JP7187844B2 - Polycarbonate diol and aqueous polyurethane dispersion using the same - Google Patents

Description

The present invention is a raw material for an aqueous polyurethane dispersion that has a good balance of chemical resistance, solvent resistance, flexibility, mechanical strength, heat resistance, hydrolysis resistance, etc., and is useful for synthetic leather, elastomers, coating agents, etc. and a water-based polyurethane dispersion using the same (hereinafter sometimes referred to as "aqueous polyurethane dispersion").

Conventionally, polyols with a molecular weight of about 500 to 5000 have been used as raw materials for the main soft segments of polyurethanes produced on an industrial scale. Typical examples include polyester polyols, polycaprolactone polyols, and polycarbonate diols. Low-molecular-weight monomers such as diisocyanates, diols, and diamines are generally used as raw materials for the hard segment portion (Non-Patent Document 1).

Of these, polycarbonate-type polyurethanes, typified by polycarbonate diol, are considered to be the most durable grades in terms of heat resistance and hydrolysis resistance, and are widely used as elastic fibers, synthetic or artificial leather, high-performance elastomers, and coating agents. It is

Among polycarbonate diols, those using a dihydroxy compound having 4 to 6 carbon atoms as a raw material, in particular, yield polyurethanes with excellent balance of physical properties such as flexibility, strength, solvent resistance, heat resistance, and hydrolysis resistance. (Patent Document 1).

On the other hand, water-based polyurethane dispersions are useful for applications such as paints, surface treatment agents, adhesives, leather, coating agents, and various binders. There is a growing movement to move to waterborne polyurethane dispersions.
In order to stably disperse hydrophobic polyurethane in water, a method is known in which a hydrophilic group such as a carboxyl group, a sulfonic acid group, or a tertiary amino group is introduced into the polyurethane used in the aqueous polyurethane dispersion. . In this method, a highly dispersible dihydroxycarboxylic acid is often used as the diol component constituting the polyurethane, and dimethylolpropionic acid, which is easily available industrially, is generally used (Patent Documents 2 to 4). ).

However, when dimethylolpropionic acid is used in urethane synthesis, the number of carbon atoms between two hydroxyl groups is as small as 3, so a carboxyl group was introduced into the hard segment (a structural unit with a short distance between urethane bonds). A polyurethane is formed. As a result, as shown in Comparative Example 1 described later, there was a problem that the flexibility and strength of the polyurethane were lowered due to aggregation of the hard segments. Synthetic leathers and elastomers made from this polyurethane have a hard texture and are inferior to natural leather in "texture."

In order to solve the above problem by introducing a carboxyl group into the soft segment, studies have been made to use a high-molecular-weight polyol containing a carboxyl group as an alternative to dimethylolpropionic acid.

For example, JP-A-6-313024 (Patent Document 5) describes a carboxyl group-containing polycaprolactone polyol obtained by ring-opening addition polymerization of lactones using a dihydroxycarboxylic acid as an initiator, an organic diisocyanate, and a chain extender. Disclosed is an aqueous polyurethane resin comprising

In addition, in Japanese Patent No. 4927621 (Patent Document 6), dimethylolpropionic acid, 1,4-butanediol, a carboxyl group-containing polyester polyol obtained by polymerizing adipic acid, an organic diisocyanate, and an aqueous polyurethane resin consisting of a chain extender is disclosed.

However, polyester polyols and polycaprolactone polyols have many ester bonds, are low in hydrolysis resistance, and are not sufficient in heat resistance. Therefore, there is a demand for a carboxyl group-containing polyol having a low ester bond rate and improved heat resistance and hydrolysis resistance.

International Publication No. 2017/204276 (Patent Document 7) reports a carboxyl group-containing polycarbonate diol synthesized by ring-opening polymerization of trimethylene carbonate using dimethylolpropionic acid as an initiator. The method described in , also has the following problems.
(1) Under polymerization reaction conditions, the carboxyl group of dimethylolpropionic acid reacts with the hydroxyl group, and a large amount of ester bonds are by-produced. Therefore, the polyurethane using this carboxyl group-containing polycarbonate diol has low durability.
(2) Since only dimethylolpropionic acid as an initiator contains a carboxylic acid, the carboxyl group may be insufficient when the molecular weight is increased to 1,000 or more. Moreover, the content of carboxyl groups in one molecule of polycarbonate diol cannot be arbitrarily adjusted.
(3) Since the average number of carbon atoms between carbonate bonds is 3, flexibility is lowered when made into polyurethane.
(4) Since it is a block polymer with a narrow molecular weight distribution obtained by ring-opening polymerization, it has a structure in which the structural units of the same polycarbonate skeleton are regularly continuous, and the cohesive force due to hydrogen bonding is strong, and the polyurethane water dispersion When used in , the cohesive force is high and the storage stability is poor.

JP-A-5-51428 Japanese Patent Publication No. 61-5485 Japanese Patent Publication No. 3-48955 Japanese Patent Publication No. 4-488 JP-A-6-313024 Japanese Patent No. 4927621 WO2017/204276

"Fundamentals and Applications of Polyurethane" pp.96-106 Supervised by Katsuji Matsunaga, CMC Publishing Co., Ltd., November 2006

As described above, carboxyl group-containing polyols that can be used as raw materials for high-performance urethane have not been provided in the past. It is difficult to achieve sufficient physical properties such as mechanical strength, heat resistance, and hydrolysis resistance, and an aqueous polyurethane dispersion that satisfies the requirements for synthetic leather, elastomer, and coating agent applications has not been realized. In addition, in the conventional technology, the partial structure in the polyol (average carbon (number, structural unit, composition) have not been sufficiently studied.

The present invention is a raw material for an aqueous polyurethane dispersion that has a good balance of chemical resistance, solvent resistance, flexibility, mechanical strength, heat resistance, hydrolysis resistance, etc., and is useful for synthetic leather, elastomers, coating agents, etc. An object of the present invention is to provide a carboxyl group-containing polycarbonate diol suitable as a.

As a result of repeated studies to solve the above-described conventional problems, the inventors of the present invention have found that the above-described The inventors have found that the problem can be solved, and completed the present invention.
That is, the gist of the present invention is as follows.

[1] A polycarbonate diol comprising a random copolymer containing two or more types of carbonate structural units and having a number average molecular weight (Mn) of 500 to 5000 and a molecular weight distribution (Mw/Mn) of 1.6 or more, The average value of the number of carbon atoms introduced into the carbonate structural unit of the polycarbonate diol derived from the carbon atoms present between the two hydroxyl groups of the raw material dihydroxy compound of the polycarbonate diol and having a structural unit containing a carboxyl group. (this value is hereinafter referred to as "average carbon number") of 3.5 to 10.0.

[2] The polycarbonate diol according to [1], wherein the average carbon number is 3.5 to 7.0.

[3] The polycarbonate diol according to [1] or [2], which has an acid value of 1 mg/g-KOH or more and 100 mg/g-KOH or less.

[4] The polycarbonate diol according to any one of [1] to [3], which contains a structural unit represented by formula (A) below and a structural unit represented by formula (B) below.

(However, R ¹ represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms and may contain a heteroatom of O, S or N.)

(However, R ² represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms, which may have a branched chain and may contain a heteroatom of O, S, N. L ¹ is a single bond or a main It is a linking group with a chain having 1 to 12 carbon atoms, and may contain a heteroatom of O, S, or N.)

[5] The ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula (B) is the molar ratio, and the structural unit represented by the formula (A): Formula (B) The polycarbonate diol according to [4], wherein the structural unit represented by = 50:50 to 99:1.

[6] The ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula (B) is the molar ratio, and the structural unit represented by the formula (A): Formula (B) The polycarbonate diol according to [5], wherein the structural unit represented by = 80:20 to 99:1.

[7] The polycarbonate diol according to any one of [4] to [6], wherein R ¹ in formula (A) is an aliphatic hydrocarbon group having 4 to 6 carbon atoms.

[8] The polycarbonate diol according to any one of [4] to [7], wherein L1 in formula (B) is a ^single bond.

[9] The polycarbonate diol according to [8], wherein the structural unit represented by the formula (B) is a structural unit represented by the following formula (B1).

[10] The polycarbonate diol according to any one of [4] to [7], wherein the structural unit represented by formula (B) is a structural unit represented by formula (D) below.

(However, R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and contain a heteroatom of O, S, or N. L ² is a heteroatom-containing linking group of 1 to 12 carbon atoms selected from O, S and N.)

[11] The polycarbonate diol according to [10], wherein the structural unit represented by the formula (D) is a structural unit represented by the following formula (D1).

(However, R ³ has the same definition as in formula (D).)

[12] The polycarbonate diol described in any one of [1] to [11] (hereinafter referred to as "polycarbonate diol 1") and a polycarbonate diol containing no carboxyl group (hereinafter referred to as "polycarbonate diol 2"). ).

[13] The polycarbonate diol composition according to [12], wherein the polycarbonate diol 2 is a polycarbonate diol containing a structural unit represented by the formula (A).

[14] A polyurethane using the polycarbonate diol according to any one of [1] to [11] or the polycarbonate diol composition according to [12] or [13].

[15] An aqueous polyurethane dispersion using the polycarbonate diol according to any one of [1] to [11] or the polycarbonate diol composition according to [11] or [12], an isocyanate and a chain extender.

[16] Artificial leather or synthetic leather using the polyurethane according to [14].

[17] A paint or coating agent using the polyurethane of [14].

[18] Elastic fibers using the polyurethane described in [14].

[19] A water-based polyurethane paint using the polyurethane according to [14].

[20] A pressure-sensitive adhesive or adhesive using the polyurethane described in [14].

[21] An active energy ray-curable polymer composition using the polycarbonate diol according to any one of [1] to [11] or the polycarbonate diol composition according to [12] or [13].

[22] A method for producing a carboxyl group-containing polycarbonate diol, wherein the following steps 1 and 2 are performed in this order.
Step 1: Polymerization step of reacting a dihydroxy compound having a carboxyl group precursor group with a carbonate compound to obtain a polycarbonate diol Step 2: Conversion of converting the carboxyl group precursor group of the polycarbonate diol obtained in Step 1 into a carboxyl group process

[23] A method for producing a carboxyl group-containing polycarbonate diol by performing the following steps 1-1 and 2-1 in this order.
Step 1-1: Polymerization step of reacting a dihydroxy compound having a protected carboxyl group with a carbonate compound to obtain a polycarbonate diol Step 2-1: Removing the protective group of the carboxyl group of the polycarbonate diol obtained in Step 1-1 Deprotection step to release

[24] A method for producing a carboxyl group-containing polycarbonate diol by performing the following steps 1-2 and 2-2 in this order.
Step 1-2: Polymerization step of reacting a dihydroxy compound having an unsaturated bond with a carbonate compound to obtain a polycarbonate diol Step 2-2: With respect to the unsaturated bond of the polycarbonate diol obtained in Step 1-2, carboxyl A carboxyl group introduction step of reacting a group-introducing compound to introduce a carboxyl group

[25] A carboxyl group for producing a polycarbonate diol having a structural unit represented by the following formula (D2) by reacting a polycarbonate diol having a structural unit represented by the following formula (X) with a compound having a mercapto group: A method for producing a contained polycarbonate diol.

(However, R ³ represents an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and may contain a heteroatom of O, S, or N. L ³ is It is a hydrocarbon group having 1 to 12 carbon atoms and may have a branched chain.)

According to the present invention, a water-based polyurethane dispersion that has a good balance of chemical resistance, solvent resistance, flexibility, mechanical strength, heat resistance, hydrolysis resistance, etc., and is useful for synthetic leather, elastomers, coating agents, etc. It is possible to provide a carboxyl group-containing polycarbonate diol suitable as a raw material for.

Artificial leather, synthetic leather, thermoplastic polyurethane elastomer, paint, and coating materials produced using the polycarbonate diol of the present invention have excellent chemical resistance, solvent resistance, flexibility, mechanical strength, heat resistance, hydrolysis resistance, etc. It is well-balanced and excellent. In addition, the polyester polycarbonate diol of the present invention is industrially very useful because the polyurethane solution can be stored for a long time when processing the polyurethane using the polycarbonate diol of the present invention.

The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the invention.

[1. Polycarbonate Diol]
The polycarbonate diol of the present invention is a polycarbonate diol comprising a random copolymer containing two or more types of carbonate structural units, having a number average molecular weight (Mn) of 500 to 5000 and a molecular weight distribution (Mw/Mn) of 1.6 or more. and having a structural unit containing a carboxyl group, the number of carbon atoms introduced into the carbonate structural unit of the polycarbonate diol originating from the carbon atoms existing between two hydroxyl groups of the raw material dihydroxy compound of the polycarbonate diol. It is characterized by having an average number (hereinafter referred to as "average carbon number") of 3.5 to 10.0.

<1-1. Average carbon number>
The average carbon number in the present invention represents the average number of carbon atoms between two hydroxyl groups of the dihydroxy compound introduced into the structural unit of the polycarbonate diol derived from the dihydroxy compound used as the raw material of the polycarbonate diol. For example, among the dihydroxy compounds introduced into the structural units, 1,6-hexanediol has 6 carbon atoms, 1,4-butanediol has 4 carbon atoms, and dimethylolpropionic acid has 3 carbon atoms. Here, the number of carbon atoms is the number of carbon atoms between two hydroxyl groups in the dihydroxy compound, and the heteroatom contained in the linking group between the two hydroxyl groups and the carbon chain branched from the linking group between the two hydroxyl groups. is not considered. The average carbon number is calculated from the carbon number of the dihydroxy compound introduced into the structural unit of the polycarbonate diol and the molar ratio of the dihydroxy compound to all dihydroxy compounds. ¹ H-NMR is used to identify the structural units of the polycarbonate diol and to analyze the molar ratio. A specific method is as described in the Examples section below.

The upper limit of the average carbon number is 10.0, preferably 9.0, more preferably 8.0, and most preferably 7.0. The lower limit of the average carbon number is 3.5, preferably 3.6, more preferably 3.7, even more preferably 3.8. If the average carbon number is less than the above lower limit, the flexibility of the polyurethane obtained using the polycarbonate diol may be insufficient, and if it exceeds the above upper limit, chemical resistance, heat resistance, and abrasion resistance may be insufficient. be.

In the carbonate diol of the present invention, by setting the average number of carbon atoms in the preferred range as described above, the resulting polyurethane has a good balance of chemical resistance, low-temperature properties, heat resistance, storage stability, etc. Details of the mechanism of action is not clear, but is estimated as follows.
When a polycarbonate diol is composed of a dihydroxy compound having an average carbon number of less than the above lower limit, the distance between carbonate bonds becomes short, and the polarity of the carbonate bonds increases the cohesive force. As the cohesion increases, chemical resistance, alkali resistance, water resistance, heat resistance, etc. are improved, but flexibility is lost, resulting in poor low-temperature properties and workability.
On the other hand, when a polycarbonate diol is composed of a dihydroxy compound having an average carbon number exceeding the above upper limit, the distance between carbonate bonds increases, and the cohesion due to the polarity of the carbonate bonds decreases. Due to the decrease in cohesive force, the flexibility is improved and the low-temperature properties and workability are excellent, but the chemical resistance, alkali resistance, water resistance, heat resistance, etc. are inferior.
On the other hand, by setting the average carbon number within the above range, the obtained polyurethane has excellent chemical resistance, low-temperature properties, heat resistance, storage stability, flexibility, etc., in a well-balanced manner.

