolysis resistance, etc. that are the disadvantages of polyether polyol and polyester polyol. It is widely used as a raw material that imparts excellent high durability.
Among the polycarbonate diols, the polycarbonate diol synthesized from 1,6-hexanediol is currently widely marketed, but since this polycarbonate diol is crystalline, the viscosity of the resulting polyurethane is used for paints and coatings. There is a problem in workability such as increase in the hardness and crystallization of the resin.

In order to solve these problems, polycarbonate diols using various diols as raw materials have been proposed.
For example, as an amorphous polycarbonate diol, a combination of two types of aliphatic linear diols, a polycarbonate diol obtained by copolymerizing 1,6-hexanediol and 1,5-pentanediol, There are polycarbonate diols obtained by copolymerizing hexanediol and 1,4-butanediol (Patent Documents 1 and 2).
When an aliphatic diol having a branched chain is copolymerized, an amorphous polycarbonate diol can be obtained by reducing the crystallinity of the polycarbonate diol. For example, a polycarbonate diol obtained by copolymerization of 2-methyl-1,3-propanediol and an aliphatic linear diol, a polycarbonate diol obtained by copolymerization of neopentyl glycol and another diol, 2-butyl-2-ethyl-1 Polycarbonate diol obtained by copolymerizing 3-propanediol and aliphatic linear diol (Patent Documents 3 to 5).

JP-A-2-289616 JP-A-5-51428 International Publication No. 2006/88152 International Publication No. 2011/074617 JP 2010-241990 A

  However, since the above-mentioned amorphous polycarbonate diol usually has a small crystallinity at the polyol portion, it can impart sufficient physical properties to the resulting polyurethane when properties such as strength, hardness and abrasion resistance are required. It was difficult.

  The present invention is a polycarbonate that is solid at room temperature but has good handleability, and when it is made into polyurethane, in addition to imparting excellent strength, hardness, heat resistance and wear resistance, it can enhance workability. The object is to provide a diol.

As a result of intensive studies to solve the above problems, the present inventor has found that a polycarbonate diol containing a structural unit derived from a specific diol satisfies the above physical properties, and has led to the present invention.
That is, the gist of the present invention is as follows.
(1) A composition containing a diaryl carbonate, a diol represented by the following formula (A) and a polycarbonate diol which is a polymer of the diol represented by the following formula (B), A polycarbonate diol-containing composition having a glass transition temperature of −20 ° C. or higher.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)
(2) The polycarbonate diol-containing composition according to (1), wherein the content of 5,5-dialkyl-1,3-dioxan-2-one is 3% by weight or less.
(3) The polycarbonate diol-containing composition according to (1) or (2), wherein the number average molecular weight determined from the hydroxyl value of the polycarbonate diol is 500 to 5,000.
(4) The ratio of the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B) is 75:25 to 99: 1 in molar ratio. The polycarbonate diol-containing composition according to any one of (1) to (3) above.
(5) The polycarbonate diol-containing composition according to any one of (1) to (4), wherein a ratio of terminal hydroxyl groups of the polycarbonate diol is 95 mol% or more.
(6) A polyurethane using the polycarbonate diol-containing composition according to any one of (1) to (5) above.
(7) A method for producing a composition containing a polycarbonate diol by polymerizing a diaryl carbonate, a diol represented by the following formula (A) and a diol represented by the following formula (B) in the presence of a metal compound catalyst. A method for producing a polycarbonate diol-containing composition, wherein the polycarbonate diol-containing composition has a glass transition temperature of -20 ° C or higher.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)
(8) The diol represented by the formula (A) and the diol represented by the formula (B) are used in a molar ratio of 75:25 to 99: 1, the preceding item (7) A method for producing a polycarbonate diol-containing composition.
(9) The method for producing a polycarbonate diol-containing composition according to (7) or (8) above, wherein the metal compound catalyst is a compound of a Group 1 metal or a Group 2 metal compound of the periodic table.

According to the present invention, the handleability is good while being solid at room temperature, and in addition to imparting excellent strength, hardness, heat resistance, and wear resistance to polyurethane, workability can be improved. A polycarbonate diol can be provided.
For example, polyurethane-based paints and coating materials produced using the polycarbonate diol of the present invention have improved workability, high durability such as wear resistance and heat resistance, and are extremely useful industrially.

  Hereinafter, although the form of this invention is demonstrated in detail, this invention is not limited to the following embodiment, Various deformation | transformation can be implemented within the range of the summary.

[1. Polycarbonate diol]
The polycarbonate diol-containing composition of the present invention is obtained by polymerizing (polycondensation) a diaryl carbonate, a diol represented by the following formula (A) and a diol represented by the following formula (B) in the presence of a metal compound catalyst. The obtained polycarbonate diol is contained.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)

The polycarbonate diol-containing composition of the present invention is mainly composed of the target polycarbonate diol by polymerizing the diaryl carbonate, the diol represented by the formula (A) and the diol represented by the formula (B). In addition, since it is obtained as a composition containing impurities such as reaction by-products and unreacted raw materials, it is referred to as a “polycarbonate diol-containing composition”. This is called “diol”.
Therefore, hereinafter, the “polycarbonate diol-containing composition of the present invention” may be referred to as “the polycarbonate diol of the present invention”.

<1-1. Structural features>
The structural unit (repeating unit) derived from the diol represented by the formula (A) contained in the polycarbonate diol of the present invention is represented by the following formula (C), for example. Moreover, the structural unit (repeating unit) derived from the diol represented by the formula (B) is represented by the following formula (D), for example.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)

In Formula (A) and Formula (C), 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. However, R ¹ and R ² are preferably an alkyl group having 15 or less carbon atoms, more preferably an alkyl group having 10 or less carbon atoms, and 5 carbon atoms because polymerization reactivity, chemical resistance, and heat resistance are improved. The following alkyl groups are more preferable, alkyl groups having 2 or less carbon atoms are particularly preferable, and a methyl group is most preferable.

In the above formulas (B) and (D), R ³ is an aliphatic or alicyclic hydrocarbon group having 1 to 15 carbon atoms which may contain a hetero atom, but has polymerization reactivity and chemical resistance, respectively. Is preferable, an aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferable, an aliphatic hydrocarbon group having 1 to 8 carbon atoms is more preferable, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferable.

The polycarbonate diol obtained by the polycarbonate diol of the present invention and the polycarbonate diol production method of the present invention is a structural unit derived from the diol represented by the formula (A) (that is, the repeating unit represented by the formula (C)). And a structural unit derived from the diol represented by the formula (B) (that is, a repeating unit represented by the formula (D)). By including the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B), good strength and heat resistance can be obtained when the polyurethane is obtained. Can do. Furthermore, the ratio between the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B) (hereinafter sometimes referred to as “(A) :( B)”). Is a molar ratio of (A) :( B) = 75: 25 to 99: 1, preferably 80:20 to 99: 1, more preferably 80:20 to 98: 2. : 20 to 97: 3 is most preferable. If the content ratio of the structural unit derived from the diol represented by the formula (A) is more than this range, the polyurethane obtained using the polycarbonate diol of the present invention is easily broken by crystallization, and the strength is sufficient. May disappear. In addition, if the content ratio of the structural unit derived from the diol represented by the formula (A) is less than this range, handling properties and heat resistance may be insufficient when polyurethane is used.
The ratio of the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B) in the polycarbonate diol of the present invention is measured by ¹ H-NMR, It can be calculated from the integral value.

The polycarbonate diol of the present invention may contain only one type of structural unit derived from the diol represented by the above formula (A), and two or more of the above formulas having different R ¹ and R ² may be used. It may contain a structural unit derived from the diol represented by (A). Similarly, the structural unit derived from the diol represented by the formula (B) may contain only one type, and two or more diols represented by the formula (B) having different R ^{3 s.} The structural unit derived from may be included.

  The total ratio of the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B) to the total structural unit derived from the dihydroxy compound of polycarbonate diol is: From the viewpoint of strength and handling properties when polyurethane is used, it is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, 95 mol%. The above is most preferable.

  The ratio of the structural unit derived from each dihydroxy compound to the total structural unit of the polycarbonate diol of the present invention can be determined by analyzing the dihydroxy compound obtained by hydrolyzing the polycarbonate diol with an alkali by gas chromatography.

  If the polycarbonate diol of the present invention contains a structural unit derived from the diol represented by the formula (A) and a structural unit derived from the diol represented by the formula (B), they are copolymers. Alternatively, it may be a mixture of different kinds of polycarbonate diols, but is preferably a copolymer because of its good hardness and strength. In the case of a copolymer, a block copolymer or a random copolymer may be used, but a polycarbonate diol of a random copolymer is more preferable because hardness and strength are improved.

<1-2. Dihydroxy Compound (Diol)>
Examples of the diol represented by the formula (A) which is a raw material dihydroxy compound of the polycarbonate diol of the present invention include 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl- 2,2-dialkyl-substituted 1,3-propanediols such as 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol ( Hereinafter, it may be described as 2,2-dialkyl-1,3-propanediol, provided that the alkyl group is an alkyl group having 15 or less carbon atoms. Among these, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, and 2,2-diethyl-1,3-propanediol are excellent in terms of availability and physical properties of the raw material dihydroxy compound. Is preferred, and neopentyl glycol is more preferred. The diol represented by the formula (A) may be used alone or in combination of two or more.

  Examples of the diol represented by the formula (B) which is a raw material dihydroxy compound of the polycarbonate diol of the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and 1,1 Linear terminal diols such as 20-eicosanediol, diols having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol and polytetramethylene glycol, thioether diols such as bishydroxyethyl thioether, 2- Ethyl-1,6- Diols having a branched chain such as xanthdiol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and 2,4-diethyl-1,5-pentanediol, 1,3- Cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 1,4-dihydroxyethylcyclohexane, isosorbide , 2,5-bis (hydroxymethyl) tetrahydrofuran, 4,4′-isopropylidene dicyclohexanol and 4,4′-isopropylidenebis (2,2′-hydroxyethoxycyclohexane) Diols in Beauty N- methyl - nitrogen-containing diols and bis (hydroxyethyl) such diethanolamine can be mentioned sulfur-containing diols such as the sulfides. Among these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 are advantageous in that the raw material dihydroxy compound is excellent in availability and physical properties. -Nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferable, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are more preferable. 1,4-butanediol and 1,6-hexanediol are more preferable. The diol represented by the formula (B) may be used alone or in combination.

  The diol represented by the formula (B) is preferably derived from a plant from the viewpoint of reducing the environmental load. Examples of the diol represented by the above formula (B) applicable as a plant origin include 1,3-propanediol, 1,4-butanediol, 1,5-propanediol, 1,9-nonanediol, 1,10. -Decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like.

