JP2023039907A - Polycarbonate polyol composition - Google Patents

Abstract

A polycarbonate polyol having a narrow molecular weight distribution, high thermal stability, low viscosity, high storage stability, and excellent handleability is provided. A composition containing a polycarbonate polyol. The polycarbonate polyol satisfies the following conditions (1) to (4). (1) at least one of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and a halogen atom, or a carbon that may have a substituent containing these atoms and may have a side chain substituent (2) a number average molecular weight (Mn) of 300 or more and 8000 or less (3) a molecular weight distribution (D) of 1.7 or less (4) a molecular weight calculated by the following formula Distribution change rate (ΔD) is 0.20 or less Molecular weight distribution change rate (ΔD)=(D1−D)/DD: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours Fig. 1

Description

TECHNICAL FIELD The present invention relates to a polycarbonate polyol composition useful as a raw material for polycarbonate-based polyurethane and a method for producing the same. The present invention also relates to a polyurethane using this polycarbonate polyol composition and a method for producing the same.

Conventionally, polyols used as raw materials for the soft segments of polyurethanes produced on an industrial scale include ether types such as polypropylene glycol and polytetramethylene glycol, polyester polyol types such as adipate esters, and polycaprolactone. It is classified into a polylactone type represented by polylactone type and a polycarbonate type represented by polycarbonate diol.

Among them, polycarbonate diol is synthesized by transesterification of a diol compound such as 1,6-hexanediol and a carbonate compound such as dimethyl carbonate. Polyurethane using polycarbonate diol is considered to be the best durable grade in terms of heat resistance and hydrolysis resistance, and is widely used as durable films, artificial leather for automobiles, (water-based) paints, and adhesives (non-patented). Reference 1).

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

Polycarbonate diols obtained by conventional transesterification reactions have a wide molecular weight distribution and contain a wide range of low-molecular-weight substances to high-molecular-weight substances. was there. Moreover, when a polycarbonate diol having a wide molecular weight distribution is used to produce a polyurethane, the high-molecular-weight component precipitates during the urethane reaction and causes turbidity after the polyurethane is formed. On the other hand, the inclusion of low-molecular-weight components poses a problem of volatile matter during heat processing and a decrease in thermal stability during use.
In addition, even polycarbonate diols with a narrow molecular weight distribution immediately after production are thermally unstable due to the influence of residual impurities. There was a problem that the physical properties of the resulting polyurethane changed.

The present invention provides a polycarbonate polyol that has a narrow molecular weight distribution and high thermal stability, which could not be achieved by conventional techniques, and is excellent in handleability due to low viscosity and high storage stability. It is an object of the present invention to provide a polycarbonate polyol composition capable of obtaining a polyurethane having an excellent balance of physical properties such as flexibility and mechanical strength in addition to the chemical resistance and heat resistance inherent in polyurethane.

Means for Solving the Problems As a result of repeated investigations to solve the above conventional problems, the inventors of the present invention have found that the above problems can be solved by a polycarbonate polyol composition containing a polycarbonate polyol that satisfies specific conditions, and have completed the present invention. completed.
That is, the gist of the present invention is as follows.

[1] A polycarbonate polyol composition containing a polycarbonate polyol, wherein the polycarbonate polyol satisfies the following conditions (1) to (4).
(1) containing a structural unit A represented by the following formula (A); (2) having a number average molecular weight (Mn) of 300 or more and 8000 or less; Calculated molecular weight distribution change rate (ΔD) after heating at 100 ° C. for 12 hours is 0.20 or less Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

(In the formula (A), R ₁ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms.)

[2] The polycarbonate polyol composition according to [1], wherein the polycarbonate polyol further contains a structural unit B represented by the following formula (B).

(In the formula (B), R ₂ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms, provided that R ₂ is different from R ₁ in the formula (A).)

[3] Among the molecular chain ends of the polycarbonate polyol, the ratio of -R ₁ -OH groups is 80 mol% or more with respect to 100% of the total molar amount of all terminal groups, [1] or [2] Polycarbonate polyol composition according to.

[4] The polycarbonate polyol composition according to any one of [1] to [3], wherein the polycarbonate polyol has 1.8 to 6.0 terminal hydroxyl groups per molecule.

[5] The polycarbonate polyol composition according to any one of [1] to [4], wherein the total content of metal elements and phosphorus elements in the composition is 150 mass ppm or less.

[6] The polycarbonate polyol composition according to any one of [1] to [5], wherein the elemental phosphorus content in the composition is 0.01 to 150 mass ppm.