<1-2. Random copolymer>
The polycarbonate diol of the present invention is characterized by being a random copolymer containing two or more carbonate structural units.
Since the polycarbonate diol of the present invention is a random copolymer, the intervals between carbonate bonds become irregular, and the cohesive force between molecules due to hydrogen bonding decreases. Good flexibility. In addition, since the cohesive force is weakened, storage stability is improved when used in a polyurethane solution or an aqueous polyurethane dispersion.

<1-3. Structural Unit Containing Carboxyl Group>
The polycarbonate diol of the present invention is characterized by containing a structural unit containing a carboxyl group.
Polyurethanes are inherently hydrophobic, but since the polycarbonate diol of the present invention has a structural unit containing a polar group, a carboxyl group, a polyurethane having a carboxyl group can be obtained using the polycarbonate diol of the present invention. This polyurethane can be stably dispersed in water, and the storage stability of the obtained aqueous polyurethane dispersion can be enhanced.
In order to fully exhibit this dispersion stability, it is important to set the carboxyl group content in the polycarbonate diol to an appropriate range. The carboxyl group content in the carboxyl group-containing polycarbonate diol can be represented by the acid value (mg/g-KOH) of the polycarbonate diol, and the preferred acid value is as described below.

<1-4. Number average molecular weight>
The polycarbonate diol of the present invention has a number average molecular weight of 500-5000. The upper limit of the number average molecular weight is preferably 4,000 or less, more preferably 3,000 or less, and particularly preferably 2,000 or less. The lower limit is preferably 500 or more, more preferably 700 or more, and particularly preferably 1000 or more. If the number-average molecular weight is less than the above lower limit, a polyurethane with a carboxyl group introduced into the hard segment (a structural unit with a short distance between urethane bonds) is formed, and the polyurethane may become hard or have poor texture. be. Further, if the above upper limit is exceeded, the viscosity of the polycarbonate diol increases, which impairs the handling during polyurethane synthesis, the polyurethane aqueous dispersion cannot be sufficiently stirred in water, resulting in poor dispersion, and the storage stability of the polyurethane aqueous dispersion is deteriorated. becomes worse.
Here, the number average molecular weight of the polycarbonate diol is a value calculated from the acid value and the hydroxyl value, and the specific calculation method is as shown in Examples below.

<1-5. Molecular Weight Distribution>
The polycarbonate diol of the present invention is characterized by having a molecular weight distribution (Mw/Mn) of 1.6 or more. The lower limit of the molecular weight distribution (Mw/Mn) of the polycarbonate diol of the present invention is preferably 1.7 or more, more preferably 1.8 or more, and the upper limit is preferably 3.0 or less, more preferably 2.5 or less. Especially preferably, it is 2.2 or less. If the molecular weight distribution (Mw/Mn) of the polycarbonate diol exceeds the above upper limit, the amount of polymer components contained increases, so that the viscosity and melting point of the polycarbonate diol increase, and there is a tendency for the handling properties during polyurethane synthesis to decrease. be. Polycarbonate diols with a molecular weight distribution less than the above lower limit contain less high-molecular-weight components, so when synthesizing polyurethane, the mechanical strength may decrease, the flexibility may decrease, and the chemical resistance may decrease. have a nature. In addition, since there are few low-molecular-weight oligomers and it is composed of components with uniform molecular weights, the cohesive force between molecules is strong, and when used in polyurethane solutions or polyurethane water dispersions, storage stability is reduced. There is In order to synthesize a polycarbonate diol with a molecular weight distribution less than the above lower limit, it is necessary to perform ring-opening polymerization using an expensive cyclic monomer and advanced purification operations such as removal of oligomers, and the economic efficiency as an industrial process is low. There is

Here, the molecular weight distribution (Mw/Mn) of the polycarbonate diol can be obtained from the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC). can. The details of the measurement method are as shown in the section of Examples below.

<1-6. Acid value>
The upper limit of the acid value of the polycarbonate diol of the present invention is preferably 100 mg/g-KOH or less, more preferably 80 mg/g-KOH or less, and even more preferably 60 mg/g-KOH or less. The lower limit of the acid value is preferably 1 mg/g-KOH or more, more preferably 5 mg/g-KOH or less, and particularly preferably 10 mg/g-KOH or more. If the acid value of the polycarbonate diol exceeds the above upper limit, the proportion of carboxyl groups is too high, causing agglomeration, which hinders the dispersion of the obtained polyurethane. Hydrolysis resistance, weather resistance, transparency and color tone may deteriorate. If the acid value of the polycarbonate diol is less than the above lower limit, the hydrophobicity of the resulting polyurethane is increased and aggregation occurs, the dispersion in water does not proceed, and the storage stability of the aqueous polyurethane dispersion deteriorates.
The method for measuring the acid value of the polycarbonate diol is as shown in the Examples section below.

<1-7. Structural Unit (A) and Structural Unit (B)>
The polycarbonate diol of the present invention comprises a structural unit represented by the following formula (A) (hereinafter sometimes referred to as "structural unit (A)") and a structural unit represented by the following formula (B) (hereinafter , sometimes referred to as “structural unit (B)”).

(However, R ¹ represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms and may contain a heteroatom of O, S or N.)

(However, R ² represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms, which may have a branched chain and may contain a heteroatom of O, S, N. L ¹ is a single bond or a main It is a linking group with a chain having 1 to 12 carbon atoms, and may contain a heteroatom of O, S, or N.)

In the structural unit (A), R ¹ is preferably ^an aliphatic hydrocarbon group having 4 to 10 carbon atoms, particularly 4 to 6 carbon atoms. Although it may have a branched or cyclic structure, R ¹ is preferably a linear aliphatic hydrocarbon group or an alkylene ether group. More preferably, R ¹ includes an alkylene group, an alkenylene group, an alkynylene group, an alkadienyl group, and the like. Among them, an alkylene group is preferable, and an alkylene group having 4 to 10 carbon atoms is particularly preferable. An alkylene group having 4 to 6 carbon atoms is preferable from the viewpoint of balance of chemical properties, etc., and a butylene group having 4 carbon atoms or a hexylene group having 6 carbon atoms is most preferable from the viewpoint of ease of availability.

The polycarbonate diol of the present invention may contain only one type of structural unit (A), or may contain two or more types of structural units (A) having different R ¹ .

Structural unit (B) is a structural unit containing one or more carboxyl groups (--COOH), and an example of structural unit (B) suitable for the present invention is formula (B) in which L ¹ is a single bond and R ² is an optionally branched aliphatic saturated hydrocarbon group having 3 to 20 carbon atoms, and specific examples include structural units represented by the following formula (B1). be done.

Further, another example of the structural unit (B) suitable for the present invention includes a structural unit represented by the following formula (D), more preferably a structural unit represented by the following formula (D1). .

(However, R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and contain a heteroatom of O, S, or N. L ² is a heteroatom-containing linking group of 1 to 12 carbon atoms selected from O, S and N.)

(However, R ³ has the same definition as in formula (D).)

In formula (D1) above, R ³ is preferably an aliphatic saturated hydrocarbon group having 3 to 12 carbon atoms.

The polycarbonate diol of the present invention may contain only one type of structural unit (B), or may contain two or more types of structural units (B) having different L ¹ and R ² .

The polycarbonate diol of the present invention has a structural unit (A) and a structural unit (B) in a molar ratio of structural unit (A):structural unit (B)=50:50 to 99:1, particularly 80:20 to 99. :1, particularly preferably in a ratio of 85:15 to 99:1.
If the structural unit (A) is larger than the above range and the structural unit (B) is smaller than the above range, the effect of improving the water dispersibility by introducing the structural unit (B) having a carboxyl group cannot be sufficiently obtained, The resulting polyurethane aqueous dispersion tends to have poor storage stability. Conversely, if the structural unit (B) is too many and the structural unit (A) is too few, the resulting polyurethane will aggregate due to too many carboxyl groups. or the acid component is too high, the durability, hydrolysis resistance, weather resistance, transparency and color tone of the resulting polyurethane may deteriorate.

The molar ratio of the structural unit (A) to the structural unit (B) in the polycarbonate diol of the present invention can be determined by ¹ H-NMR measurement, as shown in the Examples section below.

<1-8. Ester bond rate>
Although the polycarbonate diol of the present invention contains many carbonate bonds, it may contain a small amount of ester bonds.
When the ratio of the number of ester bonds to the total number of carbonate bonds and the number of ester bonds per molecule of polycarbonate diol is expressed as "ester bond rate", the ester bond rate of the polycarbonate diol of the present invention is preferably 20% or less, and 10%. % or less, more preferably 5% or less, and most preferably 0%. The presence of ester bonds may improve the flexibility of the resulting polyurethane, but when present in excess of the above upper limit, the chemical resistance, hydrolysis resistance and heat resistance of the resulting polyurethane tend to decrease. The ester bond rate of the polycarbonate diol can be measured and calculated by the method described in Examples below.

<1-9. Method for Producing Carboxyl Group-Containing Polycarbonate Diol>
The method for producing the carboxyl group-containing polycarbonate diol of the present invention having the characteristics described above will be described below.

When the polycarbonate diol is polymerized, it is preferable that there is no substituent group (referred to as a carbonate polymerization inhibiting group) that causes a side reaction of esterification or deactivation of the transesterification catalyst in the reaction system. The carbonate polymerization inhibiting group includes a carboxyl group, a methyl ester group, an ethyl ester group, and the like. When carbonate polymerization is carried out in the presence of a carbonate polymerization-inhibiting group, the carbonate polymerization does not progress and the molecular weight does not increase, or the by-produced ester bond promotes cross-linking and gelation may occur. be.

Therefore, in the present invention, in order to synthesize a carboxyl group-containing polycarbonate diol without using the above-described carbonate polymerization inhibiting group, it is preferable to produce a carboxyl group-containing polycarbonate diol through the following two steps in order. In addition, in order to improve the productivity in an actual machine, it is possible to carry out Steps 1 and 2 in one reactor, or to carry out the steps continuously without purification (one-pot production).
Step 1: Polymerization step of reacting a dihydroxy compound having a carboxyl group precursor group with a carbonate compound to obtain a polycarbonate diol Step 2: Conversion of converting the carboxyl group precursor group of the polycarbonate diol obtained in Step 1 into a carboxyl group process

The dihydroxy compound having a carboxyl group precursor group used in step 1 is a compound that is inactive during polymerization of the polycarbonate diol and capable of introducing a carboxyl group into the polycarbonate diol by a reaction after polymerization. Although there is no particular limitation as long as it has the properties, dihydroxy compounds having a protected carboxyl group and dihydroxy compounds having an unsaturated bond, which will be described later, are preferred.

Although there are no particular restrictions on the specific method for producing the carboxyl group-containing polycarbonate diol, the following production methods 1 and 2 are particularly preferred in view of the ease of raw material procurement and synthetic operations.
Production method 1: A method for producing a carboxyl group-containing polycarbonate diol by performing the following steps 1-1 and 2-1 in this order.
Step 1-1: Polymerization step of reacting a dihydroxy compound having a protected carboxyl group with a carbonate compound to obtain a polycarbonate diol Step 2-1: Removing the protective group of the carboxyl group of the polycarbonate diol obtained in Step 1-1 Removal deprotection step Manufacturing method 2: A method for manufacturing a carboxyl group-containing polycarbonate diol in which the following steps 1-2 and 2-2 are performed in this order.
Step 1-2: Polymerization step of reacting a dihydroxy compound having an unsaturated bond with a carbonate compound to obtain a polycarbonate diol Step 2-2: With respect to the unsaturated bond of the polycarbonate diol obtained in Step 1-2, carboxyl A carboxyl group introduction step of reacting a group-introducing compound to introduce a carboxyl group

<1-9-1. Manufacturing method 1>
Manufacturing method 1 will be described below.
Production method 1 is represented by the following reaction formula.

(In the above reaction formula, R ¹ has the same definition as R ¹ in formula (A), and L ¹ and R ² have the same meaning as L ¹ and R ² in formula (B). X is a carboxyl-protecting group. ^Rc represents an alkyl group, an aryl group, or an alkylene group formed by bonding two ^Rcs of a carbonate compound described later.)

Production method 1 uses a dihydroxy compound a and a dihydroxy compound b having a carboxyl group protected by a protecting group X and a carbonate compound to polymerize under polycarbonate diol polymerization conditions to obtain a polycarbonate diol c having a protected carboxyl group. It is a method of obtaining a carboxyl group-containing polycarbonate diol d by producing and deprotecting after the polymerization reaction. The polymerization method of the polycarbonate diol in production method 1 is as described in the section of the polycarbonate polymerization step.

The protecting group X for the carboxyl group is not particularly limited, but is preferably inert under the polycarbonate diol polymerization conditions, inexpensive, and easily deprotected while maintaining the polycarbonate diol skeleton after polymerization. Specifically, it has 3 carbon atoms. Alkyl groups (isopropyl, t-butyl, s-butyl, cyclopentyl, cyclohexyl, etc.) that may contain 12 branched or cyclic structures, phenyl, benzyl, p-methoxybenzyl, tetrahydro A pyranyl group, a tetrahydrofuranyl group, a methoxymethyl group, a methoxyethyl group, a phenacyl group, a p-methoxyphenacyl group, a trimethylsilyl group, a triethylsilyl group, a dimethyl t-butylsilyl group, a dimethylphenylsilyl group, etc. are preferred, and mild hydrogen A benzyl group, which can be deprotected by chemical reduction and is inexpensive, is most preferred.

The deprotection step for removing the protecting group of the carboxyl group is not particularly limited in technique, but deprotection under inert reducing conditions for the carbonate bond is preferable. Particularly in the deprotection of a benzyl group, a method of catalytic reduction using a metal catalyst and hydrogen is preferable because the deprotection proceeds under mild conditions.

In production method 1, the structural unit (A) is introduced into the carboxyl group-containing polycarbonate diol to be produced by the dihydroxy compound b, and the structural unit (B) is introduced by the dihydroxy compound a having a carboxyl group protected by the protecting group X. Therefore, the structural unit (A ) and the structural unit (B) can be adjusted.

<1-9-2. Manufacturing method 2>
Manufacturing method 2 will be described below.
Production method 2 is represented by the following reaction formula.

(In the above reaction formula, R ¹ has the same definition as R ¹ in formula (A), R ^U is a branched alkyl group having 3 to 12 carbon atoms, R ^C is an alkyl group of the carbonate compound described later, represents an aryl group or an alkylene group formed by bonding two R ^c , L ² and L ⁴ are an optionally branched alkylene group having 3 to 12 carbon atoms, and Y represents an unsaturated bond reaction described later. represents O, N, S atoms, etc. derived from the group.)