  In the production of the polycarbonate diol of the present invention, as the raw material dihydroxy compound, a diol represented by the formula (A) and a dihydroxy compound other than the diol represented by the formula (B) may be used. From the viewpoint of strength and handleability when the diol is used, the ratio of the diol represented by the formula (A) and the diol represented by the formula (B) in the total dihydroxy compound used for the production of the polycarbonate diol is 50 mol% or more. It is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 95 mol% or more.

<1-3. Carbonate compound>
Examples of the carbonate compound (sometimes referred to as “carbonic acid diester”) that can be used as a raw material for the production of polycarbonate diol include dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Of these, diaryl from the viewpoint of reactivity in the present invention. Carbonate is used.

  Specific examples of the diaryl carbonate include one or more of diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, and the like, and diphenyl carbonate is preferable.

  Specific examples of the carbonate compound other than diaryl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, and the like. The raw material carbonate compound used in the present invention is 80 mol% or more, particularly 90 to 100 mol%. Is preferably a diaryl carbonate.

<1-4. Metal Compound Catalyst>
The polycarbonate diol of the present invention can be produced by polycondensing a diaryl carbonate, a diol represented by the formula (A) and a diol represented by the formula (B) by an ester exchange reaction.
In the method for producing a polycarbonate diol of the present invention, a metal compound catalyst is used as a transesterification catalyst (hereinafter sometimes referred to as a catalyst) in order to promote polymerization. In that case, when an excessively large amount of catalyst remains in the obtained polycarbonate diol, the reaction may be inhibited or the reaction may be excessively accelerated when a polyurethane is produced using the polycarbonate diol.

  For this reason, the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and even more preferably 10 ppm by weight or less as the content in terms of catalyst metal.

  As the transesterification catalyst, any compound that is generally considered to have transesterification ability can be used without limitation.

  Examples of transesterification catalysts include compounds of Group 1 metals such as lithium, sodium, potassium, rubidium, and cesium, which are long-period periodic tables (hereinafter simply referred to as “periodic table”); magnesium, calcium, strontium, barium, and the like Periodic table Group 2 metal compounds such as titanium and zirconium; Periodic table Group 5 metal compounds such as hafnium; Group 9 metal compounds such as cobalt; Zinc and the like Periodic table Group 12 metal compounds such as aluminum; Periodic table Group 13 metal compounds such as aluminum; Periodic table Group 14 metal compounds such as germanium, tin and lead; Periodic table Group 15 metals such as antimony and bismuth Compounds: Lanthanide-based metal compounds such as lanthanum, cerium, europium, ytterbium and the like. These catalysts may be used individually by 1 type, and may mix and use 2 or more types.

  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 are preferred, Periodic table Group 1 metal compound, Periodic table A compound of Group 2 metal is more preferable, and a compound of Group 2 metal of the periodic table is more preferable. 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 are mainly used as hydroxides and salts. Examples of salts when used as salts include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonate and toluenesulfonate And sulfonates such as trifluoromethanesulfonate; phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; and acetylacetonate salts. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

  Among these, preferably, acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, alkoxide of at least one metal selected from Group 2 metals of the periodic table is used, More preferred are group 2 metal acetates, carbonates, and hydroxides of the periodic table, more preferred are magnesium, calcium acetates, carbonates, and hydroxides, and particularly preferred are magnesium and calcium. Acetate is used, most preferably magnesium acetate.

<1-5. Molecular chain end>
The molecular chain terminal of the polycarbonate diol of the present invention is mainly a hydroxyl group. However, in the case of a polycarbonate diol obtained by the reaction of a dihydroxy compound and a carbonate compound, there is a possibility that some molecular chain terminals are not hydroxyl groups as impurities. As specific examples thereof, the molecular chain terminal is an alkyloxy group or an aryloxy group, and many have a structure derived from a carbonate compound.

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

  The molecular chain terminal of the polycarbonate diol of the present invention has the number of terminals derived from the diol represented by the formula (A) and the number of terminals derived from the diol represented by the formula (B) with respect to the total number of terminals. The total number ratio is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, particularly preferably 97 mol% or more, and most preferably 99 mol% or more. By setting the amount within the above range, it becomes easy to obtain a desired molecular weight when polyurethane is used, and it becomes possible to be a raw material for polyurethane having excellent strength and heat resistance.

  The ratio of the number of terminal groups in which the molecular chain terminal of the polycarbonate diol is derived from the carbonate compound is preferably 10 mol% or less, more preferably 5 mol% or less, and still more preferably 3 mol%, based on the total number of terminals. Hereinafter, it is particularly preferably 1 mol% or less.

The lower limit of the hydroxyl value of the polycarbonate diol of the present invention is usually 14 mg-KOH / g, preferably 16 mg-KOH / g, more preferably 18 mg-KOH / g, still more preferably 22 mg-KOH / g. The upper limit is usually 450 mg-KOH / g, preferably 230 mg-KOH / g, more preferably 150 mg-KOH / g, still more preferably 120 mg-KOH / g, particularly preferably 75 mg-KOH / g, most preferably 45 mg. -KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high and handling of the polycarbonate diol may be difficult, and if it exceeds the upper limit, physical properties such as strength and heat resistance may be insufficient when polyurethane is used.
In addition, the molecular chain terminal and the hydroxyl value of polycarbonate diol are specifically measured by the method described in the section of Examples described later.

<1-6. Glass transition temperature>
The lower limit of the glass transition temperature of the polycarbonate diol of the present invention is −20 ° C., more preferably −15 ° C., and further preferably −10 ° C. When the glass transition temperature of the polycarbonate diol is less than the above lower limit, the hardness may not be sufficiently obtained when polyurethane is used.
In addition, the glass transition temperature of polycarbonate diol is specifically measured by the method as described in the item of the below-mentioned Example.

<1-7. Molecular Weight / Molecular Weight Distribution>
The lower limit of the number average molecular weight (Mn) determined from the hydroxyl value of the polycarbonate diol of the present invention is preferably 300, more preferably 400, and even more preferably 500. On the other hand, the upper limit is preferably 8,000, more preferably 7,000, and even more preferably 5,000. If the Mn of the polycarbonate diol is less than the above lower limit, sufficient flexibility may not be obtained when polyurethane is used. On the other hand, if the upper limit is exceeded, the viscosity increases and handling during polyurethane formation may be impaired.

  The weight average molecular weight / number average molecular weight (Mw / Mn), which is the molecular weight distribution of the polycarbonate diol of the present invention, is not particularly limited, but the lower limit is preferably 1.5, and more preferably 1.8. The upper limit is preferably 3.5, more preferably 3.0. When the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this polycarbonate diol, especially the elongation tends to decrease, and when trying to produce a polycarbonate diol having a molecular weight distribution less than the above range, the oligomer is excluded. Advanced purification operations may be required.

  Here, the weight average molecular weight and number average molecular weight of the polycarbonate diol are polystyrene-reduced weight average molecular weight and number average molecular weight, and can be usually obtained by measurement of gel permeation chromatography (sometimes abbreviated as GPC). . The specific measurement method is as described in the section of the examples described later.

<1-8. Production method of polycarbonate diol>
<1-8-1. Ratio of raw materials used>
In the production of the polycarbonate diol of the present invention, the amount of the carbonate compound used is not particularly limited, but is usually a molar ratio with respect to a total of 1 mol of the dihydroxy compound, and the lower limit is preferably 0.35, more preferably 0.50, still more preferably. Is 0.60, and the upper limit is preferably 1.00, more preferably 0.99, and still more preferably 0.98. If the amount of the carbonate compound used exceeds the above upper limit, the proportion of the polycarbonate diol end group that is not a hydroxyl group may increase or the molecular weight may not fall within the predetermined range. If the amount is less than the lower limit, the polymerization does not proceed to the predetermined molecular weight. There is a case.

  In producing the polycarbonate diol of the present invention, as described above, a transesterification catalyst may be used. The compounds that can be used in this case are as described above, but the amount used is preferably an amount that does not affect the performance even if it remains in the obtained polycarbonate diol, as described above.

  The amount of the transesterification catalyst used is preferably 500 ppm by weight, more preferably 100 ppm by weight, and more preferably 50 ppm by weight, as the weight ratio of the metal to the weight of the raw dihydroxy compound. It is preferably 10 ppm by weight, particularly preferably. On the other hand, the lower limit is preferably an amount that provides sufficient polymerization activity, that is, 0.01 ppm by weight, more preferably 0.1 ppm by weight, and even more preferably 1 ppm by weight.

<1-8-2. Reaction temperature>
The reaction temperature in the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. Usually, the lower limit of the reaction temperature is preferably 70 ° C, more preferably 100 ° C, and further preferably 130 ° C. The upper limit of the reaction temperature is usually preferably 250 ° C, more preferably 230 ° C, and further preferably 200 ° C. By setting the upper limit of the reaction temperature to the above value, it is possible to prevent quality problems such as coloring of the obtained polycarbonate diol and formation of an ether structure.

  Furthermore, the reaction temperature is preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and even more preferably 160 ° C. or lower throughout the entire ester exchange reaction for producing polycarbonate diol. By setting the reaction temperature to 180 ° C. or lower throughout all the steps, it is possible to prevent the color from being easily colored depending on conditions.

<1-8-3. Reaction pressure>
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, usually, in the latter half of the reaction, it is preferable to carry out the reaction while distilling off the light-boiling components under reduced pressure conditions.

  Or it is also possible to make it react, distilling off the light boiling component produced | generated by reducing pressure gradually from the middle of reaction. In particular, it is preferable to increase the degree of vacuum at the end of the reaction because the by-produced monoalcohol, phenols and cyclic carbonate can be distilled off.

  In this case, the upper limit of the reaction pressure at the end of the reaction is preferably 10 kPa, more preferably 5 kPa, and even more preferably 1 kPa. In order to effectively distill these light-boiling components, the reaction can be carried out while flowing an inert gas such as nitrogen, argon and helium through the reaction system.

  When using a low-boiling carbonate or dihydroxy compound in the transesterification reaction, the reaction is initially performed near the boiling point of the carbonate or dihydroxy compound, and the temperature is gradually raised as the reaction proceeds. A method of allowing the reaction to proceed can also be employed. This is preferable because unreacted carbonate ester can be prevented from distilling off at the beginning of the reaction.

  Furthermore, in order to prevent the distillation of these raw materials, it is possible to carry out the reaction while refluxing the carbonate ester and dihydroxy compound by attaching a reflux tube to the reactor. In this case, the amount of the reagent is not lost without losing the charged raw materials. It is preferable because the ratio can be adjusted accurately.

<1-8-4. Reaction method>
The polymerization reaction can be carried out batchwise or continuously, but is preferably carried out continuously from the standpoint of product stability. The apparatus to be used may be any of a tank type, a tube type and a tower type, and a known polymerization tank equipped with various stirring blades can be used. The atmosphere during the temperature rise of the apparatus is not particularly limited, but from the viewpoint of product quality, it is preferably carried out in an inert gas such as nitrogen gas under normal pressure or reduced pressure.