[7] The polycarbonate polyol composition according to any one of [1] to [6], wherein the elemental sodium content in the composition is 0.01 to 150 mass ppm.

[8] The polycarbonate polyol composition according to any one of [1] to [7], which contains a phosphorus compound having an aromatic ring.

[9] The content of cyclic carbonate X represented by the following formula (1) in the composition is 1% by mass or less with respect to 100% of the total mass of the composition [1] to [8] Polycarbonate polyol composition according to any one of.

(In Formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.)

[10] The polycarbonate polyol composition according to [9], wherein the cyclic carbonate X is represented by the following formula (1A).

(In formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.)

[11] The content of the structural unit A in the polycarbonate polyol is 70 mol% or more with respect to 100% of the total molar amount of all structural units constituting the polycarbonate polyol, [1] to [10] Polycarbonate polyol composition according to any one of.

[12] The polycarbonate polyol composition according to any one of [1] to [11], wherein the polycarbonate polyol is produced using a plant-derived raw material.

[13] The method according to any one of [1] to [12], comprising a step of ring-opening polymerization of a cyclic carbonate X represented by the following formula (1) in the presence of a polymerization catalyst using polyol Y as an initiator. A method for producing a polycarbonate polyol composition.

(In Formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.)

[14] The method for producing a polycarbonate polyol composition according to [13], wherein the cyclic carbonate X is represented by the following formula (1A).

(In the formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.)

[15] The method for producing a polycarbonate polyol composition according to [14], wherein the cyclic carbonate X is trimethylene carbonate.

[16] The polyol Y may have at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms. The method for producing a polycarbonate polyol composition according to any one of [13] to [15], which is a diol compound or triol compound of numbers 2 to 50.

[17] Any one of [13] to [16], wherein the polyol Y is at least one oligomer polyol selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and silicone polyols. A process for making the described polycarbonate polyol composition.

[18] The method for producing a polycarbonate polyol composition according to any one of [13] to [17], including a step of deactivating and/or removing the polymerization catalyst after the ring-opening polymerization.

[19] The ring-opening polymerization is performed using the polymerization catalyst containing elemental phosphorus in an amount of elemental phosphorus of 0.01 to 1000 ppm by mass with respect to the total weight of the cyclic carbonate X and the polyol Y, [ 13] A method for producing a polycarbonate polyol composition according to any one of [18].

[20] Any of [13] to [19], wherein the ring-opening polymerization is performed using a solvent of 50 parts by mass or less with respect to 100 parts by mass of the cyclic carbonate X and the polyol Y, or without using a solvent. 2. A method for producing a polycarbonate polyol composition according to claim 1.

[21] A polyurethane obtained using the polycarbonate polyol composition according to any one of [1] to [12].

[22] The polyurethane according to [21], which is produced using a polyisocyanate, a chain extender, and the polycarbonate polyol composition.

[23] A method for producing polyurethane using the polycarbonate polyol composition according to any one of [1] to [12].

[24] Obtaining a polycarbonate polyol composition by the method for producing a polycarbonate polyol composition according to any one of [13] to [20], and producing a polyurethane using the obtained polycarbonate polyol composition. A method for producing a polyurethane, comprising:

The polycarbonate polyol composition of the present invention has a narrow molecular weight distribution, high thermal stability, low viscosity and high storage stability, and is excellent in handleability.
In addition, the polyurethane produced using the polycarbonate polyol composition of the present invention has excellent physical property balance such as flexibility and mechanical strength in addition to the original chemical resistance and heat resistance of polyurethane using polycarbonate polyol. It is suitable for use in elastic fibers, synthetic or artificial leather, paints, high-performance elastomers, and is extremely useful industrially.

5 is a graph showing viscoelasticity measurement results (Log E′ (Pa)/temperature (° C.)) in Example 5-1 and Comparative Example 5-1. 5 is a graph showing viscoelasticity measurement results (tan δ/temperature (° C.)) in Example 5-1 and Comparative Example 5-1.

Hereinafter, the embodiments of the present invention will be described in detail, 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 present invention.

[Polycarbonate polyol composition]
The polycarbonate polyol composition of the present invention is a composition containing a polycarbonate polyol, wherein the polycarbonate polyol satisfies the following conditions (1) to (4).
(1) containing a structural unit A represented by the following formula (A); (2) having a number average molecular weight (Mn) of 300 or more and 8,000 or less; Calculated molecular weight distribution change rate (ΔD) after heating at 100 ° C. for 12 hours is 0.20 or less Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of the polycarbonate polyol composition D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

(In the formula (A), R ₁ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms.)