In production method 2, a dihydroxy compound e having an unsaturated bond, a dihydroxy compound b, and a carbonate compound are polymerized under polycarbonate diol polymerization conditions to produce a polycarbonate diol f having an unsaturated bond, and after this polymerization reaction, In this method, the unsaturated bonds of a polycarbonate diol f having unsaturated bonds are reacted with a carboxyl group-introducing compound g to obtain a carboxyl group-containing polycarbonate diol h. Also in the production method 2, the polymerization method of the polycarbonate diol is as shown in the section of the polycarbonate diol polymerization step. In addition, in order to improve the productivity in an actual machine, it is possible to carry out the above steps in one reactor, or to carry out the steps continuously without purification (one-pot production).

Dihydroxy compounds e having an unsaturated bond include 2-butene-1,4-diol, 2-pentene-1,5-diol, 3-hexene-1,6-diol, cyclohexenedimethanol, and bis(hydroxyalkyl) fumarates. etc., but bis(hydroxyalkyl) fumarate (alkyl group having 3 to 12 carbon atoms) is preferable from the viewpoint of the reactivity of the unsaturated bond. Furthermore, bis(hydroxyhexyl) fumarate having 6 carbon atoms in the alkyl group is most preferable from the viewpoint of stability during polymerization of polycarbonate diol and ease of availability. Dihydroxy compound e having an unsaturated bond may be used alone or in combination of two or more.

The carboxyl group-introduced compound g is not particularly limited, but must have at least one carboxyl group and at least one unsaturated bond reactive group. Although the unsaturated bond-reactive group is not particularly limited, it is a substituent capable of reacting with the unsaturated bond in the polycarbonate diol under conditions inert to the carboxyl group. Specific examples of the unsaturated bond reactive group include a hydroxyl group, an amino group, a mercapto group and the like, and the mercapto group is most preferable from the viewpoint of reactivity. Specific compounds are not particularly limited, but from the viewpoint of stability, compounds having a mercapto group and a carboxyl group at both ends of an alkyl group such as 1-mercaptoacetic acid, 1-mercaptopropionic acid, and 1-mercaptobutanoic acid are preferred. , 1-mercaptoacetic acid is most preferred because of its availability.
As for the carboxyl group-introducing compounds, either one type may be used alone, or two or more types may be used in combination. In the step of reacting the unsaturated bond reactive group, an additive or solvent may be used to accelerate the reaction, and when a compound containing a mercapto group is used, the addition of a tertiary amine accelerates the reaction. Sometimes.

In production method 2, the structural unit (A) is introduced into the carboxyl group-containing polycarbonate diol to be produced by the dihydroxy compound b, and the structural unit (B) is introduced by the dihydroxy compound e having an unsaturated bond. The molar ratio of the structural unit (A) to the structural unit (B) of the resulting carboxyl group-containing polycarbonate diol is adjusted by adjusting the ratio of the dihydroxy compound b used in the step and the dihydroxy compound e having an unsaturated bond. can do.

Below, as a more specific example of production method 2, fumaric acid (bisalkyl) is used as the dihydroxy compound having an unsaturated bond, one of the alkyl groups as the unsaturated bond reactive group has a mercapto group at the end, and the other has a mercapto group. An example using a compound having a terminal carboxyl group is shown.
In this method, a polycarbonate diol having a structural unit represented by the following formula (X) is reacted with a compound having a mercapto group to obtain a carboxyl group-containing polycarbonate diol having a structural unit represented by the following formula (D2). It is a manufacturing method, represented by the following reaction formula.

(However, R ³ represents an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and may contain a heteroatom of O, S, or N. L ³ is It is a hydrocarbon group having 1 to 12 carbon atoms and may have a branched chain.)

(In the above reaction scheme, R ¹ has the same meaning as R ¹ in formula (A), L ³ and R ³ have the same meaning as L ³ and R ³ in formula (D2). R ^c is the carbonate compound described later. represents an alkyl group, an aryl group, or an alkylene group formed by bonding two ^Rc 's.)

<1-9-3. Polycarbonate polymerization step>
<1-9-3-1. Ordinary dihydroxy compound>
In production methods 1 and 2, the dihydroxy compound b (hereinafter sometimes referred to as "ordinary dihydroxy compound") used for introducing the structural unit (A) is a dihydroxy In combination with a dihydroxy compound having a carboxyl group precursor group such as the compound a and the dihydroxy compound e having an unsaturated bond, the average carbon number of the obtained polycarbonate diol is used in the above range.
Usual dihydroxy compounds used in the present invention include 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,3-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20- Examples include eicosanediol, cyclohexanediol, cyclohexanedimethanol, isosorbide and the like. Among these, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol , 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, cyclohexanedimethanol, and isosorbide are preferred, and 1,4-butanediol and 1,5-pentanediol. , 1,6-hexanediol are particularly preferred, and 1,4-butanediol and 1,6-hexanediol are particularly preferred. These normal dihydroxy compounds may be used alone or in combination of two or more.

<1-9-3-2. Carbonate compound>
In the method for producing a carboxyl group-containing polycarbonate diol of the present invention, examples of carbonate compounds used as raw materials include dialkyl carbonates, alkylene carbonates and diaryl carbonates. Among them, it is preferable to contain a diaryl carbonate from the viewpoint of reactivity.

Specific examples of carbonate compounds that can be preferably used in the production of the carboxyl group-containing polycarbonate diol of the present invention include dimethyl carbonate, diethyl carbonate, ethylene carbonate and diphenyl carbonate, with diphenyl carbonate being particularly preferred.

In the production of the carboxyl group-containing polycarbonate diol of the present invention, the amount of the carbonate compound used is not particularly limited. It is more preferably 0.84, and the upper limit is preferably 1.00, more preferably 0.98, still more preferably 0.97. If the amount of the carbonate compound used exceeds the above upper limit, the ratio of non-hydroxy terminal groups in the resulting polycarbonate diol may increase, or the molecular weight may not fall within the predetermined range. It may not progress.

<1-9-3-3. transesterification catalyst>
The carboxyl group-containing polycarbonate diol of the present invention can be produced by subjecting a dihydroxy compound and a carbonate compound to polycondensation by transesterification reaction in the presence of a transesterification catalyst.
As the transesterification catalyst, any compound generally considered to have transesterification ability can be used without limitation.

Examples of transesterification catalysts include compounds of Group 1 metals of the periodic table long periodic table (hereinafter simply referred to as the "periodic table") such as lithium, sodium, potassium, rubidium, and cesium; magnesium, calcium, strontium, Compounds of Group 2 metals of the periodic table such as barium; compounds of Group 4 metals of the periodic table such as titanium and zirconium; compounds of Group 5 metals of the periodic table such as hafnium; compounds of group 9 metals of the periodic table such as cobalt; Compounds of Group 12 metals of the periodic table such as zinc; Compounds of Group 13 metals of the periodic table such as aluminum; Compounds of Group 14 metals of the periodic table such as germanium, tin and lead; Group 15 of the periodic table such as antimony and bismuth Metal compounds; compounds of lanthanide metals such as lanthanum, cerium, europium, ytterbium, and the like. Among these, from the viewpoint of increasing the transesterification reaction rate, periodic table group 1 metal compounds, periodic table group 2 metal compounds, periodic table group 4 metal compounds, periodic table group 5 metal compounds, A compound of a metal of Group 9 of the periodic table, a compound of a metal of Group 12 of the periodic table, a compound of a metal of Group 13 of the periodic table, a compound of a metal of Group 14 of the periodic table, a compound of a metal of Group 1 of the periodic table, a compound of a metal of Group 1 of the periodic table, Compounds of Group 2 metals are more preferred, and compounds of Group 2 metals of the periodic table and Group 4 metals of the periodic table are even more preferred. Among compounds of Group 2 metals of the periodic table, compounds of calcium and magnesium are more preferable. Titanium is preferable among the compounds of Group 4 metals of the periodic table. These metal compounds are mainly used as hydroxides, salts and the like. Examples of salts when used as salts include halide salts such as chlorides, bromides and iodides; carboxylates such as acetates, formates and benzoates; sulfonates such as romethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates and dihydrogen phosphates; acetylacetonate salts; Catalyst metals can also be used as alkoxides such as methoxide, ethoxide and butoxide.

Among these, preferably, at least one metal selected from group 2 and group 4 metals of the periodic table, such as acetate, nitrate, sulfate, carbonate, phosphate, hydroxide, halide, and alkoxide is used, more preferably group 2 metal acetates, carbonates, and hydroxides of the periodic table, particularly preferably magnesium and calcium acetates, and titanium alkoxides, and more preferably magnesium acetate and Titanium tetrabutoxide is used.

<1-9-3-4. Reaction temperature>
The reaction temperature for transesterification in the production of the carboxyl group-containing polycarbonate diol of the present invention is preferably 200° C. or lower. The reason for this is that deterioration of the color tone of the polycarbonate diol, by-production of allyl ends, and by-production of THF can be suppressed. The reaction temperature is more preferably 190° C. or lower, still more preferably 180° C. or lower. On the other hand, the lower limit of the reaction temperature is usually 130°C or higher, preferably 140°C or higher, more preferably 150°C or higher. If the reaction temperature is too low, the residual amount of by-products derived from carbonate compounds such as phenol and methanol increases, or the polymerization does not proceed to a predetermined molecular weight.

<1-9-3-5. Reaction pressure>
In the production of the carboxyl group-containing polycarbonate diol of the present invention, the minimum reaction pressure during the transesterification reaction is not particularly limited, but is usually 1.0 kPa or less, preferably 0.5 kPa or less. On the other hand, the lower limit of the reaction pressure is usually 0.01 kPa or higher, preferably 0.02 kPa or higher, and more preferably 0.03 kPa or higher. The lower the reaction pressure, the shorter the reaction time, which tends to suppress the deterioration of the color tone of the carboxyl group-containing polycarbonate diol obtained. For these reasons, the molecular weight of the carboxyl group-containing polycarbonate diol tends to be easily controlled.

<1-9-3-6. Reaction time>
In the production of the carboxyl group-containing polycarbonate diol of the present invention, the reaction time for the transesterification reaction is not particularly limited, but is usually 12 hours or less, preferably 10 hours or less, and more preferably 8 hours or less. On the other hand, the lower limit of the reaction time is usually 0.5 hours or longer, preferably 1 hour or longer, and more preferably 1.5 hours or longer. As the reaction time becomes longer, the residual amount of by-products derived from carbonate compounds such as phenol and methanol tends to be reduced, and as the reaction time becomes shorter, deterioration of the color tone of the resulting carboxyl group-containing polycarbonate diol tends to be suppressed. It is in.

<1-9-3-7. Reactor>
In the production of the carboxyl group-containing polycarbonate diol of the present invention, the shape of the reactor used for the transesterification reaction is not particularly limited. The polymerization reaction can be carried out batchwise or continuously, but in the present invention, it is preferably carried out continuously in view of the stability of the product.

<1-10. Polycarbonate diol composition>
The carboxyl group-containing polycarbonate diol of the present invention (hereinafter sometimes referred to as "polycarbonate diol 1") is polyurethane-formed together with a carboxyl group-free polycarbonate diol (hereinafter sometimes referred to as "polycarbonate diol 2"). Reaction is preferable because the amount of carboxyl groups during the polyurethane formation reaction can be adjusted and the flexibility and durability of the resulting polyurethane can be improved.
In this case, a polycarbonate diol composition containing polycarbonate diol 1 and polycarbonate diol 2 is subjected to the polyurethane formation reaction.

In this polycarbonate diol composition, the polycarbonate diol 2 used together with the polycarbonate diol 1 is not particularly limited. This polycarbonate diol 2 is preferably produced by using the above-described ordinary dihydroxy compound as the dihydroxy compound, because it can produce high urethane.

Preferred structural units (A) contained in polycarbonate diol 2 are the same as those preferred as structural units (A) contained in polycarbonate diol 1 . However, the structural unit (A) of the polycarbonate diol 1 and the structural unit (A) of the polycarbonate diol 2 contained in the polycarbonate diol composition need not be the same and may be different. Moreover, the polycarbonate diol 2 may be composed of one type of structural unit (A), or may be composed of two or more types of structural units (A).

The polycarbonate diol 2 preferably has a number average molecular weight of 500 to 5,000, particularly 800 to 4,000, more preferably 1,000 to 3,000, more preferably 1,000 to 2,000. When the number average molecular weight of the polycarbonate diol 2 is at least the above lower limit, the flexibility of the resulting polyurethane can be excellent. On the other hand, when the number average molecular weight is equal to or less than the above upper limit, the viscosity is lowered, resulting in excellent handleability. The method for measuring the number average molecular weight of polycarbonate diol 2 is the same as that for polycarbonate diol 1 .

The ratio of polycarbonate diol 1 and polycarbonate diol 2 contained in the polycarbonate diol composition of the present invention is not particularly limited. Generally, the weight ratio of polycarbonate diol 1:polycarbonate diol 2 is 5:95 to 99:1, especially 10:90 to 90:10, especially 10:90, although it varies depending on the amount of carboxyl groups contained in polycarbonate diol 1. to 50:50, preferably 10:90 to 40:60. If the amount of polycarbonate diol 1 is less than this range and the amount of polycarbonate diol 2 is more than this range, the above effects due to the use of polycarbonate diol 1 cannot be sufficiently obtained. As the amount of groups increases, the polyurethane becomes less durable and less flexible.

The polycarbonate diol composition of the present invention may contain one type of polycarbonate diol 1, or may contain two or more types of polycarbonate diols 1 having different types of structural units, compositions, and physical properties. good. Similarly, regarding the polycarbonate diol 2, the polycarbonate diol composition of the present invention may contain one type of polycarbonate diol 2, or may contain two or more types of polycarbonate diols 2 having different types of structural units and different physical properties. can be anything.

[2. Polyurethane]
The polycarbonate diol or polycarbonate diol composition of the present invention (hereinafter referred to as "polycarbonate diol (composition)") can be used to produce polyurethane or polyurethane water dispersion. Manufactured polyurethanes are another aspect of the invention.

The method for producing polyurethane using the polycarbonate diol (composition) of the present invention employs known polyurethane-forming reaction conditions for producing ordinary polyurethane.
For example, a polyurethane can be produced by reacting a polycarbonate diol (composition) with a polyisocyanate and a chain extender at a temperature ranging from room temperature to 200°C.
Alternatively, a polycarbonate diol (composition) and an excess of polyisocyanate are first reacted to produce a prepolymer having terminal isocyanate groups, and a chain extender is used to increase the degree of polymerization to produce a polyurethane. can be done.