<1-8-5. Reaction time>
The polymerization reaction ends when the molecular weight of the polycarbonate diol to be produced is measured while the target molecular weight is reached. The reaction time required for the polymerization varies greatly depending on the presence and type of dihydroxy compound, carbonate and catalyst used, and cannot be defined generally, but it is usually preferably 50 hours or less, It is more preferable that the time is not longer than 10 hours, and it is further preferable that the time is not longer than 10 hours.

<1-8-6. Catalyst Deactivator>
As described above, when a catalyst is used in the polymerization reaction, the catalyst is usually left in the obtained polycarbonate diol, and the polyurethane formation reaction may not be controlled by the remaining catalyst. In order to suppress the influence of the remaining catalyst, it is preferable to add a substantially equimolar amount of, for example, a phosphorus compound or the like to the transesterification catalyst used to inactivate the transesterification catalyst. Further, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment or the like as described later.

  Examples of phosphorus compounds used for inactivating the transesterification catalyst include inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, And organic phosphate esters such as triphenyl phosphate. These may be used alone or in combination of two or more.

  The amount of the phosphorus compound used is not particularly limited, but as described above, it may be approximately equimolar with the transesterification catalyst used, and specifically, with respect to 1 mol of the transesterification catalyst used. The upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol. When a smaller amount of phosphorus compound is used, the transesterification catalyst in the reaction product is not sufficiently deactivated. When the obtained polycarbonate diol is used as a raw material for polyurethane production, for example, the polycarbonate diol In some cases, the reactivity with respect to the isocyanate group cannot be sufficiently reduced. Moreover, when the phosphorus compound exceeding this range is used, the obtained polycarbonate diol may be colored.

Inactivation of the transesterification catalyst by adding a phosphorus compound can be performed at room temperature, but heat treatment is more efficient. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 180 ° C, more preferably 150 ° C, still more preferably 120 ° C, particularly preferably 100 ° C, and the lower limit is preferably 50 ° C, more preferably. Is 60 ° C., more preferably 70 ° C. When the temperature is lower than this, it takes time to inactivate the transesterification catalyst, which is not efficient, and the degree of inactivation may be insufficient. On the other hand, at a temperature exceeding 180 ° C., the obtained polycarbonate diol may be colored.
The time for reacting with the phosphorus compound is not particularly limited, but is usually 1 to 5 hours.

<1-8-7. Purification>
The reaction product is purified for the purpose of removing impurities that do not have a hydroxyl group at the polymer terminal, phenols, raw dihydroxy compounds, carbonates, by-product light-boiling cyclic carbonates and added catalysts in the product. be able to.

  For 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 and thin film distillation, and any method can be adopted, but thin film distillation is particularly effective.

Although there is no restriction | limiting in particular as thin film distillation conditions, As for the temperature at the time of thin film distillation, it is preferable that an upper limit is 250 degreeC, and it is preferable that it is 200 degreeC. Moreover, it is preferable that a minimum is 120 degreeC, and it is more preferable that it is 150 degreeC.
By setting the lower limit of the temperature during thin film distillation to the above value, the effect of removing light boiling components is sufficient. Further, by setting the upper limit to 250 ° C., it is possible to prevent the polycarbonate diol obtained after thin film distillation from being colored.

  The upper limit of the pressure during thin film distillation is preferably 500 Pa, more preferably 150 Pa, still more preferably 70 Pa, and particularly preferably 50 Pa. By setting the pressure during thin film distillation to the above upper limit or less, the effect of removing light boiling components can be sufficiently obtained.

Moreover, the upper limit of the temperature of the polycarbonate diol just before thin film distillation is preferably 250 ° C, and more preferably 150 ° C. Moreover, it is preferable that a minimum is 80 degreeC, and it is more preferable that it is 120 degreeC.
By setting the temperature for keeping the polycarbonate diol just before the thin film distillation to the above lower limit or more, it is possible to prevent the flowability of the polycarbonate diol just before the thin film distillation from being lowered. On the other hand, by setting it to the upper limit or less, it is possible to prevent the polycarbonate diol obtained after thin film distillation from being colored.

  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 to be dissolved in water can be arbitrarily selected.

<1-9. Residual monomers, etc.>
When diaryl carbonate such as diphenyl carbonate is used as a raw material, phenols are by-produced during the production of polycarbonate diol. Since phenols are monofunctional compounds, they may be an inhibitory factor in the production of polyurethane, and the urethane bonds formed by phenols are weak in their bonding strength, so they are heated by subsequent processes. It can be dissociated and the isocyanates and phenols can be regenerated to cause problems. Moreover, since phenols are also stimulating substances, it is preferable that the residual amount of phenols in the polycarbonate diol is smaller. Specifically, the residual amount of phenols in the polycarbonate diol is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, and particularly preferably 100 ppm or less as a weight ratio to the polycarbonate diol. In order to reduce the phenols in the polycarbonate diol, as described above, the pressure of the polymerization reaction of the polycarbonate diol is set to a high vacuum of 1 kPa or less with the absolute pressure of the polycarbonate diol, or thin film distillation is performed after the polymerization reaction of the polycarbonate diol. Is effective.

  In polycarbonate diol, the carbonic acid diester used as a raw material at the time of manufacture may remain. The residual amount of the carbonic acid diester in the polycarbonate diol is not limited, but a smaller amount is preferable, and the upper limit of the weight ratio with respect to the polycarbonate diol is preferably 5% by weight, more preferably 3% by weight, still more preferably 1% by weight. is there. If the carbonic diester content of the polycarbonate diol is too large, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit is not particularly limited, but is preferably 0.1% by weight, more preferably 0.01% by weight, and still more preferably 0% by weight.

  In polycarbonate diol, the dihydroxy compound used at the time of manufacture may remain. The residual amount of the dihydroxy compound in the polycarbonate diol is not limited, but a smaller amount is preferable, and the weight ratio with respect to the polycarbonate diol is preferably 1% by weight or less, more preferably 0.1% by weight or less, and still more preferably. Is 0.05% by weight or less. If the residual amount of the dihydroxy compound in the polycarbonate diol is large, the molecular length of the soft segment portion when polyurethane is used may be insufficient, and desired physical properties may not be obtained.

  In polycarbonate diol, the cyclic carbonate (cyclic oligomer) byproduced in the case of manufacture may be contained. For example, when 2,2-dialkyl-1,3-propanediol is used as the diol represented by the formula (A), 5,5-dialkyl-1,3-dioxan-2-one or two of these molecules In some cases, a cyclic carbonate or the like may be generated and contained in the polycarbonate diol. More specifically, when 2,2-dimethyl-1,3-propanediol is used as the diol represented by the formula (A), 5,5-dimethyl-1,3-dioxan-2-one or In addition, there may be cases in which two or more molecules of these become cyclic carbonates are formed and contained in the polycarbonate diol. These compounds may cause side reactions in the polyurethane formation reaction and cause turbidity. Therefore, the pressure of the polymerization reaction of the polycarbonate diol is set to a high vacuum of 1 kPa or less as an absolute pressure, or the synthesis of the polycarbonate diol is performed. It is preferable to remove as much as possible by performing thin film distillation or the like later. The content of cyclic carbonate such as 5,5-dialkyl-1,3-dioxane-3-one contained in the polycarbonate diol is not limited, but is preferably 3% by weight or less, more preferably as a weight ratio with respect to the polycarbonate diol. It is 1% by weight or less, more preferably 0.5% by weight or less.

[2. Polyurethane]
Polyurethane can be produced using the above-described polycarbonate diol of the present invention.
In the method for producing the polyurethane of the present invention using the polycarbonate diol of the present invention, generally known polyurethane reaction conditions for producing a polyurethane are used.

For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol of the present invention with a polyisocyanate and a chain extender in the range of room temperature to 200 ° C.
Also, the polycarbonate diol of the present invention is reacted with an excess of polyisocyanate to produce a prepolymer having an isocyanate group at the terminal, and the degree of polymerization is increased using a chain extender to produce the polyurethane of the present invention. be able to.

<2-1. Polyisocyanate>
Examples of the polyisocyanate used when the polyurethane is produced using the polycarbonate diol of the present invention include various known polyisocyanate compounds such as aliphatic, alicyclic or aromatic.
For example, the carboxyl groups of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid were converted to isocyanate groups. Aliphatic diisocyanates such as dimerisocyanate; 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) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane Alicyclic diisocyanates such as xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 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 ′ -Aromatics such as biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate Isocyanate, and the like. These may be used alone or in combination of two or more.

  Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone are preferable in that the balance of physical properties of the obtained polyurethane is preferable and that a large amount can be obtained industrially at low cost. Diisocyanate is preferred.

<2-2. 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 in the production of a prepolymer having an isocyanate group, which will be described later. And polyamines.

  Specific examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. Linear diols such as 1,10-decanediol and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2 2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanedi Diols having a branched chain such as diol and dimer diol; diols having an ether group such as diethylene glycol and propylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, etc. Diols having an alicyclic structure, diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4′-methylenebis (hydroxyethylbenzene); glycerin, trimethylolpropane, pentaerythritol, etc. Polyols; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethyleneto Amine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropyl Polyamines such as ethylenediamine, 4,4′-diphenylmethanediamine, methylenebis (o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, N, N′-diaminopiperazine; and water be able to.

These chain extenders may be used alone or in combination of two or more. Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, 4, 4'-diaminodicyclohexylmethane is preferred.
Moreover, the chain extender in the case of producing the prepolymer having a hydroxyl group described later is a low molecular weight compound having at least two isocyanate groups, specifically <2-1. And polyisocyanates>.

<2-3. 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.
These chain terminators include aliphatic monools such as methanol, ethanol, propanol, butanol and hexanol having one hydroxyl group, diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having one amino group. And aliphatic monoamines such as morpholine.
These may be used alone or in combination of two or more.

<2-4. Catalyst>
In the polyurethane formation reaction in producing the polyurethane of the present invention, an amine catalyst such as triethylamine, N-ethylmorpholine, triethylenediamine, or an acid catalyst such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, trimethyltin laurate Further, known urethane polymerization catalysts represented by tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, and organic metal salts such as titanium compounds can also be used. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

<2-5. Polyols Other than Polycarbonate Diol of the Present Invention>
In the polyurethane formation reaction when producing the polyurethane of the present invention, the polycarbonate diol of the present invention may be used in combination with other polyols as necessary. Here, the polyol other than the polycarbonate diol of the present invention is not particularly limited as long as it is used in normal polyurethane production. For example, a polyether polyol, a polyester polyol, a polycaprolactone polyol, and a polycarbonate polyol other than the present invention are used. Can be mentioned. Here, the weight ratio of the polycarbonate diol of the present invention to the combined weight of the polycarbonate diol of the present invention and the other polyol is preferably 70% or more, and more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is small, the strength and handling properties of the polyurethane, which is a feature of the present invention, may be lost.