<2-1. Polyisocyanate>
Polyisocyanates used in producing polyurethanes using polycarbonate diols (compositions) include various known aliphatic, alicyclic or aromatic polyisocyanate compounds.
For example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid carboxyl groups are converted to isocyanate groups. 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and Alicyclic diisocyanates such as 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane; 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, tetraalkyl Aromatic diisocyanates such as diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate, etc. mentioned. These may be used individually by 1 type, and may use 2 or more types together.

Among these, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and Isophorone diisocyanate is preferred.

<2-2. Chain extender>
In addition, the chain extender used in producing polyurethane is a low-molecular-weight compound having at least two active hydrogens that react with isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later. and polyamines.

Specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,9-nonanediol. , 1,10-decanediol, 1,12-dodecanediol, and other linear diols; 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-methyl-1,4-butanediol, 1,2-butanediol, 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 - diols having branched chains such as 1,3-propanediol and dimer diol; diols having ether groups such as diethylene glycol and propylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4 - diols having an alicyclic structure such as dihydroxyethylcyclohexane, diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene); glycerin, trimethylolpropane , pentaerythritol and other polyols; N-methylethanolamine, N-ethylethanolamine and other hydroxyamines; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4 '-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethane polyamines such as diamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, N,N'-diaminopiperazine; and water.

These chain extenders may be used alone or in combination of two or more. Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, 4 ,4′-diaminodicyclohexylmethane is preferred.

In addition, the chain extender in the case of producing a prepolymer having a hydroxyl group, which will be described later, is a low molecular weight compound having at least two isocyanate groups, specifically <2-1. polyisocyanate>.

<2-3. Chain terminator>
For the purpose of controlling the molecular weight of the resulting polyurethane, a chain terminating agent having one active hydrogen group can be used, if necessary, when producing the polyurethane.
These chain terminators include aliphatic monools having one hydroxyl group such as methanol, ethanol, propanol, butanol and hexanol, diethylamine, dibutylamine, n-butylamine, monoethanolamine and diethanolamine having one amino group. , and morpholine.
These may be used individually by 1 type, and may use 2 or more types together.

<2-4. Catalyst>
Amine-based catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine, acid-based catalysts such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, trimethyltin laurate, and dibutyltin, in the polyurethane-forming reaction during the production of polyurethane. Known urethane polymerization catalysts typified by tin-based compounds such as dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanate, and organic metal salts such as titanium-based 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 1 and Polycarbonate Diol 2>
In the polyurethane-forming reaction when producing polyurethane, the polycarbonate diol (composition) of the present invention and, if necessary, polyols other than polycarbonate diol 1 and polycarbonate diol 2 (hereinafter also referred to as "other polyols") are used. They may be used together.
Here, other polyols are not particularly limited as long as they are used in normal polyurethane production. Polycarbonate diols are mentioned. For example, when used in combination with polyether polyol, it is possible to obtain a polyurethane with further improved flexibility, which is a feature of the polycarbonate diol of the present invention.

When other polyols are used in combination, the weight ratio of the polycarbonate diol 1 of the present invention to the total weight of the polycarbonate diol 1 of the present invention and other polyols including the polycarbonate diol 2 is preferably 70% or more, and preferably 90% or more. is more preferred. If the weight ratio of the polycarbonate diol 1 of the present invention is small, there is a possibility that the properties and handleability of the polyurethane that characterize the present invention will be lost.

When other polyols than Polycarbonate Diol 1 and Polycarbonate Diol 2 are used together in the production of polyurethane, the polycarbonate diol (composition) of the present invention, other polyols, and other raw materials must be sufficiently compatible with each other. If the compatibility is not sufficient, the urethanization reaction proceeds unevenly, and the molecular weight distribution of the polyurethane obtained broadens or the molecular weight decreases, resulting in gelation of the polyurethane solution, deterioration in storage stability, The strength, solvent resistance, weather resistance, and heat resistance of polyurethane may decrease.

<2-6. Modification of polycarbonate diol (composition)>
In the present invention, the polycarbonate diol (composition) of the present invention can be modified and used for the production of polyurethane. Methods for modifying the polycarbonate diol (composition) include adding an epoxy compound such as ethylene oxide, propylene oxide, or butylene oxide to the polycarbonate diol (composition) to introduce an ether group; - There is a method of introducing an ester group by reacting with a cyclic lactone such as caprolactone, a dicarboxylic acid compound such as adipic acid, succinic acid, sebacic acid, terephthalic acid, or an ester compound thereof. Ether modification is preferable because modification with ethylene oxide, propylene oxide, or the like lowers the viscosity of the polycarbonate diol (composition) and improves handling properties. In particular, the polycarbonate diol (composition) of the present invention is modified with ethylene oxide or propylene oxide to reduce the crystallinity of the polycarbonate diol (composition) and improve the flexibility at low temperatures. Since the water absorption and moisture permeability of the polyurethane produced using the ethylene oxide-modified polycarbonate diol (composition) are increased, the performance as an artificial leather/synthetic leather may be improved. However, when the added amount of ethylene oxide or propylene oxide increases, the mechanical strength, heat resistance, chemical resistance, and other physical properties of the polyurethane produced using the modified polycarbonate diol (composition) decrease. The amount added to the product) is preferably 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 30% by weight, based on the weight of the polycarbonate diol (composition). Further, in the method of introducing an ester group, modification with ε-caprolactone is preferable because the viscosity of the polycarbonate diol (composition) is lowered and the handleability and the like are improved. The amount of ε-caprolactone added to the polycarbonate diol (composition) is preferably 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 5% by weight, based on the weight of the polycarbonate diol (composition). ~30% by weight. When the amount of ε-caprolactone added exceeds 50% by weight, the hydrolysis resistance, chemical resistance, etc. of the polyurethane produced using the modified polycarbonate diol (composition) are lowered.

<2-7. Solvent>
A solvent may be used in the polyurethane-forming reaction to produce the polyurethane.
Preferred solvents include amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxide solvents such as dimethylsulfoxide; ketone solvents such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; ether-based solvents; ester-based solvents such as methyl acetate, ethyl acetate and butyl acetate; and aromatic hydrocarbon-based solvents such as toluene and xylene. These solvents may be used alone or as a mixed solvent of two or more.
Preferred organic solvents among these are dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide, methyl ethyl ketone, ethyl acetate, toluene and the like.
Aqueous dispersion polyurethane can also be produced from a polyurethane composition containing the polycarbonate diol (composition) of the present invention, polydiisocyanate, and the chain extender.

<2-8. Polyurethane manufacturing method>
As a method for producing polyurethane using the above-mentioned reactants, production methods that are generally used experimentally or industrially can be used.
Examples thereof include a method of collectively mixing and reacting the polycarbonate diol (composition) of the present invention, other polyols, polyisocyanate, and chain extender used as necessary (hereinafter referred to as a “one-step method”). ), or a method of first reacting the polycarbonate diol (composition) of the present invention, other polyols 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 the “two-stage method”), etc.

In the two-step method, the polycarbonate diol (composition) of the present invention and optionally other polyols are reacted in advance with 1 or more equivalents of polyisocyanate to obtain both of the parts corresponding to the soft segments of the polyurethane. It goes through a step of preparing a terminal isocyanate intermediate. In this way, if the prepolymer is once prepared and then reacted with a chain extender, it may be easier to adjust the molecular weight of the soft segment portion, and when it is necessary to ensure phase separation between the soft segment and the hard segment. is useful for

<2-9. Single stage method>
The one-step method, which is also called a one-shot method, is a method in which the polycarbonate diol (composition) of the present invention, other polyols, polyisocyanate and chain extender are charged all at once to carry out the reaction.
The amount of polyisocyanate used in the one-step method is not particularly limited, but the sum of the total number of hydroxyl groups of the polycarbonate diol (composition) of the present invention and other polyols, the number of hydroxyl groups and the number of amino groups of the chain extender is In terms of equivalents, 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 2.0 equivalents, still 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 viscosity of the resulting polyurethane will tend to be too high, making handling difficult and flexibility likely to be impaired. If it is too much, the molecular weight of the polyurethane will not be sufficiently large, and there will be a tendency that sufficient polyurethane strength will not be obtained.
The amount of the chain extender used is not particularly limited, but when the number obtained by subtracting the number of isocyanate groups of the polyisocyanate from the total number of hydroxyl groups of the polycarbonate diol (composition) of the present invention and other polyols is taken as one equivalent. , the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2 0 equivalent, more preferably 1.5 equivalent, and particularly preferably 1.1 equivalent. If the amount of chain extender used is too large, the resulting polyurethane tends to be difficult to dissolve in the solvent and processing becomes difficult. In some cases, retention performance cannot be obtained, and in some cases, heat resistance deteriorates.

<2-10. Two-step method>
The two-step method, also called a prepolymer method, mainly includes the following methods.
(a) The polycarbonate diol (composition) of the present invention and other polyols and excess polyisocyanate are added in advance so that the reaction equivalent ratio of polyisocyanate/(polycarbonate diol (composition) of the present invention and other polyols) is 1. to 10.0 or less to produce a prepolymer having an isocyanate group at the molecular chain end, and then adding a chain extender thereto to produce a polyurethane.
(b) a polyisocyanate and an excess of polycarbonate diol (composition) and other polyols are added in advance so that the reaction equivalent ratio of polyisocyanate/(polycarbonate diol (composition) and other polyols of the present invention) is 0.1 or more; to less than 1.0 to produce a prepolymer having a hydroxyl group at the molecular chain end, and then reacting this with a polyisocyanate having an isocyanate group at the end as a chain extender to produce a polyurethane.

The two-step method can be carried out without solvent or in the presence of solvent.
Polyurethane production by the two-step method can be carried out by any one of the methods (1) to (3) described below.
(1) Without using a solvent, first, a polyisocyanate, a polycarbonate diol (composition) and other polyols are directly reacted to synthesize a prepolymer, which is used as it is for a chain extension reaction.
(2) A prepolymer is synthesized by the method of (1), then dissolved in a solvent and used for subsequent chain extension reaction.
(3) Using a solvent from the beginning, reacting polyisocyanate, polycarbonate diol (composition), and other polyols, followed by chain extension reaction.

In the case of the method (1), in the chain extension reaction, the chain extension agent is dissolved in the solvent, or the prepolymer and the chain extension agent are dissolved in the solvent at the same time. It is important to obtain
The amount of polyisocyanate used in the two-step method (a) is not particularly limited, but the number of isocyanate groups when the total number of hydroxyl groups of the polycarbonate diol (composition) and other polyols is 1 equivalent. , the lower limit is preferably an amount exceeding 1.0 equivalents, more preferably 1.2 equivalents, more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, still more preferably is in the range of 3.0 equivalents.

If the amount of isocyanate used is too large, the excessive isocyanate groups cause side reactions, making it difficult to achieve the desired physical properties of the polyurethane. If the amount is too small, the molecular weight of the resulting polyurethane may not be sufficiently increased and the strength and thermal stability may be lowered.
The amount of the chain extender to be used is not particularly limited, but the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.5 equivalent, with respect to one equivalent of isocyanate groups contained in the prepolymer. 8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and still more preferably 2.0 equivalents.

For the purpose of adjusting the molecular weight, monofunctional organic amines and alcohols may coexist during the chain extension reaction.

In the two-step method (b), the amount of polyisocyanate to be used when preparing a prepolymer having a terminal hydroxyl group is not particularly limited. As the number of isocyanate groups when the number is 1 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 equivalents, still more preferably 0.97 equivalents.

If the amount of isocyanate used is too small, the subsequent chain elongation reaction takes a long time to obtain the desired molecular weight, and production efficiency tends to decrease. It may decrease, or the handling property may be poor and the productivity may be inferior.
The amount of the chain extender used is not particularly limited, but when the total number of hydroxyl groups of the polycarbonate diol (composition) used in the prepolymer and other polyols is taken as 1 equivalent, the equivalent of isocyanate groups used in the prepolymer , the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99. Equivalents, more preferably in the range of 0.98 equivalents.

For the purpose of adjusting the molecular weight, monofunctional organic amines and alcohols may coexist during the chain extension reaction.

The chain extension reaction is usually carried out at 0° C. to 250° C., but this temperature varies depending on the amount of solvent, reactivity of raw materials used, reaction equipment, etc., and is not particularly limited. If the temperature is too low, the progress of the reaction slows down, and the production time may be lengthened due to the low solubility of the raw materials and polymer. . The chain extension reaction may be performed under reduced pressure while defoaming.

Moreover, a catalyst, a stabilizer, etc. can also be added to a chain extension reaction as needed.
Examples of the catalyst include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. may be used together.
Stabilizers include, for example, 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, tris(dinonylphenyl)phosphite. and the like, and may be used alone or in combination of two or more. If the chain extender is highly reactive such as a short-chain aliphatic amine, the reaction may be carried out without adding a catalyst.

<2-11. Aqueous Polyurethane Dispersion>
Using the polycarbonate diol (composition) of the present invention, it is also possible to produce an aqueous polyurethane dispersion, and compared with conventional polycarbonate diols, an aqueous polyurethane dispersion with higher dispersibility can be produced. In addition, the water-based polyurethane dispersion has excellent storage stability because it hardly aggregates during storage.
In that case, compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups when reacting a polyol containing a polycarbonate diol (composition) with excess polyisocyanate to produce a prepolymer are mixed to form a prepolymer, and an aqueous polyurethane dispersion is obtained through a process of neutralization and chlorination of hydrophilic functional groups, an emulsification process by adding water, and a chain extension reaction process. Raw materials, additives, catalysts, solvents, and the like used in the prepolymer formation and chain extension reaction steps can be the same as those used in the production of polyurethane.

As used herein, the hydrophilic functional groups of compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups are, for example, carboxyl groups and sulfonic acid groups neutralized with alkaline groups. is a possible group. In addition, 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. It doesn't matter if you are.

Specific examples of compounds 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 and the like. Also included are diaminocarboxylic acids such as lysine, cystine, 3,5-diaminocarboxylic acid and the like. These may be used individually by 1 type, and may use 2 or more types together. When these are actually used, they are neutralized with amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine, and alkaline compounds such as sodium hydroxide, potassium hydroxide and ammonia. be able to.

When producing a water-based polyurethane dispersion, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups to increase the dispersibility in water, the lower limit thereof is the polycarbonate. It is preferably 1% by weight, more preferably 5% by weight, still more preferably 10% by weight, relative to the total weight of the diol (composition) and other polyols. On the other hand, if too much is added, the properties of the polycarbonate diol 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.

When producing an aqueous polyurethane dispersion, 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 step, or may be carried out without a solvent. Moreover, when using a solvent, it is preferable to distill off the solvent by distillation after producing an aqueous dispersion.

When the solvent-free aqueous polyurethane dispersion is produced using the polycarbonate diol (composition) of the present invention as a raw material, the upper limit of the number average molecular weight obtained from the hydroxyl value of the polycarbonate diol (composition) is preferably 5000, or more. It is preferably 4,000, more preferably 3,000, and particularly preferably 2,000. Also, the lower limit of the number average molecular weight is preferably 300, more preferably 500, still more preferably 800. If the number average molecular weight obtained from the hydroxyl value exceeds the above upper limit or is smaller than the above lower limit, it may become difficult to form a dispersion.

Moreover, when producing an aqueous polyurethane dispersion, the polycarbonate diol (composition) of the present invention may be used in combination with other polyols, if necessary.
Here, other polyols are not particularly limited as long as they are used in normal polyurethane production. and polycarbonate diols other than 2. For example, when used in combination with polyether polyol, it is possible to obtain a polyurethane with further improved flexibility, which is a feature of the polycarbonate diol of the present invention.

When other polyols are used in combination, the weight ratio of the polycarbonate diol 1 of the present invention to the total weight of the polycarbonate diol (composition) of the present invention and other polyols is preferably 70% or more, and more preferably 90% or more. preferable. If the weight ratio of the polycarbonate diol 1 of the present invention is small, there is a possibility that the properties and handleability of the polyurethane that characterize the present invention will be lost.

When other polyols are used together in the production of the aqueous polyurethane dispersion, the polycarbonate diol (composition) of the present invention, other polyols used as necessary, and other raw materials are sufficiently dispersed in the aqueous solvent. Or need to dissolve. If the dispersibility is not sufficient, the urethanization reaction proceeds unevenly, and the molecular weight distribution of the resulting water-based polyurethane dispersion widens, or the molecular weight decreases, resulting in aggregation of the water-based polyurethane dispersion and poor storage stability. becomes worse. Moreover, the strength, solvent resistance, weather resistance, heat resistance, etc. of the polyurethane obtained from the water-based polyurethane dispersion may deteriorate.

In the synthesis or storage of aqueous polyurethane dispersions, anionic compounds represented by higher fatty acids, resin acids, fatty acid alcohols, sulfate esters, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinate esters, etc. are used. Cationic surfactants such as surfactants, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, or ethylene oxide and long-chain fatty alcohols or phenols The emulsification stability may be maintained by using a nonionic surfactant represented by the known reaction product of .

In addition, when forming an aqueous polyurethane dispersion, water is mechanically mixed with a prepolymer solution in an organic solvent in the presence of an emulsifier at high shear, if necessary, without a neutralization and chlorination step, to obtain a dispersion. It can also be manufactured.
The aqueous polyurethane dispersion thus produced can be used for various purposes. In particular, there is a recent demand for chemical raw materials with less environmental impact, and it is possible to replace conventional products for the purpose of not using organic solvents.

Specific uses of water-based polyurethane dispersions include, for example, coating agents, water-based paints, adhesives, synthetic leathers, and artificial leathers. In particular, the aqueous polyurethane dispersion produced using the polycarbonate diol (composition) of the present invention has the structural unit (A) in the polycarbonate diol (composition), and thus has chemical resistance and hydrolysis resistance. Excellent heat resistance and weather resistance. In addition, since it has the structural unit (B), it has flexibility and smoothness, so it can be effectively used as a coating agent, etc., compared to conventional water-based polyurethane dispersions using polycarbonate diols. be.

<2-12. Storage Stability of Polyurethane Solution and Aqueous Polyurethane Dispersion>
The storage stability of a polyurethane solution and an aqueous polyurethane dispersion produced using an organic solvent and/or water using the polycarbonate diol (composition) of the present invention depends on the concentration of polyurethane in the solution or dispersion (hereinafter referred to as , sometimes referred to as "solid content concentration") is adjusted to 1 to 80% by weight, stored under specific temperature conditions, and the presence or absence of changes in the solution or dispersion can be visually measured. .

For example, a polyurethane solution (N,N-dimethylformamide/toluene mixture, solid content concentration of 30% by weight), the period during which no change is visually observed in the polyurethane solution when stored at -10°C is preferably 8 hours, more preferably 1 day or more, still more preferably 3 days or more. is more than 7 days. The period during which no change is visually observed in the polyurethane solution and polyurethane dispersion when stored at 0° C. is preferably 1 month, more preferably 3 months or more, and still more preferably 6 months or more.

Further, for example, an aqueous polyurethane dispersion produced using the polycarbonate diol (composition) of the present invention, 4,4′-dicyclohexylmethane diisocyanate, and ethylenediamine (dispersed in N-methyl-2-pyrrolidone/water mixture, solid content Concentration: 30% by weight), when stored at 20°C, the period during which no change is visually observed in the aqueous polyurethane dispersion is preferably 1 day, more preferably 3 days, more preferably 7 days or more, and even more preferably. is 14 days, particularly preferably 1 month or more.

<2-13. Additive>
The polyurethane produced using the polycarbonate diol (composition) of the present invention contains heat stabilizers, light stabilizers, colorants, fillers, stabilizers, UV absorbers, antioxidants, antiblocking agents, flame retardants, Various additives such as anti-aging agents and inorganic fillers can be added and mixed as long as the properties of the polyurethane are not impaired.

Compounds that can be used as heat stabilizers include phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl Phosphorus compounds such as pentaerythritol diphosphite and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; Compounds containing sulfur; tin-based compounds such as tin malate, dibutyltin monoxide, and the like can be used.

Specific examples of hindered phenol compounds include "Irganox1010" (trade name: manufactured by BASF Japan Ltd.), "Irganox1520" (trade name: manufactured by BASF Japan Ltd.), "Irganox245" (trade name: manufactured by BASF Japan Ltd.). ) and the like.

Phosphorus compounds include "PEP-36", "PEP-24G", "HP-10" (all trade names: manufactured by ADEKA Corporation), "Irgafos 168" (manufactured by BASF Japan Ltd.), etc. is mentioned.

Specific examples of sulfur-containing compounds include thioether compounds such as dilaurylthiopropionate (DLTP) and distearylthiopropionate (DSTP).

Examples of light stabilizers include benzotriazole-based compounds and benzophenone-based compounds. ”, “SANOL LS-765” (manufactured by Sankyo Co., Ltd.) and the like can be used.

Examples of ultraviolet absorbers include "TINUVIN328" and "TINUVIN234" (manufactured by Ciba Specialty Chemicals Co., Ltd.).

Colorants include dyes such as direct dyes, acid dyes, basic dyes and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide and mica; Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments can be used.

Examples of inorganic fillers include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, and clay.

Examples of flame retardants include additive and reactive flame retardants such as phosphorous and halogen containing organic compounds, bromine or chlorine containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide and the like.

These additives may be used alone, or two or more of them may be used in any combination and ratio.
As for the amount of these additives added, the lower limit is preferably 0.01% by weight, more preferably 0.05% by weight, and still more preferably 0.1% by weight, and the upper limit is preferably 10% by weight, as a weight ratio to polyurethane. % by weight, more preferably 5% by weight, and even more preferably 1% by weight. If the amount of the additive added is too small, the effect of addition cannot be sufficiently obtained, and if it is too large, it may precipitate in the polyurethane or cause turbidity.

<2-14. Polyurethane film/polyurethane plate>
When a film is produced using polyurethane, the thickness of the film preferably has a lower limit of 10 µm, more preferably 20 µm, and still more preferably 30 µm, and an upper limit of preferably 1000 µm, more preferably 500 µm, and even more preferably 100 µm. be.
If the thickness of the film is too thick, there is a tendency that sufficient moisture permeability cannot be obtained.

<2-15. Molecular weight>
The molecular weight of the polyurethane is appropriately adjusted according to its use, and is not particularly limited, but is preferably 50,000 to 500,000, more preferably 100,000 to 30, as a polystyrene equivalent weight average molecular weight (Mw) measured by GPC. 10,000 is more preferable. If Mw is less than the above lower limit, sufficient strength and hardness may not be obtained.

<2-16. Room temperature tensile test>
<2-16-1. Tensile breaking elongation and strength in room temperature tensile test>
Polyurethane is a strip-shaped sample with a width of 10 mm, a length of 100 mm, and a thickness of about 50 to 100 μm, with a chuck distance of 50 mm, a tensile speed of 500 mm/min, a temperature of 23° C., and a relative humidity of 60%. The elongation and breaking strength are preferably within the following ranges.

The lower limit of breaking elongation is preferably 200%, more preferably 300%, and still more preferably 350%, and the upper limit is preferably 1000%, more preferably 800%, and still more preferably 600%. If the elongation at break is less than the above lower limit, there is a tendency to impair handleability such as workability, and if it exceeds the above upper limit, sufficient solvent resistance may not be obtained.
The lower limit of breaking strength is preferably 30 MPa, more preferably 40 MPa, and still more preferably 50 MPa, and the upper limit is preferably 200 MPa, more preferably 100 MPa, and still more preferably 80 MPa. If the breaking strength is less than the above lower limit, the handling property such as processability tends to be impaired, and if it exceeds the above upper limit, the flexibility may be impaired.

<2-16-2. 100% modulus in room temperature tensile test, 300% modulus>
Polyurethane was measured on a strip-shaped sample with a width of 10 mm, a length of 100 mm, and a thickness of about 50 to 100 μm at a chuck distance of 50 mm and a tensile speed of 500 mm/min at a temperature of 23° C. and a relative humidity of 60%. The lower limit of modulus (100% M) is preferably 1.0 MPa, more preferably 2.0 MPa, still more preferably 3.0 MPa, and the upper limit is preferably 20 MPa, more preferably 10 MPa, still more preferably 8 MPa. If the 100% modulus is less than the above lower limit, the hardness may not be sufficient, and if it exceeds the above upper limit, the flexibility tends to be insufficient, and the handleability such as workability tends to be impaired. Furthermore, the lower limit of the 300% modulus (300% M) of polyurethane is preferably 5 MPa, more preferably 8 MPa, even more preferably 10 MPa. The upper limit is preferably 100 MPa, more preferably 50 MPa, still more preferably 30 MPa. If the 300% modulus is less than the above lower limit, the hardness may be insufficient. If the 300% modulus exceeds the above upper limit, flexibility may be insufficient, and handling properties such as workability may be impaired.

<2-18. Solvent resistance>
<2-18-1. Olein resistance>
Polyurethane is evaluated, for example, by the method described in the section of Examples below, the rate of change (%) in the weight of the polyurethane test piece after immersion in oleic acid with respect to the weight of the polyurethane test piece before immersion in oleic acid. However, it is preferably 200% or less, more preferably 150% or less, still more preferably 120% or less, particularly preferably 100% or less, and most preferably 80% or less. If the weight change rate exceeds the above upper limit, sufficient oleic acid resistance may not be obtained.

<2-18-2. Ethanol resistance>
Polyurethane is evaluated, for example, by the method described in the Examples section below, and the rate of change (%) in the weight of the polyurethane test piece after immersion in ethanol with respect to the weight of the polyurethane test piece before immersion in ethanol is It is preferably 50% or less, more preferably 45% or less, even more preferably 40% or less, particularly preferably 35% or less, most preferably 30% or less.
If the weight change rate exceeds the above upper limit, sufficient ethanol resistance may not be obtained.

<2-20. Application>
Polyurethane has excellent solvent resistance, good flexibility, and mechanical strength. It can be widely used for synthetic leather, coating agents, water-based polyurethane coatings, active energy ray-curable polymer compositions, and the like.
In particular, when the polyurethane of one embodiment 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, and coating agents, solvent resistance and flexibility are improved. Because it has a good balance of durability and mechanical strength, it is highly durable in areas where it comes into contact with human skin, or where cosmetic chemicals or alcohol for disinfection are used. Good properties such as resistance to impact can be imparted. In addition, it can be suitably used for automotive applications such as automobile members that require heat resistance, and outdoor applications that require weather resistance.

Polyurethanes can be used in thermoset elastomers, cast polyurethane elastomers. Specific applications include rolling rolls, paper manufacturing rolls, office equipment, rolls such as pretension rolls, solid tires for forklifts, automobile vehicle nutrams, trolleys, trucks, casters, etc. Industrial products include conveyor belt idlers and guides. Rolls, pulleys, steel pipe linings, ore rubber screens, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. It can also be used for OA equipment belts, paper feed rolls, copying cleaning blades, snow plows, toothed belts, surf rollers and the like.

Polyurethanes also find application as thermoplastic elastomers. For example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment used in the food and medical fields, coating equipment, analytical equipment, physical and chemical equipment, metering pumps, water treatment equipment, industrial robots, and the like. In addition, it is used as a belt such as a round belt, a V belt, a flat belt, etc. in various transmission mechanisms, spinning machines, packing machines, printing machines, and the like. It can also be used for heel tops and soles of footwear, couplings, packings, pole joints, bushes, gears, machine parts such as rolls, sporting goods, leisure goods, watch belts and the like. Automobile parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain substitutes. Also, it can be used for films such as keyboard films and films for automobiles, curled cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leathers, dipping products, adhesives and the like.

Polyurethane 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 sporting goods. It can also be used for automobile repair as tar epoxy urethane.
Polyurethane can be used as a component of moisture-curable one-pack paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, UV-curable paints, and water-based urethane paints. Paints, strippable paints, coating agents for magnetic tapes, floor tiles, floor materials, paper, overprint varnishes such as wood grain printing films, varnishes for wood, coil coats for high processing, optical fiber protective coatings, solder resists, tops for metal printing It can be applied to coatings, vapor deposition base coats, white coats for food cans, and the like.

Polyurethanes can also be applied as pressure-sensitive adhesives and adhesives to food packaging, shoes, footwear, magnetic tape binders, decorative papers, lumber, structural members, etc. They can also be used as low-temperature adhesives and hot-melt components. can be done.
Polyurethane can be used as a binder for magnetic recording media, inks, castings, baked bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortar, resin mortar, rubber chip binders, recycled foam, glass fiber sizing, etc. be.

Polyurethane can be used as a component of a fiber processing agent for shrink-proofing, wrinkle-proofing, water-repellent finishing, and the like.
When polyurethane is used as the elastic fiber, the fiberization method is not particularly limited as long as it can be spun. For example, a melt spinning method can be employed in which the material is pelletized, melted, and spun directly through a spinneret. When elastic fibers are obtained from polyurethane 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 can be used as a bare thread as it is, or can be used as a covered thread after being covered with other fibers. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton and polyester fibers, among which polyester fibers are preferably used in the present invention. In addition, the elastic fiber using polyurethane may contain a dyeing type disperse dye.

Polyurethane is used as a sealant and caulking for concrete walls, induced joints, around sashes, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Light-weight Concrete) joints, board joints, composite glass sealants, and heat insulating sash sealants. , automotive sealants, etc.
Polyurethane can be used as a medical material, including blood compatible materials such as tubes, catheters, artificial hearts, artificial blood vessels, and artificial valves, and disposable materials such as catheters, tubes, bags, surgical gloves, and artificial kidneys. It can be used as a potting material.
Polyurethanes can be used as raw materials for UV curable coatings, electron beam curable coatings, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, etc. by modifying the terminals.

<2-21. Urethane (meth)acrylate oligomer>
A urethane (meth)acrylate oligomer can be produced by subjecting a polyisocyanate and a hydroxyalkyl (meth)acrylate to an addition reaction using the polycarbonate diol (composition) of the present invention. When other raw material compounds such as a polyol and a chain extender are used in combination, the urethane (meth)acrylate oligomer can be produced by subjecting the polyisocyanate to an addition reaction with these other raw material compounds. .