  In the present invention, the above-mentioned polycarbonate diol of the present invention can be modified for use in the production of polyurethane. As a modification method of the polycarbonate diol, a method of introducing an ether group by adding an epoxy compound such as ethylene oxide, propylene oxide or butylene oxide to the polycarbonate diol, a cyclic lactone such as ε-caprolactone, adipic acid, or succinic acid is used as the polycarbonate diol. There is a method of introducing an ester group by reacting with dicarboxylic acid compounds such as sebacic acid and terephthalic acid and ester compounds thereof. In the ether modification, the viscosity of the polycarbonate diol is lowered by modification with ethylene oxide, propylene oxide or the like, which is preferable for reasons such as handling. In particular, the polycarbonate diol of the present invention is modified with ethylene oxide or propylene oxide, thereby reducing the crystallinity of the polycarbonate diol and improving the flexibility at low temperatures. In the case of ethylene oxide modification, it is manufactured using ethylene oxide modified polycarbonate diol. Since the water absorption and moisture permeability of the formed polyurethane are increased, the performance as an artificial leather / synthetic leather may be improved. However, if the addition amount of ethylene oxide or propylene oxide increases, the physical properties such as mechanical strength, heat resistance, chemical resistance and the like of the polyurethane produced using the modified polycarbonate diol decrease. -50 wt% is suitable, preferably 5-40 wt%, more preferably 5-30 wt%. In addition, the method of introducing an ester group is preferable for reasons such as handling because the viscosity of the polycarbonate diol is reduced by modification with ε-caprolactone. The amount of ε-caprolactone added to the polycarbonate diol is preferably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. When the added amount of ε-caprolactone exceeds 50% by weight, the hydrolysis resistance, chemical resistance, etc. of the polyurethane produced using the modified polycarbonate diol are lowered.

<2-6. Solvent>
You may use a solvent for the polyurethane formation reaction at the time of manufacturing the polyurethane of this invention.
Preferred solvents include amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ketone solvents such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; tetrahydrofuran, dioxane and the like. Examples include ether solvents; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents may 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 of an aqueous dispersion can also be manufactured from the polyurethane composition with which the polycarbonate diol of this invention, polyisocyanate, and the said chain extender were mix | blended.

<2-7. Polyurethane production method>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagent, a production method generally used experimentally or industrially can be used.
Examples thereof include a method in which the polycarbonate diol of the present invention, other polyol, polyisocyanate and chain extender are mixed and reacted together (hereinafter sometimes referred to as “one-step method”). A method of reacting a polycarbonate diol, other polyol and polyisocyanate to prepare a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with a chain extender (hereinafter sometimes referred to as “two-stage method”). There is).

  In the two-stage method, the polycarbonate diol of the present invention and the other polyol are reacted with one or more equivalents of a polyisocyanate in advance to prepare a step for preparing a both-end isocyanate intermediate corresponding to the soft segment of the polyurethane. Is. 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.

<2-8. One-step method>
The one-stage method is also called a one-shot method, and is a method in which the reaction is carried out by charging the polycarbonate diol of the present invention, other polyols, polyisocyanate and chain extender all at once.
The amount of polyisocyanate used in the one-stage method is not particularly limited, but the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols and the total number of hydroxyl groups and amino groups of the chain extender is 1 equivalent. The lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably Is 2.0 equivalents, more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

If the amount of polyisocyanate used is too large, unreacted isocyanate groups will cause side reactions, and the resulting polyurethane will have too high a viscosity, making it difficult to handle and tending to reduce flexibility. If it is too high, the molecular weight of the polyurethane will not be sufficiently large, and sufficient polyurethane strength will not be obtained.
The amount of chain extender used is not particularly limited, but when the number obtained by subtracting the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols from the number of isocyanate groups of the polyisocyanate is 1 equivalent, the lower limit is preferably Is 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, Preferably it is 1.5 equivalent, Most preferably, it is 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. There is a case where the holding performance cannot be obtained or the heat resistance is deteriorated.

<2-9. Two-stage method>
The two-stage method is also called a prepolymer method, and mainly includes the following methods.
(A) The polycarbonate diol of the present invention and other polyols and an excess of polyisocyanate are preliminarily added to the polyisocyanate / (polycarbonate diol of the present invention and other polyols) in an amount exceeding 1 to 10. A method of producing a polyurethane by reacting at 0 or less to produce a prepolymer having a molecular chain terminal at an isocyanate group, and then adding a chain extender thereto.
(B) A polyisocyanate, an excess of a polycarbonate diol and other polyols in advance, and a reaction equivalent ratio of polyisocyanate / (polycarbonate diol of the present invention and other polyols) is from 0.1 to less than 1.0. A process for producing a polyurethane by reacting to produce a prepolymer having a molecular chain terminal at a hydroxyl group, and then reacting it with a polyisocyanate having an isocyanate group at the terminal as a chain extender.

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, a polycarbonate diol and a polyol other than that are directly reacted to synthesize a prepolymer, and used as it is in a chain extension reaction.
(2) A prepolymer is synthesized by the method of (1), then dissolved in a solvent and used for the subsequent chain extension reaction.
(3) Using a solvent from the beginning, polyisocyanate, polycarbonate diol and other polyol are reacted, and then chain extension reaction is performed.

In the case of the method (1), in the chain extension reaction, the polyurethane coexists with the solvent by dissolving the chain extender in the solvent or simultaneously dissolving the prepolymer and the chain extender in the solvent. It is important to get in.
The amount of polyisocyanate used in the method of the two-stage method (a) is not particularly limited, but the lower limit is preferable as the number of isocyanate groups when the number of total hydroxyl groups of polycarbonate diol and other polyols is 1 equivalent. Is an amount exceeding 1.0 equivalent, more preferably 1.2 equivalent, still more preferably 1.5 equivalent, and the upper limit is preferably 10.0 equivalent, more preferably 5.0 equivalent, still more preferably 3.0 equivalent. Equivalent range.

If the amount of polyisocyanate used is too large, there is a tendency that excess isocyanate groups cause side reactions and it is difficult to reach the desired properties of polyurethane. If the amount is too small, the molecular weight of the resulting polyurethane does not increase sufficiently, and strength and heat Stability may be reduced.
The amount of chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and even more preferably 0 with respect to the number of 1 equivalent of isocyanate groups contained in the prepolymer. 0.8 equivalent, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and even more preferably 2.0 equivalents.

When performing the chain extension reaction, monofunctional organic amines or alcohols may coexist for the purpose of adjusting the molecular weight.
The amount of polyisocyanate used in preparing the prepolymer having a hydroxyl group at the end in the two-stage method (b) is not particularly limited, but the total number of hydroxyl groups of polycarbonate diol and other polyols is 1 As the number of isocyanate groups in the case of equivalent, the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0.98 equivalent, more preferably 0.97 equivalent.

If the amount of polyisocyanate used is too small, the process for obtaining the desired molecular weight in the subsequent chain extension reaction tends to be long and production efficiency tends to decrease. If it is too large, the viscosity becomes too high and the flexibility of the resulting polyurethane is increased. May be reduced, and handling may be poor and productivity may be inferior.
The amount of chain extender used is not particularly limited, but when the total number of hydroxyl groups of the polycarbonate diol and other polyols used in the prepolymer is 1 equivalent, the total of the isocyanate groups used in the prepolymer is added. As the equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99 equivalents, still more preferably. Is in the range of 0.98 equivalents.

When performing the chain extension reaction, monofunctional organic amines or alcohols may coexist for the purpose of adjusting the molecular weight.
The chain extension reaction is usually carried out at 0 ° C. 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 delayed, or the production time may be prolonged due to low solubility of the raw materials and the polymer, and if it 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 compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one kind may be used alone, or two or more kinds may be used. You may use together. Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N, N′-di-2-naphthyl-1,4-phenylenediamine, tris (dinonylphenyl) phosphite, and the like. These compounds may be used, and one kind may be used alone, or two or more kinds may be used in combination. In the case where the chain extender is highly reactive such as a short chain aliphatic amine, the reaction may be carried out without adding a catalyst.

<2-10. Water-based polyurethane emulsion>
It is also possible to produce an aqueous polyurethane emulsion using the polycarbonate diol of the present invention.
In that case, when a prepolymer is produced by reacting a polyol containing polycarbonate diol and excess polyisocyanate, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is mixed. A prepolymer is formed, and an aqueous polyurethane emulsion is obtained through a neutralization chlorination step of hydrophilic functional groups, an emulsification step by addition of water, and a chain extension reaction step.

  The hydrophilic functional group of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used here is, for example, a carboxyl group or a sulfonic acid group, and can be neutralized with an alkaline group. It is a basic group. The isocyanate-reactive group is a group that generally reacts with isocyanate to form a urethane bond or a urea bond, such as a hydroxyl group, a primary amino group, or a secondary amino group, and these are mixed in the same molecule. It does not matter.

  Specific examples of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2′-dimethylolpropionic acid, 2,2-methylolbutyric acid, 2,2 ′. -Dimethylol valeric acid etc. are mentioned. Further, diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid and the like can also be mentioned. These may be used alone or in combination of two or more. When these are actually used, they are used after neutralizing with an amine such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine or triethanolamine, or an alkaline compound such as sodium hydroxide, potassium hydroxide or ammonia. be able to.

  When an aqueous polyurethane emulsion is produced, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is used in order to increase the dispersion performance in water. Preferably it is 1 weight% with respect to the total weight of polycarbonate diol and the other polyol, More preferably, it is 5 weight%, More preferably, it is 10 weight%. On the other hand, if too much is added, the properties of the polycarbonate diol of the present invention may not be maintained, so the upper limit is preferably 50% by weight, more preferably 40% by weight, and even more preferably 30% by weight. It is.

In the case of producing an aqueous polyurethane emulsion, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone or N-methyl-2-pyrrolidone in the prepolymer process, or may be carried out without a solvent. Moreover, when using a solvent, after manufacturing an aqueous | water-based emulsion, it is preferable to distill a solvent off by distillation.
The upper limit of the number average molecular weight determined from the hydroxyl value of the polycarbonate diol is preferably 5,000, more preferably 4,500, even more preferably when producing the aqueous polyurethane emulsion without the solvent using the polycarbonate diol of the present invention as a raw material. Is 4,000. The lower limit of the number average molecular weight is preferably 300, more preferably 500, and still more preferably 800. When the number average molecular weight obtained from the hydroxyl value exceeds 5,000 or is smaller than 300, emulsification may be difficult.