In the present invention, the expression "(meth)acrylic" such as (meth)acrylate or (meth)acrylic acid means acrylic and/or methacrylic.
In addition, the charging ratio of each raw material compound at that time is substantially the same as or the same as the composition of the desired 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 theoretically equimolar.

When producing a urethane (meth)acrylate-based oligomer, the amount of hydroxyalkyl (meth)acrylate used is determined by hydroxyalkyl (meth)acrylate, polycarbonate diol (composition), and other raw material compounds used as necessary. Generally 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and usually 70 mol % or less, preferably 50 mol % or less. The molecular weight of the resulting urethane (meth)acrylate oligomer can be controlled according to this ratio. 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 1 of the present invention used is preferably 25 mol% or more, more preferably 50 mol% or more, based on the total amount of the polycarbonate diol (composition) of the present invention and other polyols used. , more preferably 70 mol % or more. When the amount of polycarbonate diol 1 used is at least the above lower limit, the elongation, hardness, weather resistance, and stain resistance of the resulting cured product tend to be good, which is preferable.

The amount of the polycarbonate diol 1 of the present invention used is preferably 10% by weight or more, more preferably 30% by weight, based on the total amount of the polycarbonate diol (composition) of the present invention and other polyols used. % by weight or more, more preferably 50% by weight or more, particularly preferably 70% by weight or more. When the amount of polycarbonate diol 1 used is at least the above lower limit, the viscosity of the obtained composition is lowered and the workability is improved, and the mechanical strength, hardness and abrasion resistance of the obtained cured product tend to be improved. and is preferable.

Furthermore, when using a chain extender, the polycarbonate diol (composition) and other The amount of polyol used is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and particularly preferably 95 mol % or more. If it is above the lower limit, the liquid stability tends to be improved, which is preferable.

A solvent can be used for the purpose of adjusting the viscosity during the production of the urethane (meth)acrylate oligomer. A solvent may be used individually by 1 type, and may be used in mixture of 2 or more types. Any known solvent can be used as the solvent. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and the like. The solvent can be used in an amount of less than 300 parts by weight per 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 produced urethane (meth)acrylate oligomer and its raw material compound is preferably 20% by weight or more, preferably 40% by weight, based on the total amount of the reaction system. % or more is more preferable. The upper limit of this total content is 100% by weight. When the total content of the urethane (meth)acrylate-based oligomer and its raw material compounds is 20% by weight or more, the reaction rate tends to be high and the production efficiency tends to be improved, which is preferable.

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 dioctate, dioctyltin dilaurate, and dioctyltin dioctate. The addition reaction catalyst may be used alone or in combination of two or more. Among these, the addition reaction catalyst is preferably dioctyltin dilaurate from the viewpoint 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 Used at 30 ppm by weight.
Moreover, when a (meth)acryloyl group is included in the reaction system 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 and dibutylhydroxytoluene; amines such as phenothiazine and diphenylamine; copper salts such as copper dibutyldithiocarbamate; Salts, nitro compounds, nitroso compounds and the like are included. A polymerization inhibitor may be used individually by 1 type, and may be used in mixture of 2 or more types. Among these, the polymerization inhibitor is preferably a phenol.

The upper limit of the polymerization inhibitor is usually 3000 ppm by weight, preferably 1000 ppm by weight, particularly preferably 500 ppm by weight, with respect to the total content of the urethane (meth) acrylate oligomer and its raw material compound to be produced, A lower limit is usually used of 50 ppm by weight, preferably 100 ppm by weight.
During the production of the urethane (meth)acrylate oligomer, the reaction temperature is usually 20° C. or higher, preferably 40° C. or higher, more preferably 60° C. or higher. A reaction temperature of 20° C. or higher is preferable because the reaction rate tends to increase and the production efficiency tends to improve. Moreover, the reaction temperature is usually 120° C. or lower, preferably 100° C. or lower. When the reaction temperature is 120° C. or lower, it is preferable because side reactions such as allophanate reaction are less likely to occur. Further, when the reaction system contains a solvent, the reaction temperature is preferably below the boiling point of the solvent, and when (meth)acrylate is contained, it is 70 ° C. from the viewpoint of preventing the reaction of the (meth)acryloyl group. The following are preferable. The reaction time is usually about 5 to 20 hours.

The number average molecular weight of the urethane (meth)acrylate oligomer thus obtained is preferably 500 or more, particularly preferably 1,000 or more, and preferably 10,000 or less, particularly preferably 5,000 or less, particularly preferably 3,000 or less. When the number average molecular weight of the urethane (meth)acrylate oligomer is at least the above lower limit, the three-dimensional processability of the resulting cured film is favorable, and the balance between the three-dimensional processability and stain resistance tends to be excellent, which is preferable. When the number average molecular weight of the urethane (meth)acrylate oligomer is equal to or less than the above upper limit, the cured film obtained from the composition has good stain resistance, and tends to have an excellent balance between suitability for three-dimensional processing and stain resistance. Therefore, it is preferable. This is because three-dimensional processing suitability and stain resistance depend on the distance between cross-linking points in the network structure. It is presumed that this is because the structure becomes a strong structure and is excellent in stain resistance.

<2-22. Polyester Elastomer>
The polycarbonate diol (composition) of the present invention can be used as a polyester elastomer. Polyester-based elastomers are copolymers composed of hard segments mainly composed of aromatic polyesters and soft segments mainly composed of aliphatic polyethers, aliphatic polyesters or aliphatic polycarbonates. When the polycarbonate diol (composition) of the present invention is used as a constituent component of the soft segment, physical properties such as heat resistance and water resistance are superior to those in which aliphatic polyethers and aliphatic polyesters are used. In addition, compared to known polycarbonate diols, the resulting polycarbonate polyester elastomer has fluidity when melted, that is, a melt flow rate suitable for blow molding and extrusion molding, and has an excellent balance with mechanical strength and other physical properties. , fibers, films, sheets and other molding materials, for example, elastic yarns and molding materials such as boots, gears, tubes and packings. Specifically, it can be effectively applied to applications such as joint boots for automobiles, household appliance parts, etc., which require heat resistance and durability, and electric wire coating materials.

<2-23. Active energy ray-curable polymer composition>
An active energy ray-curable polymer composition containing the above urethane (meth)acrylate oligomer (hereinafter sometimes simply referred to as "active energy ray-curable polymer composition") will be described.
The active energy ray-curable polymer composition preferably has a calculated molecular weight between crosslink points in the network of 500 to 10,000.

In the present specification, the calculated network cross-linking point molecular weight of the composition is the average molecular weight between the active energy ray-reactive groups (hereinafter sometimes referred to as "crosslinking points") forming the network structure in the entire composition. represents a value. The molecular weight between the calculated network cross-linking points has a correlation with the network area at the time of forming the network structure, and the larger the molecular weight between the calculated network cross-linking points, the smaller the cross-linking 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 a "monofunctional compound") reacts, it becomes a linear polymer, while active energy A network structure is formed when a compound having two or more linear reactive groups (hereinafter sometimes referred to as a "polyfunctional compound") reacts.

Therefore, here, the active energy ray reactive group possessed by the polyfunctional compound is a cross-linking point, the calculation of the molecular weight between the calculated network cross-linking points is centered on the polyfunctional compound having the cross-linking point, and the monofunctional compound is possessed by the polyfunctional compound. The molecular weight between the cross-linking points is treated as having the effect of extending the molecular weight between the cross-linking points, and the molecular weight between the cross-linking points of the calculated network is calculated. Further, the calculation of the molecular weight between cross-linking points in the calculated network 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 with the irradiation of the active energy ray. .

In a polyfunctional compound single system composition in which only one type of polyfunctional compound reacts, twice the average molecular weight per active energy ray-reactive group possessed by the polyfunctional compound is the molecular weight between the calculated network crosslink points. . 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 weight between the calculated network crosslink 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 It is the molecular weight between the calculated network crosslink points of the composition. For example, in a composition comprising a mixture of 4 mols of a bifunctional compound with a molecular weight of 1,000 and 4 mols of a trifunctional compound with a molecular weight of 300, the total number of active energy ray-reactive groups in the composition is 2×4+3×4=20. and the calculated molecular weight between network crosslink 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 a molar equivalent to each of the active energy ray reactive groups (i.e., cross-linking points) of the polyfunctional compound and a monofunctional compound linked to the cross-linking points is calculated. Assuming that the reaction is located in the center of the chain, the amount of elongation of the molecular chain by the monofunctional compound at one cross-linking 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 base. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per one cross-linking point, the amount extended by the monofunctional compound with respect to the calculated molecular weight between the calculated network cross-linking points for the polyfunctional compound is , is a value obtained by dividing the total molecular weight of monofunctional compounds by the total number of active energy ray-reactive groups of polyfunctional compounds in the composition.

For example, in a composition comprising a mixture of 40 mols of a monofunctional compound with a molecular weight of 100 and 4 mols of a bifunctional compound with a molecular weight of 1,000, the number of active energy ray reactive groups of the polyfunctional compound is 2×4=8. , the extension amount due to the monofunctional compound in the molecular weight between cross-linking points in the calculated network is 100×40/8=500. That is, the molecular weight between calculated network crosslink points of the composition is 1000+500=1500.
From the above, it can be seen that for a mixture of M _A moles of monofunctional compound of molecular weight W _A , M _B moles of f _B -functional compound of molecular weight W _B and M _C moles of f _C -functional compound of molecular weight W _C , the composition The molecular weight between calculated network cross-linking points of a compound can be expressed by the following formula.

The calculated molecular weight between network crosslink points of the active energy ray-curable polymer composition calculated in this way is preferably 500 or more, more preferably 800 or more, and 1,000 or more. It is more preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less, and even more preferably 4,000 or less. 000 or less is particularly preferred.

When the molecular weight between calculated network cross-linking points is 10,000 or less, the cured film obtained from the composition has good stain resistance and tends to have an excellent balance between suitability for three-dimensional processing and stain resistance, which is preferable. Further, when the molecular weight between the cross-linking points of the calculated network is 500 or more, the three-dimensional processability of the resulting cured film becomes favorable, and the balance between the three-dimensional processability and stain resistance tends to be excellent, which is preferable. This is because three-dimensional processing aptitude and stain resistance depend on the distance between cross-linking points in the network structure, and the longer this distance is, the more flexible and stretchable the structure becomes, which is excellent in three-dimensional processing aptitude, and the shorter this distance is. It is presumed that this is because the network structure becomes a strong structure and is excellent in stain resistance.

The active energy ray-curable polymer composition may further contain components other than the urethane (meth)acrylate oligomer. Such other components include, for example, active energy ray-reactive monomers, active energy ray-curable oligomers, polymerization initiators, photosensitizers, additives, and solvents.

In the active energy ray-curable polymer composition, the content of the urethane (meth)acrylate-based oligomer is 40% by weight or more with respect to the total amount of active energy ray-reactive components including the urethane (meth)acrylate-based oligomer. is preferred, and 60% by weight or more is more preferred. The upper limit of this content is 100% by weight. When the content of the urethane (meth)acrylate oligomer is 40% by weight or more, the curability is improved, and the three-dimensional processability tends to be improved without excessively increasing the mechanical strength of the cured product. It is preferable because

In addition, in the active energy ray-curable polymer composition, the content of the urethane (meth)acrylate oligomer is preferably large in terms of elongation and film-forming properties. Less is better. From this point of view, the content of the urethane (meth)acrylate oligomer is preferably 50% by weight or more with respect to the total amount of all components including other components in addition to the active energy ray-reactive component. , more preferably 70% by weight or more. The upper limit of the content of the urethane (meth)acrylate oligomer is 100% by weight, and the content is preferably 100% by weight or less.

In addition, in the active energy ray-curable polymer composition, the total content of the active energy ray-reactive components including the urethane (meth)acrylate-based oligomer is such that the composition has excellent curing speed and surface curability, and tackiness. is preferably 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and 95% by weight, based on the total amount of the composition. % or more is particularly preferable. The upper limit of this content is 100% by 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 and hydrophobicity of the urethane (meth)acrylate oligomer, and the physical properties such as the hardness and elongation of the cured product when the resulting composition is cured. be done. The active energy ray-reactive monomers may be used singly or in combination of two or more.

Examples of such active energy ray-reactive monomers include vinyl ethers, (meth)acrylamides, and (meth)acrylates, and specific examples include styrene, α-methylstyrene, α-chlorostyrene. , vinyltoluene, and divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, divinyl adipate, and other vinyl monomers 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-dimethylmethacryl Amide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, Nt-butyl(meth)acrylamide, (meth)acryloylmorpholine, methylenebis(meth)acrylamide, etc. (Meth) acrylamides; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, -n-butyl (meth) acrylate, (meth) acrylic acid - i-butyl, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, ( meth)dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylate Monofunctional (meth)acrylates such as isobornyl acrylate and phenyl (meth)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 to 14), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, di(meth)acrylate polypropylene glycol acrylate (n = 5 to 14), 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polybutylene glycol di(meth)acrylate ( n = 3 to 16), poly(1-methylbutylene glycol) di(meth)acrylate (n = 5 to 20), di(meth)acrylic acid-1,6-hexanediol, di(meth)acrylic acid- 1,9-nonanediol, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanediol di(meth)acrylate, tricyclo di(meth)acrylate Decane, 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 hexa(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, trimethylolpropane trioxypropyl (meth)acrylate, trimethylolpropane polyoxyethyl (meth)acrylate, trimethylolpropane poly Oxypropyl (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 addition bisphenol F di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol F di(meth)acrylate, tri polyfunctional (meth)acrylates such as cyclodecane dimethanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate;

Among these, in applications where coating properties are particularly required, (meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Having 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, and 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, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol Polyfunctional (meth)acrylates such as tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred. .

In the active-energy-ray-curable polymer composition, the content of the active-energy-ray-reactive monomer is adjusted to the total amount of the composition from the viewpoint of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less.

The said active-energy-ray-curable oligomer may be used individually by 1 type, and may be used in mixture of 2 or more types. Examples of the active energy ray-curable oligomers include epoxy (meth)acrylate oligomers and acrylic (meth)acrylate oligomers.
In the active energy ray-curable polymer composition, the content of the active energy ray-reactive oligomer is 50 wt. %, more preferably 30% by weight or less, even more 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 the polymerization reaction that proceeds upon exposure to active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a radical photopolymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known radical photopolymerization initiator can be used. One of the polymerization initiators may be used alone, or two or more of them may be used in combination. Furthermore, a photoradical polymerization initiator and a photosensitizer may be used in combination.

Examples of photoradical polymerization initiators include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis(diethylamino)benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1-[4-(methylthio)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-hydroxycyclohexylphenyl ketone, 2,4,6 are preferred because the curing speed is fast and the crosslink 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 Preferably 1-hydroxycyclohexylphenyl 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.

Further, when the active energy ray-curable polymer composition contains a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group, as a polymerization initiator, a photocationically A polymerization initiator may be included. Any known photocationic polymerization initiator can be used.

The content of these polymerization initiators in the active energy ray-curable polymer composition is preferably 10 parts by weight or less, and 5 parts by weight with respect to a total of 100 parts by weight of the active energy ray-reactive components. The following are more preferable. When the content of the polymerization initiator is 10 parts by weight or less, the mechanical strength is less likely to be lowered by decomposition products of the initiator, which is preferable.

The photosensitizer can be used for the same purpose as the polymerization initiator. The photosensitizers may be used singly or in combination of two or more. As the photosensitizer, any known photosensitizer can be used as long as the effect of the present invention can be 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, 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, and 5 parts by weight. Part or less is more preferable. When the content of the photosensitizer is 10 parts by weight or less, the mechanical strength is less likely to decrease due to the decrease in the crosslink density, which is preferable.

The additive is optional, and various materials added to compositions used for similar purposes can be used as additives. Additives may be used singly or in combination of two or more. Examples of such additives include glass fibers, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxides, metal fibers, iron, lead, metal powders, and the like. Fillers: carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (hereinafter, fillers and carbon materials may be collectively referred to as "inorganic components"); oxidation prevention agent, heat stabilizer, ultraviolet absorber, HALS (hindered amine light stabilizer), anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slip agent, plasticizer, release agent, antifoaming agent, leveling agent, Anti-settling agents, surfactants, thixotropic agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, modifiers such as silane coupling agents; coloring agents such as pigments, dyes, and hue modifiers agents; and monomers and/or oligomers thereof, or curing agents, catalysts, curing accelerators necessary for synthesizing inorganic components; and the like.

In the active energy ray-curable polymer composition, the content of the additive is preferably 10 parts by weight or less, and 5 parts by weight or less with respect to the total 100 parts by weight of the active energy ray-reactive components. is more preferable. When the content of the additive is 10 parts by weight or less, the mechanical strength is less likely to decrease due to the decrease in crosslink density, which is preferable.
The solvent can be used for the purpose of adjusting the viscosity of the active energy ray-curable polymer composition according to, for example, the coating method for forming the coating film of the active energy ray-curable polymer composition. 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 can be obtained. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and the like. The solvent can usually be used in an amount of less than 200 parts by weight per 100 parts by weight of the solid content of the active energy ray-curable polymer composition.

The method for adding optional components such as the above-described additives to the active energy ray-curable polymer composition is not particularly limited, and conventionally known mixing and dispersing methods and the like can be mentioned. In order to more reliably disperse the optional components, it is preferable to perform the dispersion treatment using a disperser. Specifically, for example, two-roll, three-roll, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, segvariator, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact A method of treating with a mill, a kneader, a homogenizer, an ultrasonic disperser, or the like can be mentioned.

The viscosity of the active energy ray-curable polymer composition can be appropriately adjusted according to the application, mode of use, etc. of the composition. The viscosity at 25° C. in a type viscometer (rotor 1°34′×R24) is preferably 10 mPa s or more, more preferably 100 mPa s or more, and on the other hand, 100,000 mPa s. It is preferably 50,000 mPa·s or less, more preferably 50,000 mPa·s or less. The viscosity of the active energy ray-curable polymer composition can be adjusted by, for example, the content of the above-mentioned urethane (meth)acrylate-based oligomer, the types of the above-mentioned optional components, their mixing ratios, and the like.

Examples of coating methods for the active energy ray-curable polymer composition include 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, and a lip coater. A known method such as a method, a die coater method, a slot die coater method, an air knife coater method, a dip coater method can be applied, and among them, a bar coater method and a gravure coater method are preferable.

<2-24. Cured Film and Laminate>
The active energy ray-curable polymer composition can be made into a cured film by irradiating it with an active energy ray.
Infrared rays, visible rays, ultraviolet rays, X rays, electron beams, α rays, β rays, γ rays, etc. can be used as the active energy rays used when curing the above composition. From the viewpoint of equipment cost and productivity, it is preferable to use electron beams or ultraviolet rays. Lasers, He--Cd lasers, solid-state lasers, xenon lamps, high-frequency induction mercury lamps, sunlight, etc. are suitable.

The irradiation dose of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, in the case of curing by electron beam irradiation, the irradiation dose is preferably 1 to 10 Mrad. In the case of ultraviolet irradiation, it is preferably 50 to 1,000 mJ/cm ² . The atmosphere during curing may be air or an inert gas such as nitrogen or argon. Alternatively, irradiation may be performed in a closed space between the film or glass and the metal mold.

The thickness of the cured film can be appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. Also, the upper limit is preferably 200 μm, more preferably 100 μm, and particularly preferably 50 μm. When the film thickness is 1 μm or more, the appearance of design and functionality after three-dimensional processing is good, and on the other hand, when it is 200 μm or less, internal curability and suitability for three-dimensional processing are good, which is preferable. For industrial use, the lower limit of the film 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.

It is possible to obtain a laminate having a layer composed of the above cured film on a substrate. This laminate is not particularly limited as long as it has a layer composed of a cured film, and may have a layer other than the substrate and the cured film between the substrate and the cured film, or may have a layer other than the substrate and the cured film. may have. Moreover, the laminate may have a plurality of substrates and cured films.
As a method for obtaining a laminate having a cured film of multiple layers, there is a method in which all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured or semi-cured with active energy rays and then A known method such as a method of applying an upper layer and curing again with an active energy ray, and a method of applying each layer to a release film or a base film and then bonding the layers together in an uncured or semi-cured state. Although applicable, from the viewpoint of enhancing adhesion between layers, a method of laminating in an uncured state and then curing with an active energy ray is preferable. As a method of laminating in an uncured state, a known method such as sequential coating in which the lower layer is applied and then the upper layer is applied, or simultaneous multilayer coating in which two or more layers are applied at the same time from multiple slits is applied. It is possible, but not limited to this.

Examples of substrates include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate, and (meth)acrylic resins, and various plates made of glass or metal. shaped articles.
The cured film can be made into a film that is excellent in stain resistance and hardness against general household contaminants such as ink and ethanol. It can be excellent in protection.

In addition, considering the calculated molecular weight between network crosslink points, the active energy ray-curable polymer composition has flexibility, breaking elongation, mechanical strength, stain resistance, and A cured film having hardness at the same time can be provided.
In addition, the active energy ray-curable polymer composition is expected to enable the simple production of a thin resin sheet by single-layer coating.

The breaking elongation of the cured film was measured by cutting the cured film into a width of 10 mm and using a Tensilon tensile tester (Tensilon UTM-III-100, manufactured by Orientec Co., Ltd.) at a temperature of 23 ° C. and a tensile speed of 50 mm / min between chucks. The value measured by performing a tensile test at 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 films and laminates described above can be used as coating substitute films, and can be effectively applied, for example, to interior and exterior building materials, automobiles, various members of home appliances, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.

〔Evaluation method〕
Evaluation methods for the polycarbonate diols and polyurethanes obtained in the following examples and comparative examples are as follows.

[Evaluation of Polycarbonate Diol]
<Molar Ratio of Structural Unit (A) to Structural Unit (B)>
Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (AVANCE 400 manufactured by Bruker) was measured, and the molar ratio of structural unit (A) and structural unit (B) was determined from the signal position of each component.

<Average carbon number>
The molar ratio of the structural unit (A) and the structural unit (B) determined above, and the number of carbon atoms between the two hydroxyl groups of the dihydroxy compounds used as raw materials for the structural unit (A) and the structural unit (B) From, the average carbon number was calculated.

<Hydroxyl value>
According to JIS K1557-1, the hydroxyl value of the polycarbonate diol was measured by automatic titration using an acetylation reagent.

<Acid value>
The acid value of the polycarbonate diol was measured according to the indicator titration method of JIS K 1557.

<Number average molecular weight>
The number average molecular weight was calculated from the above acid value and hydroxyl value. Considering that the acid value affects the titration measurement of the hydroxyl value, the number average molecular weight was calculated by the following formula using the following acid value corrected hydroxyl value for calculation of the number average molecular weight.
Acid value corrected hydroxyl value = hydroxyl value + acid value Number average molecular weight = 2 × 56.1 / [acid value corrected hydroxyl value × 10 ^-3 ]

<Molecular weight distribution>
Polystyrene-equivalent weight-average molecular weight (Mw) and polystyrene-equivalent number-average molecular weight (Mn) of the polycarbonate diol were determined by GPC measurement under the following conditions, and the molecular weight distribution (Mw/Mn) was calculated.
Apparatus: HLC-8220 manufactured by Tosoh Corporation
Column: TSKgel superHZM-N
(6.0mm I.D. x 15cmL x 3 pieces)
Reference column: superH-RC (6.0mmI.D. x 15cmL x 1)
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0 mL/min
Column temperature: 40°C
RI detector: RI (device HLC-8220 built-in)

<Ester bond rate>
The polycarbonate diol was dissolved in CDCl ₃ and subjected to 400 MHz ¹ H-NMR (AVANCE 400 manufactured by Bruker) to determine the number of carbonate bonds and the number of ester bonds per molecule of polycarbonate diol from the signal position of each component. The ratio of the number of ester bonds to the total number of carbonate bonds and the number of ester bonds was calculated as the ester bond ratio.

[Evaluation of Polyurethane]
<Isocyanate group concentration>
After diluting 20 mL of a mixed solution of di-n-butylamine/toluene (weight ratio: 2/25) with 90 mL of acetone, titration was performed with a 0.5N hydrochloric acid aqueous solution to measure the amount of hydrochloric acid aqueous solution required for neutralization, and the blank value. and After that, 1 to 2 g of the reaction solution was taken out, 20 mL of a mixed solution of di-n-butylamine/toluene was added, and the mixture was stirred at room temperature for 30 minutes. The amount of aqueous hydrochloric acid solution required for neutralization was measured by titration with , and the amount of residual amine was quantified. The concentration of isocyanate groups was determined from the volume of the aqueous hydrochloric acid solution required for neutralization by the following formula.
Isocyanate group concentration (% by weight) = A x 42.02/D
A: isocyanate group (mol mol) contained in the sample used for this measurement
A = (BC) x 0.5/1000 x f
B: Amount (mL) of 0.5 N hydrochloric acid aqueous solution required for blank measurement
C: Amount (mL) of 0.5 N hydrochloric acid aqueous solution required for this measurement
f: titer of hydrochloric acid aqueous solution D: sample used for this measurement (g)

<Molecular weight>
The molecular weight of the polyurethane was determined by preparing a dimethylacetamide solution so that the concentration of the polyurethane was 0.14% by weight, and using a GPC apparatus [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TskgelGMH-XL, 2 columns)]. was used to measure the weight average molecular weight (Mw) in terms of standard polystyrene.

<Room temperature tensile test>
According to JISK6301, a strip-shaped polyurethane test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm is measured between chucks using a tensile tester [manufactured by Orientec, product name "Tensilon UTM-III-100"]. A tensile test was performed at a distance of 50 mm and a tensile speed of 500 mm / min at a temperature of 23 ° C. (relative humidity of 60%), and the stress when the test piece was elongated 100% and 300%, and the elongation when it broke (break Elongation) and stress (breaking strength) were measured.

<Solvent resistance>
The polyurethane solution was applied onto a fluorine resin sheet (fluorine tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 9.5 mil applicator, and then heated at 50°C for 5 hours, at 100°C for 0.5 hours, It was dried under vacuum conditions at 100° C. for 0.5 hours and at 80° C. for 15 hours in that order. A test piece of 3 cm x 3 cm was cut out from the obtained polyurethane film, placed in a glass petri dish with an inner diameter of 10 cmφ containing 50 mL of the test solvent, and the weight after immersion in each test solvent at the following temperature for the following time was determined. Measure the weight change rate (%) between the weight of the test piece before immersion and the weight of the test piece after immersion (= (weight of test piece after immersion - weight of test piece before immersion) / test before immersion Weight of piece x 100) was calculated. Here, the closer the weight change rate is to 0%, the better the solvent resistance.
Oleic Acid Resistance: A test piece was immersed in oleic acid at 80° C. for 16 hours.
Ethanol resistance: A test piece was immersed in ethanol at room temperature for 1 hour.

<Storage stability>
An aqueous polyurethane dispersion (polyurethane concentration: 30% by weight) was allowed to stand at 20° C., and changes in the aqueous polyurethane dispersion were visually observed every other week. Based on the period during which changes such as precipitation and aggregation were observed in the aqueous polyurethane dispersion from the start of storage, evaluation was made as follows.
Change within 1 week from the start of storage: ×
Change within 1 month from the start of storage: △
No change for more than 1 month from the start of storage: ○

[Synthesis and Evaluation of Carboxyl Group-Containing Polycarbonate Diol]
[ Reference Example I-1]

<Step A: Production of protected carboxyl group-containing dihydroxy compound>
A 500 mL four-necked flask equipped with a thermometer and a cooling tube was charged with a magnetic stirrer and a nitrogen atmosphere, and then 20.0 g of dimethylolpropionic acid and 150 mL of dimethylformamide were added. After adding 20.9 g of potassium carbonate and 24.0 g of benzyl bromide while cooling the internal temperature to 5° C. or less in an ice bath, the mixture was heated to 20° C. and stirred for 5 hours. After confirming the disappearance of benzyl bromide by ¹ H-NMR, 250 mL of desalted water was added dropwise while the internal temperature was maintained at 10° C. or lower in an ice bath. The obtained reaction mixture was extracted with 250 mL of ethyl acetate, and the obtained organic phase was washed with 200 mL of demineralized water three times, and then concentrated by an evaporator. 30 mL of heptane was added to 200 mL of the obtained concentrate, and the precipitated solid was separated by filtration. The obtained solid was dried under reduced pressure to obtain 19.8 g of a white solid of dimethylolpropionic acid (compound 1-A) having a benzyl-protected carboxyl group (yield based on benzyl bromide: 63%).

<Step B: Polymerization step>
In a 50 mL reaction tube equipped with a stirrer, distillate trap and pressure regulator, 179.2 g of 1,4-butanediol and benzyl-protected dimethylolpropionic acid (compound 1-A) on the carboxyl group obtained in step A were added. : 49.5 g, diphenyl carbonate: 434.3 g, and magnesium acetate tetrahydrate: 10 mg were introduced, and the inside of the reaction tube was replaced with nitrogen. While stirring, the internal temperature was raised to 160° C. to heat and dissolve the contents. After that, the pressure was lowered to 24 kPa over 2 minutes, and the reaction was allowed to proceed for 90 minutes while removing phenol out of the system. The pressure was then lowered to 0.4 kPa over 120 minutes. Further, the temperature was raised to 170° C. in 30 minutes to remove phenol and unreacted dihydroxy compound out of the system, and reaction was continued for 5 hours to obtain 242 g of polycarbonate diol 1-B. Analysis by ¹ H-NMR revealed that the molar ratio of structural units derived from 1,4-butanediol and structural units derived from compound 1-A in the product was 89:11.