  In the synthesis or storage of water-based polyurethane emulsions, anionic interfaces represented by higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oil, sulfosuccinate esters, etc. Activators, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, cationic surfactants such as pyridinium salts, or ethylene oxide and long-chain fatty alcohols or phenols Emulsion stability may be maintained by using a nonionic surfactant or the like typified by a known reaction product.

In addition, when preparing a water-based polyurethane emulsion, water is mechanically mixed under high shear in the presence of an emulsifier in the presence of an emulsifier in a prepolymer organic solvent solution, if necessary, to produce an emulsion. You can also
The water-based polyurethane emulsion thus produced can be used for various applications. In particular, recently, there has been a demand for chemical raw materials with a small environmental load, and it is possible to replace conventional products for the purpose of using no organic solvent.

  As a specific use of the water-based polyurethane emulsion, for example, use in coating agents, water-based paints, adhesives, synthetic leather, and artificial leather is preferable. In particular, the aqueous polyurethane emulsion produced using the polycarbonate diol of the present invention has a structural unit derived from the diol represented by the above formula (B) in the polycarbonate diol, so that it has flexibility and a coating agent. For example, it can be used more effectively than a conventional water-based polyurethane emulsion using a polycarbonate diol.

<2-11. Additives>
The polyurethane of the present invention produced using the polycarbonate diol of the present invention includes a heat stabilizer, a light stabilizer, a colorant, a filler, a stabilizer, an ultraviolet absorber, an antioxidant, an anti-tacking agent, a flame retardant, and aging. Various additives such as an inhibitor and an inorganic filler can be added and mixed as long as the properties of the polyurethane of the present invention are not impaired.

  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; 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 BASF Japan Ltd.), “Irganox 1520” (trade name: manufactured by BASF Japan Ltd.), “Irganox 245” (trade name: manufactured by BASF Japan Ltd.). ) And the like.
Examples of phosphorus compounds include “PEP-36”, “PEP-24G”, “HP-10” (all trade names: manufactured by ADEKA Corporation), “Irgafos 168” (trade name: manufactured by BASF Japan Corporation), and the like. Is mentioned.

Specific examples of the sulfur-containing compound include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).
Examples of the light stabilizer include benzotriazole-based compounds, benzophenone-based compounds, and the like. Specifically, “TINUVIN 622LD”, “TINUVIN 765” (manufactured by Ciba Specialty Chemicals Co., Ltd.), “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 Co., Ltd.).

  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 phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like, and reactive flame retardants.

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

  The lower limit of the addition 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. % By weight, more preferably 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.

<2-12. Polyurethane Film / Polyurethane Plate>
When a film is produced using the polyurethane of the present invention, the lower limit of the thickness of the film is preferably 10 μm, more preferably 20 μm, still more preferably 30 μm, and the upper limit is preferably 1000 μm, more preferably 500 μm, still more preferably. Is 100 μm.
If the film is too thick, sufficient moisture permeability tends not to be obtained, and if it is too thin, pinholes are formed or the film tends to be blocked and difficult to handle.

  The polyurethane film can be preferably used for medical adhesive films, sanitary materials, packaging materials, decorative films, and other moisture-permeable materials. The film may be applied to a support such as a cloth or a non-woven fabric. In this case, the thickness of the polyurethane film itself may be even thinner than 10 μm.

  It is also possible to produce a polyurethane plate using the polyurethane of the present invention. In this case, the upper limit of the thickness of the plate is not particularly limited, and the lower limit is usually preferably 0.5 mm, more preferably 1 mm, and further preferably 3 mm.

<2-13. Molecular weight>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited, but is preferably 50,000 to 500,000 as a weight average molecular weight (Mw) in terms of polystyrene measured by GPC. More preferably, it is 10,000 to 300,000. If Mw is smaller than the lower limit, sufficient strength and hardness may not be obtained. If Mw is larger than the upper limit, handling properties such as workability tend to be impaired.

<2-14. Wet solidification>
The polyurethane of the present invention is obtained by obtaining polyurethane by a one-step method in which 4,4′-diphenylmethane diisocyanate and 1,4-butanediol are reacted with the polycarbonate diol of the present invention in dimethylformamide. When water is added to 100 g of a polyurethane solution having a solid content concentration of 1% by weight, the lower limit of the amount of water added that causes the polyurethane solution to become cloudy is preferably 8 ml, more preferably 9 ml, and more preferably 10 ml. More preferably. If the white turbidity starting water amount is less than the lower limit, the solution may be unstable with respect to moisture absorption, and the liquid stability may be reduced when an aqueous paint is used.
In addition, this water addition amount is specifically measured as the cloudiness start water amount described in the section of Examples described later.

<2-15. 100% modulus, 300% modulus>
When the polyurethane of the present invention is obtained by a one-step process using 4,4′-diphenylmethane diisocyanate and 1,4-butanediol with respect to the polycarbonate diol of the present invention, the width is 10 mm, the length is 100 mm, and the thickness is about 50. The lower limit of 100% modulus (100% M) measured at a temperature of 23 ° C. and a relative humidity of 50% at a distance between chucks of 50 mm, a tensile speed of 500 mm / min for a strip-shaped sample of ˜100 μm is preferably 5. The upper limit is preferably 30 MPa, more preferably 25 MPa, and even more preferably 20 MPa, and is preferably 0 MPa, more preferably 6.0 MPa, and even more preferably 8.0 MPa. If the 100% modulus is less than the above lower limit, the hardness may not be sufficient, and if it exceeds the upper limit, handling properties such as workability tend to be impaired. Furthermore, the lower limit of the 300% modulus (300% M) of the polyurethane is preferably 20 MPa, more preferably 25 MPa, still more preferably 30 MPa, and the upper limit is preferably 70 MPa, more preferably 60 MPa, and even more preferably 50 MPa. If the 300% modulus is less than the lower limit, the hardness may be insufficient. When the 300% modulus exceeds the above upper limit, handling properties such as workability may be impaired.

<2-16. Application>
The polyurethane of the present invention is excellent in strength and hardness, has good heat resistance and wear resistance, and is excellent in workability. Therefore, the polyurethane, elastomer, elastic fiber, paint, fiber, pressure-sensitive adhesive, adhesive, floor It can be widely used for materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, powder paints, active energy ray-curable polymer compositions, and the like.

  In particular, when the polyurethane of the present invention is used for applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc., heat resistance, abrasion resistance, weather resistance Therefore, a dry tactile sensation that is strong against physical impacts and has no tack can be imparted. Further, it can be suitably used for automotive applications that require heat resistance and outdoor applications that require weather resistance. In particular, in the case of powder coating, the polycarbonate diol of the present invention is solid at room temperature and has a glass transition temperature of −20 ° C. or higher, so that a hard coating film can be formed.

  The polyurethane of the present invention can be used as a cast polyurethane elastomer. Specific applications include rolling rolls, papermaking rolls, office equipment, rolls such as pre-tension rolls, forklifts, solid tires for automobile vehicles, trams, carts, etc., casters, industrial products such as conveyor belt idlers, guides There are rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, and cyclone liners. It can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, surferers, and the like.

  The polyurethane of the present invention is also applied for use as a thermoplastic elastomer. For example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment, industrial robots and the like used in the food and medical fields. Moreover, it is used for various power transmission mechanisms, spinning machines, packing equipment, printing machines and the like as belts such as round belts, V belts, and flat belts. Also, it can be used for footwear heel tops, shoe soles, couplings, packings, pole joints, bushes, gears, rolls and other equipment parts, sports equipment, leisure goods, watch belts, and the like. Furthermore, examples of automobile parts include oil stoppers, gear boxes, spacers, chassis parts, interior parts, tire chain substitutes, and the like. In addition, it can be used for films such as keyboard films and automobile films, curl cords, cable sheaths, bellows, transport belts, flexible containers, binders, synthetic leather, depinning products, adhesives, and the like.

The polyurethane of the present invention can also be applied as a solvent-based two-component paint, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sports equipment. Moreover, it can be used for automobile repair as tar epoxy urethane.
The polyurethane of the present invention can be used as a component of a moisture-curable one-component paint, a blocked isocyanate solvent paint, an alkyd resin paint, a urethane-modified synthetic resin paint, an ultraviolet curable paint, a water-based urethane paint, etc. Paints for plastic bumpers, strippable paints, magnetic tape coatings, floor tiles, flooring materials, overprint varnishes for paper, wood grain printing films, wood varnishes, coil coils for high processing, optical fiber protective coatings, solder resists, metals It can be applied to a top coat for printing, a base coat for vapor deposition, a white coat for food cans, and the like.

The polyurethane of the present invention can also be applied to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. as adhesives and adhesives, and as low-temperature adhesives and hot melt components Can also be used.
The polyurethane of the present invention can be used as a binder for magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular agricultural chemicals, polymer cement mortars, resin mortars, rubber chip binders, recycled foams, glass fiber sizing, etc. It can be used.

The polyurethane of the present invention can be used as a component of a fiber processing agent for shrink-proofing, anti-molding, water-repellent processing, and the like.
When the polyurethane of the present invention is used as an elastic fiber, the fiberizing method can be carried out without any limitation as long as it can be spun. For example, a melt spinning method in which the pellets are once pelletized, melted, and directly spun through a spinneret can be employed. When elastic fibers are obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250 ° C. or lower, more preferably 200 ° C. or higher and 235 ° C. or lower.

  The polyurethane elastic fiber of the present invention can be used as a bare yarn as it is, or can be coated with another fiber and used as a coated yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers. Among them, polyester fibers are preferably used in the present invention. The polyurethane elastic fiber of the present invention may contain a dyeing type disperse dye.

The polyurethane of the present invention is used as a sealant caulking for concrete wall, induction joint, sash area, wall PC (PrecastConcrete) joint, ALC (Autoclaved Light-weightConcrete) joint, board joint, composite glass sealant, heat insulating sash sealant. Can be used for automobile sealant.
The polyurethane of the present invention can be used as a medical material. As a blood compatible material, a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc., and as a disposable material, a catheter, a tube, a bag, and a surgical glove. It can be used for artificial kidney potting materials.
The polyurethane of the present invention can be used as a raw material for UV curable paints, electron beam curable paints, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating materials, etc. by modifying the ends. it can.

<2-17. Urethane (meth) acrylate oligomer>
Using the polycarbonate diol of the present invention, a urethane (meth) acrylate-based oligomer can be produced by addition reaction of polyisocyanate and hydroxyalkyl (meth) acrylate. When a polyol, which is another raw material compound, and a chain extender are used in combination, the urethane (meth) acrylate oligomer can be produced by addition reaction of these other raw material compounds with polyisocyanate. .

In the present invention, when “(meth) acryl” is displayed like (meth) acrylate or (meth) acrylic acid, it means acrylic and / or methacrylic.
In addition, the charging ratio of each raw material compound at that time is substantially equal to or the same as the composition of the target urethane (meth) acrylate oligomer.
The amount of all isocyanate groups in the urethane (meth) acrylate oligomer and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually equimolar in theory.

  When producing urethane (meth) acrylate oligomers, the amount of hydroxyalkyl (meth) acrylate used is hydroxyalkyl (meth) acrylate, the polycarbonate diol of the present invention, and other raw material compounds used as necessary. Usually 10 mol% or more, preferably 15 mol based on the total amount of the polyol (hereinafter sometimes referred to as “other polyol”) and the compound containing a functional group that reacts with isocyanate such as a chain extender. % Or more, more preferably 25 mol% or more, and usually 70 mol% or less, preferably 50 mol% or less. According to this ratio, the molecular weight of the urethane (meth) acrylate oligomer obtained can be controlled. When the proportion of hydroxyalkyl (meth) acrylate is large, the molecular weight of the urethane (meth) acrylate oligomer tends to be small, and when the proportion is small, the molecular weight tends to be large.

The amount of the polycarbonate diol of the present invention is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol, based on the total amount of the polycarbonate diol of the present invention and other polyols. % Or more. It is preferable that the amount of the polycarbonate diol used in the present invention is equal to or more than the above lower limit value because the resulting cured product tends to have good hardness and stain resistance. Moreover, when the usage-amount of the polycarbonate diol of this invention is more than the said lower limit, it will become the tendency for the elongation of a hardened | cured material obtained and a weather resistance to improve, and it is preferable.
The amount of the polycarbonate diol of the present invention is preferably 10% by weight or more, more preferably 30% by weight or more, and still more preferably with respect to the total amount of the polycarbonate diol of the present invention and other polyols. Is 50% by weight or more, particularly preferably 70% by weight or more. When the amount of the polycarbonate diol of the present invention is not less than the above lower limit, the viscosity of the resulting composition is lowered and workability is improved, and the mechanical strength, hardness and wear resistance of the resulting cured product are improved. This is preferable.

  Further, when a chain extender is used, the polycarbonate diol of the present invention is used in an amount of 70 mol% or more with respect to the total amount of the polycarbonate diol of the present invention and the other polyol and chain extender combined. More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more, Most preferably, it is 95 mol% or more. It is preferable that the amount of the polycarbonate diol of the present invention is not less than the above lower limit value because the liquid stability tends to be improved.

  In the production of the urethane (meth) acrylate oligomer, a solvent can be used for the purpose of adjusting the viscosity. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can be used usually in an amount of less than 300 parts by weight with respect to 100 parts by weight of the solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer, the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compound is preferably 20% by weight or more based on the total amount of the reaction system, and is 40% by weight. % Or more is more preferable. The upper limit of the total content is 100% by weight. It is preferable for the total content of the urethane (meth) acrylate oligomer and its raw material compound to be 20% by weight or more because the reaction rate tends to increase and the production efficiency tends to improve.

  An addition reaction catalyst can be used in the production of the urethane (meth) acrylate oligomer. Examples of the addition reaction catalyst include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. An addition reaction catalyst may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, the addition reaction catalyst is preferably dioctyltin dilaurate from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

The addition reaction catalyst has an upper limit of usually 1000 ppm by weight, preferably 500 ppm by weight, and a lower limit of usually 10 ppm by weight, preferably relative to the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Used at 30 ppm by weight.
Further, when the reaction system contains a (meth) acryloyl group during the production of the urethane (meth) acrylate oligomer, a polymerization inhibitor can be used in combination. Examples of such polymerization inhibitors include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese such as manganese acetate. Examples thereof include salts, nitro compounds, and nitroso compounds. A polymerization inhibitor may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, phenols are preferable as the polymerization inhibitor.

  The polymerization inhibitor has an upper limit of usually 3000 ppm, preferably 1000 ppm by weight, particularly preferably 500 ppm by weight, particularly preferably 500 ppm by weight, based on the total content of the urethane (meth) acrylate oligomer to be produced and its raw material compounds. Usually, 50 ppm by weight, preferably 100 ppm by weight is used.

  During the production of the urethane (meth) acrylate oligomer, the reaction temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. A reaction temperature of 20 ° C. or higher is preferable because the reaction rate increases and the production efficiency tends to improve. Moreover, reaction temperature is 120 degrees C or less normally, and it is preferable that it is 100 degrees C or less. It is preferable for the reaction temperature to be 120 ° C. or lower because side reactions such as an allohanato reaction hardly occur. When the reaction system contains a solvent, the reaction temperature is preferably lower than the boiling point of the solvent. When (meth) acrylate is contained, the reaction temperature is 70 ° C. from the viewpoint of preventing the reaction of the (meth) acryloyl group. The following is preferable. The reaction time is usually about 5 to 20 hours.

  The number average molecular weight in terms of polystyrene measured by GPC of the urethane (meth) acrylate oligomer thus obtained is preferably 500 or more, particularly preferably 1,000 or more, and particularly preferably 10,000 or less. It is preferably 5,000 or less, particularly 3,000 or less. When the number average molecular weight of the urethane (meth) acrylate oligomer is not less than the above lower limit, the resulting cured film has good three-dimensional workability and tends to have an excellent balance between three-dimensional workability and stain resistance. When the number average molecular weight of the urethane (meth) acrylate oligomer is not more than the above upper limit, the cured film obtained from the composition has good contamination resistance and tends to have a good balance between three-dimensional processability and contamination resistance. Therefore, it is preferable. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure, and as this distance increases, the structure becomes flexible and easily stretched, and the three-dimensional workability is superior. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

<2-18. Polyester elastomer>
Furthermore, the polycarbonate diol of the present invention can be used as a polyester-based elastomer. The polyester elastomer is a copolymer composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of aliphatic polyether, aliphatic polyester or aliphatic polycarbonate. When the polycarbonate diol of the present invention is used as a constituent component of the soft segment, physical properties such as heat resistance and water resistance are excellent as compared with the case of using an aliphatic polyether or aliphatic polyester. Compared to known polycarbonate diols, it has a melt flow rate, that is, a melt flow rate suitable for blow molding and extrusion molding, and a polycarbonate ester elastomer with an excellent balance between mechanical strength and other physical properties. It can be suitably used for various molding materials including fibers, films and sheets, for example, molding materials such as elastic yarns and boots, gears, tubes and packings. Specifically, it can be effectively applied to applications such as joint boots such as automobiles and home appliance parts that require heat resistance and durability, and wire covering materials.

<2-19. Active energy ray-curable polymer composition>
Hereinafter, the active energy ray-curable polymer composition containing the urethane (meth) acrylate oligomer described above (hereinafter sometimes referred to as “the active energy ray-curable polymer composition of the present invention”) will be described. To do.
The active energy ray-curable polymer composition of the present invention preferably has a molecular weight between calculated network crosslinking points of 500 to 10,000.

  In the present specification, the molecular weight between calculated network cross-linking points of the composition is the average molecular weight between active energy ray reactive groups (hereinafter sometimes referred to as “cross-linking points”) that form a network structure in the entire composition. Represents a value. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter, sometimes referred to as “monofunctional compound”) reacts, it becomes a linear polymer, while the active energy A network structure is formed when a compound having two or more linear reactive groups (hereinafter sometimes referred to as “polyfunctional compound”) reacts.

  Therefore, the active energy ray reactive group of the polyfunctional compound is a crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound has the polyfunctional compound. The molecular weight between the crosslinking points is treated as having an effect of extending the molecular weight, and the molecular weight between the calculation network crosslinking points is calculated. In addition, the calculation of the molecular weight between the calculation network crosslinking points is performed on the assumption that all the active energy ray reactive groups have the same reactivity and that all the active energy ray reactive groups react by irradiation with the active energy ray. .

In a polyfunctional compound single-system composition in which only one type of polyfunctional compound reacts, the molecular weight between the calculated network cross-linking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. . For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1,000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.
In a polyfunctional compound mixed system composition in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition is This is the molecular weight between the calculated network crosslinking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1,000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of reactive energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2/20 = 520.

  When a monofunctional compound is included in the composition, a molecule formed by calculation and equimolar to the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound, and the monofunctional compound linked to the crosslinking point Assuming that the reaction takes place in the middle of the chain, the extension of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, and the total active energy ray reaction of the polyfunctional compound in the composition. Half of the value divided by the radix. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition.

  For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1,000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the calculated network cross-linking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinking points of the composition is 1000 + 500 = 1500. From the above, in the mixture of the monofunctional compound MA having the molecular weight WA, the fB functional compound MB mol having the molecular weight WB, and the fC functional compound MC mole having the molecular weight WC, the molecular weight between the calculated network cross-linking points of the composition Can be expressed by the following formula.

  The molecular weight between the calculated network crosslinking points of the active energy ray-curable polymer composition of the present invention calculated in this way is preferably 500 or more, more preferably 800 or more, and 1,000 or more. More preferably, it is preferably 10,000 or less, more preferably 8,000 or less, further preferably 6,000 or less, and even more preferably 4,000 or less. 3,000 or less is particularly preferable.

  A molecular weight between calculated network crosslinking points of 10,000 or less is preferable because the cured film obtained from the composition has good stain resistance and tends to have a good balance between three-dimensional processability and stain resistance. Moreover, it is preferable that the molecular weight between the calculation network cross-linking points is 500 or more because the obtained cured film has good three-dimensional workability and tends to have an excellent balance between the three-dimensional workability and the stain resistance. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the three-dimensional processability is excellent. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

The active energy ray-curable polymer composition of the present invention may further contain components other than the urethane (meth) acrylate oligomer. Examples of such other components include an active energy ray reactive monomer, an active energy ray curable oligomer, a polymerization initiator, a photosensitizer, an additive, and a solvent.
In the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer is 40% by weight or more based on the total amount of active energy ray-reactive components including the urethane (meth) acrylate oligomer. It is preferable that it is 60% by weight or more. In addition, the upper limit of this content is 100 weight%. When the content of the urethane (meth) acrylate oligomer is 40% by weight or more, the curability is good and the three-dimensional workability tends to be improved without excessively increasing the mechanical strength of the cured product. This is preferable.

  Moreover, in the active energy ray-curable polymer composition of the present invention, the content of the urethane (meth) acrylate oligomer is preferably large in terms of elongation and film-forming property, and on the other hand, the viscosity is reduced. In terms of points, a smaller number is preferable. From such a viewpoint, the content of the urethane (meth) acrylate oligomer is preferably 50% by weight or more based on the total amount of all components including other components in addition to the active energy ray-reactive component. 70% by weight or more is more preferable. In addition, the upper limit of content of a urethane (meth) acrylate type oligomer is 100 weight%, and it is preferable that this content is less than that.

  Moreover, in the active energy ray-curable polymer composition of the present invention, the content of the total amount of the active energy ray-reactive component including the urethane (meth) acrylate oligomer depends on the curing rate and surface curability of the composition. From the standpoint of excellent and no tack remaining, it is preferably 60% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more based on the total amount of the composition. 95% by weight or more is particularly preferable. In addition, the upper limit of this content is 100 weight%.