<Step C: Deprotection step>
Polycarbonate diol 1-B: 120 g obtained in step B and 2-butanone: 600 mL were placed in a 1 L eggplant flask equipped with a magnetic stirrer and dissolved. product) (manufactured by N.A Chemcat) was added. The mixture was degassed under reduced pressure while stirring at 20° C., and hydrogen gas was introduced from a hydrogen gas-filled balloon. Thereafter, while maintaining the hydrogen atmosphere, the mixture was stirred at 20° C. for 3 hours, and disappearance of the benzyl group was confirmed by ¹ H-NMR to terminate the reaction. 0.17 mL of a 0.085% aqueous phosphoric acid solution was added to a polycarbonate diol solution obtained by filtering Pd carbon powder through a PTFE filter, and the mixture was stirred. Thereafter, 2-butanone was distilled off while stirring under reduced pressure (temperature: 40°C, pressure: 30 hPa) to obtain a composition containing carboxyl group-containing polycarbonate diol 1-1.

The resulting composition containing carboxyl group-containing polycarbonate diol 1-1 was fed to a thin film distillation apparatus at a flow rate of 20 g/min, and subjected to thin film distillation (temperature: 210°C, pressure: 53 Pa) to obtain carboxyl group-containing polycarbonate diol 1. -1 was obtained. As the thin-film distillation apparatus, a molecular distillation apparatus MS-300 special type manufactured by Shibata Scientific Co., Ltd. with an internal condenser and a jacket having a diameter of 50 mm, a height of 200 mm and an area of 0.0314 m ² was used.

This carboxyl group-containing polycarbonate diol 1-1 contains a structural unit represented by the following formula (A1) and a structural unit represented by the following formula (B1), and the analysis results thereof are as follows. .

Hydroxyl value: 22.9mg/g-KOH
Acid value: 48.9mg/g-KOH
Number average molecular weight: 1578
Molecular weight distribution (Mw/Mn): 1.85 (Mw: 5124, Mn: 2770)
Structural unit (A1): Structural unit (B1) = 90:10 (molar ratio)
Average carbon number: 3.9
Ester bond rate: 0%

[Example I-2]

<Step D: Production of unsaturated bond-containing dihydroxy compound>
1,6-Hexanediol (16HD): 331.1 g, diethyl fumarate: 179.0 g, titanium tetra n-butoxide: 1 in a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator. 0.45 g was added, and the atmosphere was replaced with nitrogen gas. While stirring, the internal temperature was raised to 120° C., the reaction was carried out at normal pressure for 1 hour while removing the distilled ethanol, and the pressure was lowered to 10 kPa over 2 hours. After confirming that ethanol equivalent to twice the molar amount of diethyl fumarate was distilled, a solution of a mixture of bis(hydroxyhexyl) fumarate (compound 2-A) and 1,6-hexanediol (16HD) was added. Obtained.

<Step E: Polymerization step>
Diethyl carbonate (DEC): 1810.5 g was added to the solution of the mixture of bis(hydroxyhexyl) fumarate (compound 2-A) and 1,6-hexanediol (16HD) obtained in step D, and the mixture was heated to 100-180°C. The temperature was raised over 6 hours, and the reaction was carried out under normal pressure while distilling off ethanol, and then the pressure was reduced to 10 kPa over 5 hours. Thereafter, the pressure was reduced to 1 kPa to distill off the remaining monomers to obtain polycarbonate diol 2-B having unsaturated bonds.

<Step F: Carboxyl Group Introduction Step>
After cooling the reaction solution in step E to 90° C., 36.7 g of triethylamine and 16.7 g of 2-mercaptoacetic acid were added and heated at 90° C. for 3 hours. The resulting reaction solution was evacuated to 1 kPa to distill off the remaining monomer to obtain a carboxyl group-containing polycarbonate diol 1-2.

The obtained carboxyl group-containing polycarbonate diol 1-2 contains a structural unit represented by the following formula (A2) and a structural unit represented by the following formula (B2), and the analysis results are as follows. Met.

Hydroxyl value: 50.1mg/g-KOH
Acid value: 13.1mg/g-KOH
Number average molecular weight: 1774
Molecular weight distribution (Mw/Mn): 1.80 (Mw: 5892, Mn: 3273)
Structural unit (A2): Structural unit (B2) = 97:3 (molar ratio)
Average carbon number: 6.3
Ester bond rate: 5.7%

[Synthesis and Evaluation of Polycarbonate Diol Not Containing Carboxyl Group]
[Reference example 1]
A polycarbonate diol was synthesized in the same manner as in step B of Reference Example I-1 without using compound 1-A.
1,4-butanediol (14BD): 380.7 g, diphenyl carbonate: 819.2 g, magnesium acetate tetrahydrate: 18 mg in a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator was added, and in the same manner as in step B, a polycarbonate diol 2-1 containing no carboxyl group was obtained.
The obtained polycarbonate diol 2-1 was composed only of structural units represented by the following formula (A1), and the analysis results thereof were as follows.

Hydroxyl value: 75.0mg/g-KOH
Acid value: 0.01 mg/g-KOH or less Number average molecular weight: 1496
Average carbon number: 4.0
Ester bond rate: 0%

[Production and Evaluation of Polyurethane]
[Example II-1]
A separable flask equipped with a thermocouple and a cooling tube was charged with 69.8 g of the carboxyl group-containing polycarbonate diol 1-1 obtained in Example I-1 and 2-1 of the polycarbonate diol obtained in Reference Example 1: 111 g. 1 g of N-methylpyrrolidone, 100 g of N-methylpyrrolidone, and 53.9 g of 4,4′-dicyclohexylmethane diisocyanate (H12MDI, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the temperature was raised to 80°C. Thereafter, 12 mg of Neostan U-830 (hereinafter referred to as U-830, manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization catalyst, the temperature of the oil bath was raised to 100° C., and the mixture was further stirred for about 4 hours. The concentration of isocyanate groups was analyzed to confirm that the theoretical amount of isocyanate groups had been consumed. After that, 5.5 g of triethylamine was added, and the mixture was further heated at 60° C. for 1 hour to obtain a prepolymer liquid (hereinafter abbreviated as PP liquid).

287 g of demineralized water was added to a 1 L SUS reactor equipped with a stirrer (PRE LUTION manufactured by PREMIX). After that, 287 g of PP liquid heated to 60° C. was slowly added while stirring at 2000 rpm to disperse the PP liquid in water. Thereafter, 4.4 g of ethylenediamine was added as a chain extender and stirred at 20°C. Stirring was continued while the molecular weight was analyzed by GPC, and after 5 hours, 3.3 g of diethylamine was added to terminate the chain extension reaction to obtain an aqueous polyurethane dispersion (polyurethane concentration: 30% by weight).
This aqueous polyurethane dispersion was applied to a glass plate in a uniform film thickness and dried in a dryer to obtain a polyurethane film.
Table 1 shows the evaluation results of the physical properties of this polyurethane aqueous dispersion and polyurethane film.

[Comparative Example 1]
Dimethylolpropionic acid was used in place of the carboxyl group-containing polycarbonate diol 1-1 so that the molar amount of carboxyl groups contained in the aqueous polyurethane dispersion was the same as that of the aqueous polyurethane dispersion produced in Example II-1. Then, the composition was determined and synthesized.

In a separable flask equipped with a thermocouple and a cooling tube, dimethylolpropionic acid: 15.4 g, polycarbonate diol 2-1 obtained in Reference Example 1: 299.7 g, N-methylpyrrolidone: 244 g, 4,4' -Dicyclohexylmethane diisocyanate (H12MD, manufactured by Tokyo Chemical Industry Co., Ltd.): 141.1 g was added, and the temperature was raised to 80°C. Thereafter, 28 mg of Neostan U-830 (hereinafter referred to as U-830, manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization catalyst, the temperature of the oil bath was raised to 100° C., and the mixture was further stirred for about 4 hours. The concentration of isocyanate groups was analyzed to confirm that the theoretical amount of isocyanate groups had been consumed. After that, 11.0 g of triethylamine was added and further heated at 60° C. for 1 hour to obtain a prepolymer liquid (PP liquid).

275 g of demineralized water was added to a 1 L SUS reactor equipped with a stirrer (PRE LUTION manufactured by PREMIX). After that, 275 g of a PP liquid heated to 60° C. was slowly added while stirring at a rotation speed of 2000 rpm to disperse the PP liquid in water. Thereafter, 4.4 g of ethylenediamine was added as a chain extender and stirred at 20°C. Stirring was continued while the molecular weight was analyzed by GPC, and after 5 hours, 3.3 g of diethylamine was added to terminate the chain extension reaction to obtain an aqueous polyurethane dispersion (polyurethane concentration: 30% by weight).
This aqueous polyurethane dispersion was applied to a glass plate in a uniform film thickness and dried in a dryer to obtain a polyurethane film.
Table 1 shows the evaluation results of the physical properties of this polyurethane aqueous dispersion and polyurethane film.

In the tables, polycarbonate diol 1-1 is abbreviated as "PCD1-1", polycarbonate diol 2-1 as "PCD2-1", and dimethylolpropionic acid as "DMPA".

Comparison between Example II-1 and Comparative Example 1 reveals the following.
The polyurethane of Example II-1 has smaller values of 100% M and 300% M in a tensile test than the polyurethane of Comparative Example 1, and has high flexibility. Further, the polyurethane of Example II-1 has a higher breaking elongation value and a higher strength than the polyurethane of Comparative Example 1 in a tensile test.
Further, the polyurethane of Example II-1 has a smaller weight change rate in the solvent resistance test than the polyurethane of Comparative Example 1, and has high solvent resistance.
Furthermore, the aqueous urethane dispersion of Example II-1 can be stored for a long period of time without agglomeration, and has high storage stability.

Claims (22)

Consisting of a random copolymer containing two or more carbonate structural units,
A polycarbonate diol having a number average molecular weight (Mn) of 500 to 5000 and a molecular weight distribution (Mw/Mn) of 1.6 or more,
having a structural unit containing a carboxyl group,
The average value of the number of carbon atoms introduced into the carbonate structural unit of the polycarbonate diol derived from the carbon atoms present between the two hydroxyl groups of the raw material dihydroxy compound of the polycarbonate diol (hereinafter, this value is referred to as the "average carbon number ”) is 3.5 to 10.0 ,
A polycarbonate diol comprising a structural unit represented by the following formula (D) .

(However, R ³ and R ⁴ each independently represent an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and contain a heteroatom of O, S, or N. L ² is a heteroatom-containing linking group of 1 to 12 carbon atoms selected from O, S and N.) 2. The polycarbonate diol according to claim 1, wherein the average carbon number is 3.5 to 7.0. 3. The polycarbonate diol according to claim 1, which has an acid value of 1 mg/g-KOH or more and 100 mg/g-KOH or less. 4. The polycarbonate diol according to any one of claims 1 to 3, comprising a structural unit represented by the following formula (A).

(However, R ¹ represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms and may contain a heteroatom of O, S, N. ) The ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula ( D ) is represented by the molar ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula (D) . 5. The polycarbonate diol according to claim 4, wherein the structural unit is 50:50 to 99:1. The ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula ( D ) is represented by the molar ratio of the structural unit represented by the formula (A) to the structural unit represented by the formula (D) . 6. The polycarbonate diol according to claim 5, wherein the structural unit is 80:20 to 99:1. 7. The polycarbonate diol according to any one of claims 4 to 6, wherein R ¹ in formula (A) is an aliphatic hydrocarbon group having 4 to 6 carbon atoms. 8. The polycarbonate diol according to any one of claims 1 to 7, wherein the structural unit represented by formula (D) is a structural unit represented by formula (D1) below.

(However, R ³ has the same definition as in formula (D).) The polycarbonate diol according to any one of claims 1 to 8 (hereinafter referred to as "polycarbonate diol 1") and a polycarbonate diol containing no carboxyl group (hereinafter referred to as "polycarbonate diol 2"). Polycarbonate diol composition. 10. The polycarbonate diol composition according to claim 9 , wherein said polycarbonate diol 2 is a polycarbonate diol containing a structural unit represented by said formula (A). A polyurethane using the polycarbonate diol according to any one of claims 1 to 8 or the polycarbonate diol composition according to claim 9 or 10 . An aqueous polyurethane dispersion using the polycarbonate diol according to any one of claims 1 to 8 or the polycarbonate diol composition according to claim 9 or 10 , an isocyanate and a chain extender. Artificial leather or synthetic leather using the polyurethane according to claim 11 . A paint or coating agent using the polyurethane according to claim 11 . An elastic fiber using the polyurethane according to claim 11 . A water-based polyurethane paint using the polyurethane according to claim 11 . A pressure-sensitive adhesive or adhesive using the polyurethane according to claim 11 . An active energy ray-curable polymer composition using the polycarbonate diol according to any one of claims 1 to 8 or the polycarbonate diol composition according to claim 9 or 10 . In the method for producing a polycarbonate diol according to any one of claims 1 to 8,
A method for producing a carboxyl group-containing polycarbonate diol in which the following steps 1 and 2 are performed in this order.
Step 1: Polymerization step of reacting a dihydroxy compound having a carboxyl group precursor group with a carbonate compound to obtain a polycarbonate diol Step 2: Conversion of converting the carboxyl group precursor group of the polycarbonate diol obtained in Step 1 into a carboxyl group process In the method for producing a polycarbonate diol according to any one of claims 1 to 8,
A method for producing a carboxyl group-containing polycarbonate diol by performing the following steps 1-1 and 2-1 in this order.
Step 1-1: Polymerization step of reacting a dihydroxy compound having a protected carboxyl group with a carbonate compound to obtain a polycarbonate diol Step 2-1: Removing the protective group of the carboxyl group of the polycarbonate diol obtained in Step 1-1 Deprotection step to release In the method for producing a polycarbonate diol according to any one of claims 1 to 8,
A method for producing a carboxyl group-containing polycarbonate diol by performing the following steps 1-2 and 2-2 in this order.
Step 1-2: Polymerization step of reacting a dihydroxy compound having an unsaturated bond with a carbonate compound to obtain a polycarbonate diol Step 2-2: With respect to the unsaturated bond of the polycarbonate diol obtained in Step 1-2, carboxyl A carboxyl group introduction step of reacting a group-introducing compound to introduce a carboxyl group In the method for producing a polycarbonate diol according to any one of claims 1 to 8,
A carboxyl group-containing polycarbonate diol for producing a polycarbonate diol having a structural unit represented by the following formula (D2) by reacting a polycarbonate diol having a structural unit represented by the following formula (X) with a compound having a mercapto group. manufacturing method.

(However, R ³ represents an aliphatic hydrocarbon group having a main chain of 4 to 12 carbon atoms, may have a branched chain, and may contain a heteroatom of O, S, or N. L ³ is It is a hydrocarbon group having 1 to 12 carbon atoms and may have a branched chain.)