  Any known active energy ray-reactive monomer can be used as the active energy ray-reactive monomer. These active energy ray reactive monomers are used for the purpose of adjusting the hydrophilicity / hydrophobicity of urethane (meth) acrylate oligomers and the physical properties such as hardness and elongation of the cured product when the resulting composition is cured. Is done. An active energy ray reactive monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Examples of such active energy ray reactive monomers include vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specific examples include styrene, α-methylstyrene, α-chlorostyrene. Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate Ester monomers; Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; Allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth) acrylamide, N, N-dimethylacrylamide N, N-dimethylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acryloylmorpholine (Meth) acrylamides such as methylenebis (meth) acrylamide; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl , (Meth) acrylic acid-i-butyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Stearyl, tetrahydrofurfuryl (meth) acrylate, (meth) a Morpholyl laurate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate , (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) Monofunctional (meth) acrylic acid such as phenyl acrylate And ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ( n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (meth) Polypropylene glycol acrylate (n = 5-14), di (meth) acrylic acid-1,3-butylene glycol, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid polybutylene glycol ( n = 3-16), di (meth) acrylic acid poly Li (1-methylbutylene glycol) (n = 5-20), di (meth) acrylic acid-1,6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) acrylic acid Neopentyl glycol, hydroxypivalate neopentyl glycol di (meth) acrylate, di (meth) acrylate dicyclopentanediol, di (meth) acrylate tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpropane polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate , Propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri Black decanedimethanol di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate; and the like.

  Among these, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid, especially in applications where coating properties are required. Has a ring structure in the molecule, such as trimethylcyclohexyl, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc. Monofunctional (meth) acrylates are preferred. On the other hand, in applications where mechanical strength of the resulting cured product is required, di (meth) acrylic acid-1,4-butanediol, di (meth) acrylic acid-1, 6-hexanediol, di (meth) acrylic acid-1,9-nonanediol, di (meth) Neopentyl glycol acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

  In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive monomer is selected from the viewpoints of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. It is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less, based on the total amount of the composition.

The active energy ray-curable oligomer may be used alone or in combination of two or more. Examples of the active energy ray-curable oligomer include epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers.
In the active energy ray-curable polymer composition of the present invention, the content of the active energy ray-reactive oligomer is based on the total amount of the composition from the viewpoint of adjusting physical properties such as hardness and elongation of the obtained cured product. 50% by weight or less, more preferably 30% by weight or less, further preferably 20% by weight or less, and particularly preferably 10% by weight or less.

  The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used. A polymerization initiator may be used individually by 1 type, and 2 or more types may be mixed and used for it. Furthermore, you may use together radical photopolymerization initiator and a photosensitizer.

  Examples of the photo radical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ] 2-Methyl-propan-1-one is more preferred.

In addition, when the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radical polymerizable group, as a polymerization initiator, a photocation together with the above-mentioned photo radical polymerization initiator. A polymerization initiator may be included. Any known cationic photopolymerization initiator can be used.
The content of these polymerization initiators in the active energy ray-curable polymer composition of the present invention is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components, More preferably, it is 5 parts by weight or less. It is preferable for the content of the polymerization initiator to be 10 parts by weight or less because the mechanical strength is not easily lowered by the initiator decomposition product.

  The photosensitizer can be used for the same purpose as the polymerization initiator. A photosensitizer may be used individually by 1 type and may be used in mixture of 2 or more types. As the photosensitizer, any known photosensitizer can be used as long as the effects of the present invention are obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, And 4-dimethylaminoacetophenone.

In the active energy ray-curable polymer composition of the present invention, the content of the photosensitizer is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components. More preferably, it is 5 parts by weight or less. When the content of the photosensitizer is 10 parts by weight or less, it is preferable that the mechanical strength does not decrease due to the decrease in the crosslinking density.
The said additive is arbitrary and can use the various materials added to the composition used for the same use as an additive. An additive may be used individually by 1 type, and 2 or more types may be mixed and used for it. Examples of such additives include glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, and metal powder. Fillers such as carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as “inorganic components”); Agent, heat stabilizer, UV absorber, HALS (hindered amine light stabilizer), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, Anti-settling agents, surfactants, thixotropy imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents and other modifiers; pigments, dyes, hue adjustments Colorants and the like; and, monomer and / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts, curing accelerators like; and the like.

In the active energy ray-curable polymer composition of the present invention, the content of the additive is preferably 10 parts by weight or less with respect to a total of 100 parts by weight of the active energy ray reactive components. It is more preferable that the amount is not more than parts by weight. It is preferable for the content of the additive to be 10 parts by weight or less because it is difficult for the mechanical strength to decrease due to a decrease in crosslink density.
The solvent is used for the purpose of adjusting the viscosity of the active energy ray-curable polymer composition of the present invention, for example, depending on the coating method for forming the coating film of the active energy ray-curable polymer composition of the present invention. Can be used. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used as long as the effects of the present invention are obtained. Preferable solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. A solvent can be normally used in less than 200 weight part with respect to 100 weight part of solid content of an active energy ray curable polymer composition.

  There are no particular limitations on the method of incorporating the active energy ray-curable polymer composition of the present invention into optional components such as the aforementioned additives, and examples thereof include conventionally known mixing and dispersion methods. In addition, in order to disperse | distribute the said arbitrary component more reliably, it is preferable to perform a dispersion | distribution process using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact Examples of the processing method include a mill, a kneader, a homogenizer, and an ultrasonic disperser.

  The viscosity of the active energy ray-curable polymer composition of the present invention can be appropriately adjusted according to the use and usage of the composition, but the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc. From the above, the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, 000 mPa · s or less is preferable, and 50,000 mPa · s or less is more preferable. The viscosity of the active energy ray-curable polymer composition can be adjusted by, for example, the content of the urethane (meth) acrylate oligomer of the present invention, the type of the optional component, the blending ratio thereof, and the like.

  As a coating method of the active energy ray-curable polymer composition of the present invention, a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll coater method Known methods such as a lip coater method, a die coater method, a slot die coater method, an air knife coater method and a dip coater method can be applied. Among them, a bar coater method and a gravure coater method are preferable.

<2-20. Cured film and laminate>
The active energy ray-curable polymer composition of the present invention can be made into a cured film by irradiating this with active energy rays.
As the active energy rays used when the composition is cured, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He—Cd lasers, solid lasers, xenon lamps, high frequency induction mercury lamps, sunlight, and the like are suitable.

The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when curing is performed by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. Moreover, in the case of ultraviolet irradiation, it is preferable that it is 50-1,000 mJ / cm < ² >. The atmosphere during curing may be air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.

  The thickness of the cured film is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, particularly preferably 50 μm. When the film thickness is 1 μm or more, the design properties and functionality after three-dimensional processing are improved, and when it is 200 μm or less, the internal curability and the three-dimensional workability are preferable. In industrial use, the lower limit of the thickness of the cured film is preferably 1 μm, and the upper limit is preferably 100 μm, more preferably 50 μm, particularly preferably 20 μm, and most preferably 10 μm.

A laminate having a layer made of the above cured film can be obtained on a substrate.
The laminate is not particularly limited as long as it has a layer made of a cured film, and may have a layer other than the base material and the cured film between the base material and the cured film, or may be present outside the layer. You may do it. Moreover, the said laminated body may have multiple layers of a base material and a cured film.
As a method of obtaining a laminate having a multi-layer cured film, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured. Apply a known method such as applying the upper layer and curing again with active energy rays, or applying each layer to the release film or base film and then laminating the layers in an uncured or semi-cured state. Although possible, a method of curing with an active energy ray after laminating in an uncured state is preferable from the viewpoint of improving adhesion between layers. As a method of laminating in an uncured state, a known method such as sequential coating in which the upper layer is applied after the lower layer is applied or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits is applied. Yes, but not necessarily.

Examples of the base material include various shapes such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate, and (meth) acrylic resin, or plates formed of metal. The article is mentioned.
The cured film can be a film excellent in stain resistance and hardness against general household contaminants such as ink and ethanol, and the laminate using the cured film as a coating on various substrates has a design property and surface. It can be excellent in protection.

In addition, the active energy ray-curable polymer composition of the present invention is capable of following deformation during three-dimensional processing, taking into account the molecular weight between the calculation network cross-linking points, elongation at break, mechanical strength, contamination resistance. A cured film having both properties and hardness can be provided.
Moreover, it is expected that the active energy ray-curable polymer composition of the present invention can easily produce a thin film-like resin sheet by single-layer coating.

  The breaking elongation of the cured film was determined by cutting the cured film to a width of 10 mm and using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100) at a temperature of 23 ° C., a tensile speed of 50 mm / min, between chucks. The value measured by performing a tensile test under the condition of a distance of 50 mm is preferably 50% or more, more preferably 75% or more, further preferably 100% or more, and 120% or more. Is particularly preferred.

  The cured film and the laminate can be used as a coating substitute film, and can be effectively applied to, for example, interior / exterior building materials, various members of automobiles, home appliances, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is exceeded.

  In the following, 1,4-butanediol is 14BD, 1,6-hexanediol is 16HD, neopentyl glycol is NPG, 5,5-dimethyl-1,3-dioxan-2-one is NPC, dimethylformamide is DMF, Diphenylmethane diisocyanate is sometimes abbreviated as MDI.

  Below, the evaluation method of each physical property value is as follows.

[Evaluation method: Polycarbonate diol]
<Quantification of phenoxy group content, dihydroxy compound content, NPC content and phenol content>
Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) was measured, phenoxy group, dihydroxy compound, and phenol were identified from the signal position of each component, and each integrated value was determined. The content of was calculated. The detection limit at that time is 100 ppm as the weight of phenol with respect to the weight of the entire sample, 0.1 wt% as the weight of NPC, the diol represented by the formula (A), the diol represented by the formula (B), etc. The dihydroxy compound is 0.1% by weight. The ratio of the phenoxy group is determined from the ratio of the integral value of one proton of the phenoxy group to the integral value of one proton of the whole terminal, and the detection limit of the phenoxy group is 0.05% with respect to the whole terminal. .

<Molar ratio between the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B)>
A polycarbonate diol is dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) is measured. From the signal position of each component, the structural unit derived from the diol represented by the formula (A) And the molar ratio of the structural unit derived from the diol represented by the formula (B) (hereinafter, abbreviated as (A) :( B) and the composition as abbreviated as (A) / (B). is there). Moreover, it calculated | required similarly about the molar ratio of the terminal derived from the diol represented by the said Formula (A), and the terminal derived from the diol represented by the said Formula (B).

<Ratio of terminal hydroxyl group of polycarbonate diol>
Polycarbonate diol was dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AL-400 manufactured by JEOL Ltd.) was measured. From the signal position of each component, the phenoxy group and the methylene at the α-position of the hydroxyl group were identified. A value obtained by dividing the integrated value of methylene at the α-position by the sum of the integrated values of methylene at the α-position of the phenoxy group and the hydroxyl group was determined, and the ratio of the terminal hydroxyl group of the polycarbonate diol was expressed as a percentage.

<Hydroxyl value, number average molecular weight>
Based on JIS K1557-1, the hydroxyl value of polycarbonate diol was measured by a method using an acetylating reagent. The number average molecular weight was calculated by the following formula based on the hydroxyl value and the ratio of terminal hydroxyl groups.
Number average molecular weight = {(56.11 × 1000) / OH number} × 2

<Molecular weight distribution Mw / Mn>
The molecular weight distribution was calculated by obtaining polystyrene-converted Mn and Mw values by GPC measurement under the following conditions.
Apparatus: HLC-8020 manufactured by Tosoh Corporation
Column: TSKgel GMHxL-L (7.8 mm ID × 30 cmL × 4)
Eluent: THF (tetrahydrofuran)
Flow rate: 0.8 mL / min
Column temperature: 40 ° C
RI detector: RI

<Measurement of glass transition temperature (Tg)>
About 10 mg of polycarbonate diol is enclosed in an aluminum pan, EXSTAR
Using DSC6200 (manufactured by Seiko Instruments Inc.), in a nitrogen atmosphere at a rate of 20 ° C / min, 30 ° C to 150 ° C, at a rate of 40 ° C / min, 150 ° C to -120 ° C, at a rate of 20 ° C / min The temperature increase / decrease operation was performed from −120 ° C. to 120 ° C., and the inflection point at the second temperature increase was defined as the glass transition temperature (Tg).

[Evaluation method: Polyurethane]
<Measurement of solution viscosity>
A solution of polyurethane dissolved in dimethylformamide (concentration: 30% by weight) was set on a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) with a 3 ° × R14 rotor, and the solution viscosity of the polyurethane solution was measured at 23 ° C. .

<Molecular weight measurement>
Prepare a dimethylacetamide solution so that the polyurethane has a molecular weight of 0.14% by weight and a GPC apparatus (product name “HLC-8220” manufactured by Tosoh Corporation (column: Tskel GMH-XL × 2)) The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of standard polystyrene were measured.

<Room temperature tensile test method>
In accordance with JISK6301, a polyurethane test piece with a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm was measured between chucks using a tensile tester (Orientec, product name “Tensilon UTM-III-100”). A tensile test was performed at a temperature of 23 ° C. (relative humidity 55%) at a distance of 50 mm and a tensile speed of 500 mm / min, and when the test piece was stretched 100%, the stress was 100% M and 300%. The stress was measured as 300% M.

<Water turbidity start water volume>
While stirring 100 g of DMF solution of 1% by weight of polyurethane, distilled water was dropped into this solution, and the value of the amount of water dripping when polyurethane coagulation started at 25 ± 1 ° C and became slightly cloudy was measured. did. Moreover, the DMF used for the measurement used that having a water content of 0.03% or less. When the polyurethane DMF solution was slightly cloudy in advance, the amount of water dripping when the solidification of the polyurethane started and the degree of cloudiness changed was taken as the cloudiness start water amount.

[Production and evaluation of polycarbonate diol]
[Synthesis Example 1]
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 1,4-butanediol: 81.7 g, neopentyl glycol: 1255.2 g, diphenyl carbonate: 2663.1 g, magnesium acetate 4 Hydrate aqueous solution: 6.6 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 58 mg) was added, and nitrogen gas substitution was performed. Under stirring, the internal temperature was raised to 160 ° C., and the contents were dissolved by heating. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol out of the system. Next, the pressure is lowered to 9.3 kPa over 90 minutes and further lowered to 0.7 kPa over 30 minutes, and then the reaction is continued, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compounds out of the system. For 30 minutes to obtain a polycarbonate diol-containing composition.

The obtained polycarbonate diol-containing composition was fed to a thin film distillation apparatus at a flow rate of 20 g / min, and thin film distillation (temperature: 200 ° C., pressure: 53 to 67 Pa) was performed. As the thin-film distillation apparatus, an internal condenser having a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m2, a special model of molecular distillation apparatus MS-300 manufactured by Shibata Kagaku Co., Ltd. with a jacket was used.
Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

[Synthesis Example 2]
In the production of the polycarbonate diol of Synthesis Example 1, 143.1 g of 14BD, 1275.6 g of NPG, 2641.3 g of diphenyl carbonate, and 6.7 mL of magnesium acetate tetrahydrate aqueous solution (concentration: 8.4 g / L, acetic acid) Except for the use of magnesium tetrahydrate: 57 mg), the reaction was carried out under the same conditions and methods to obtain a polycarbonate diol-containing composition.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Synthesis Example 1. Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

[Synthesis Example 3]
In the production of the polycarbonate diol of Synthesis Example 1, 27HD of 16HD, 953.0 g of NPG, 2276.6 g of diphenyl carbonate, and 5.8 mL of magnesium acetate tetrahydrate aqueous solution (concentration: 8.4 g / L, acetic acid) Except for the use of magnesium tetrahydrate (49 mg), the reaction was carried out under the same conditions and methods to obtain a polycarbonate diol-containing composition.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Synthesis Example 1. Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

[Synthesis Example 4]
In the production of the polycarbonate diol of Synthesis Example 1, 147.1 was 607.1 g, NPG was 701.6 g, diphenyl carbonate was 2691.4 g, and magnesium acetate tetrahydrate aqueous solution was 6.9 mL (concentration: 8.4 g / L, acetic acid). Except for the use of magnesium tetrahydrate: 60 mg), the reaction was carried out under the same conditions and methods to obtain a polycarbonate diol-containing composition.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Synthesis Example 1. Table 1 shows the evaluation results of properties and physical properties of the polycarbonate diol obtained by thin film distillation.

[Production and evaluation of polyurethane]
[Example 1]
To the 1 L separable flask, 85.2 g of the polycarbonate diol produced in Synthesis Example 1 and 249.7 g of dimethylformamide were added and immersed in an oil bath set at 55 ° C. to dissolve. Stirring was started at about 100 rpm, and 3.9 g of 1,4-butanediol and 0.023 g of Neostan U-830 (manufactured by Nitto Kasei Co., Ltd.) were added dropwise as a urethanization catalyst. Next, 16.8 g of diphenylmethane diisocyanate was added at such a rate that the liquid temperature did not exceed 70 ° C. Thereafter, 0.9 g of diphenylmethane diisocyanate was gradually added until the weight average molecular weight measured by GPC exceeded 150,000 to obtain a polyurethane solution having a solid content of 30% by weight. This polyurethane solution was applied on a polyethylene film with a doctor blade with a uniform film thickness and dried with a dryer to obtain a polyurethane film.
Table 2 shows the evaluation results of the physical properties of the obtained polyurethane solution and polyurethane film.

[Example 2]
Except for using 81.2 g of polycarbonate diol prepared in Synthesis Example 2 as polycarbonate diol, 243.6 g of DMF, 3.6 g of 14BD, 0.019 g of Neostan U-830, and 20.0 g of MDI in total. A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1. The evaluation results of the physical properties are shown in Table 2.

[Example 3]
Except for using 100.1 g of polycarbonate diol produced in Synthesis Example 3 as polycarbonate diol, 299.4 g of DMF, 4.6 g of 14BD, 0.027 g of Neostann U-830, and 25.7 g of MDI in total. A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1. The evaluation results of the physical properties are shown in Table 2.

[Comparative Example 1]
Except for using 84.5 g of polycarbonate diol prepared in Synthesis Example 4 as polycarbonate diol, 257.1 g of DMF, 3.9 g of 14BD, 0.020 g of Neostann U-830, and 22.3 g of MDI in total. A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1. The evaluation results of the physical properties are shown in Table 2.

[Comparative Example 2]
Other than using 85.6 g of Duranol T-6002 (manufactured by Asahi Kasei Chemicals Corporation) as polycarbonate diol, 258.8 g of DMF, 3.9 g of 14BD, 0.018 g of Neostan U-830, and 21.0 g of MDI in total. Obtained a polyurethane solution and a polyurethane film in the same manner as in Example 1. The evaluation results of the physical properties are shown in Table 2.

  In the “tensile test” in Table 2, the values of both the 100% M and 300% M in the examples are larger than those in the comparative examples, indicating that the strength and hardness are good. Further, since the value of “solution viscosity” is small, it is understood that the handling property is high and the workability is good. Therefore, it can be seen that the polycarbonate diol of the present invention is a polycarbonate diol which is a raw material of polyurethane having excellent strength and hardness and high processability as compared with the conventional polycarbonate diol.

Claims (9)

A composition containing diaryl carbonate, a diol represented by the following formula (A) and a polycarbonate diol which is a polymer of the diol represented by the following formula (B), the glass transition temperature of the polycarbonate diol-containing composition Is a polycarbonate diol-containing composition, wherein the composition is -20 ° C or higher.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)   The polycarbonate diol-containing composition according to claim 1, wherein the content of 5,5-dialkyl-1,3-dioxan-2-one is 3% by weight or less.   The number average molecular weight calculated | required from the hydroxyl value of the said polycarbonate diol is 500-5,000, The polycarbonate diol containing composition of Claim 1 or 2 characterized by the above-mentioned.   The ratio of the structural unit derived from the diol represented by the formula (A) and the structural unit derived from the diol represented by the formula (B) is 75:25 to 99: 1 in molar ratio. The polycarbonate diol-containing composition according to any one of claims 1 to 3.   The polycarbonate diol-containing composition according to any one of claims 1 to 4, wherein a ratio of terminal hydroxyl groups of the polycarbonate diol is 95 mol% or more.   The polyurethane using the polycarbonate diol containing composition of any one of Claims 1-5. A method for producing a composition containing a polycarbonate diol by polymerizing a diaryl carbonate, a diol represented by the following formula (A) and a diol represented by the following formula (B) in the presence of a metal compound catalyst. The method for producing a polycarbonate diol-containing composition, wherein the polycarbonate diol-containing composition has a glass transition temperature of -20 ° C or higher.

(However, 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. You may have an atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these.)

(Wherein, R ³ represents an aliphatic or alicyclic hydrocarbon group 1 to 15 carbon atoms which may contain heteroatoms.)   The polycarbonate according to claim 7, wherein the diol represented by the formula (A) and the diol represented by the formula (B) are used in a molar ratio of 75:25 to 99: 1. A method for producing a diol-containing composition.   The method for producing a polycarbonate diol-containing composition according to claim 7 or 8, wherein the metal compound catalyst is a compound of a Group 1 metal or a Group 2 metal compound of the periodic table.