The polycarbonate polyol composition of the present invention is a polycarbonate polyol produced by ring-opening polymerization using a polyol Y having two or more hydroxyl groups and a cyclic carbonate X as initiators serving as polymerization starting points, as described later. A polymerization catalyst is usually used for this ring-opening polymerization to promote the ring-opening polymerization.
The number of hydroxyl groups in one molecule of the polycarbonate polyol produced in this way is equal to the number of hydroxyl groups in one molecule of the initiator polyol Y unless a side reaction occurs.

On the other hand, the produced polycarbonate polyol contains, in addition to the target polycarbonate polyol, impurities such as by-products with non-hydroxyl-terminated terminals and residual polymerization catalysts and raw material monomers, so it is called a "polycarbonate polyol composition." However, the content of the polycarbonate polyol in the polycarbonate polyol composition is usually 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more with respect to 100% by mass of the total mass of the polycarbonate polyol composition, It is more preferably 95% by mass or more, particularly preferably 98% by mass or more, and is generally marketed or handled as "polycarbonate polyol".
Therefore, hereinafter, the polycarbonate polyol composition of the present invention is referred to as "the polycarbonate polyol of the present invention" or simply "polycarbonate polyol", but as described above, the polycarbonate polyol contains a polymerization catalyst and other impurities.

<Structural unit A>
The polycarbonate polyol in the present invention contains a structural unit A represented by the following formula (A).

(In the formula (A), R ₁ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms.)

Structural unit A is a structural unit derived from cyclic carbonate X described below, which is a raw material for producing the polycarbonate polyol of the present invention.
R ₁ may be derived from the cyclic carbonate X described later and introduced into the polycarbonate polyol of the present invention. R ₁ has 3 or more carbon atoms, and there is no particular upper limit. From the viewpoint of chemical resistance, low-temperature properties, and heat resistance of the polyurethane obtained using the polycarbonate polyol, the number of carbon atoms in R ₁ is preferably as small as possible, and the number of carbon atoms in R ₁ is preferably 20 or less, more preferably 10 or less. A carbon number of 8 or less is more preferable, and a carbon number of 6 or less is particularly preferable.
In particular, the number of carbon atoms in the main chain portion of R ₁ , excluding side chain substituents, is preferably 3 to 10, particularly 3 to 6, and particularly preferably 3 to 4. From the point of view, 3 is most preferable.

<Structural unit B>
The polycarbonate polyol in the present invention may contain a structural unit B represented by the following formula (B) in addition to the structural unit A described above.

(In the formula (B), R ₂ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms, provided that R ₂ is different from R ₁ in the formula (A).)

Structural unit B is a structural unit derived from later-described polyol Y, which is a raw material for producing the polycarbonate polyol of the present invention.
R ₂ may be derived from polyol _Y described later and introduced into the polycarbonate polyol of the present invention. In particular, when it is 8 or more, the flexibility, mechanical strength and hydrolysis resistance of the polyurethane obtained using the polycarbonate polyol of the present invention are excellent, which is preferable. Although not particularly limited, the upper limit of the number of carbon atoms in R ₂ is usually 50 or less when the monomer polyol Y is used.

In formula (B) above, R ₂ is defined to be different from R ₁ in formula (A), but R ₁ and R ₂ being the same are not excluded. That is, when the cyclic carbonate X and the polyol Y have the same R ₁ -introducing portion and R ₂ -introducing portion, the structural unit A and the structural unit B are the same even if their origins are different. becomes.

A wide variety of substituents and linking groups can be introduced into the structural unit B derived from polyol Y described later, and various functions can be imparted by the substituents and linking groups.

For example, when a polyol having three or more hydroxyl groups is used as the polyol Y, a structural unit having a crosslinked structure represented by the following formula (B-1) is introduced as the structural unit B into the polycarbonate polyol of the present invention. be done. By introducing such a crosslinked structure, the polyurethane obtained using the polycarbonate polyol of the present invention may be improved in solvent resistance, heat resistance, tensile strength and hardness.

(In formula (B-1), R ₃ represents a residue when R ₂ in formula (B) has a side chain substituent via an oxygen atom.)

<Substituent in Polycarbonate Polyol>
The above structural unit (A) and structural unit (B) are each at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms. may have. In particular, polyol Y from which the structural unit (B) is derived is easily available as a compound having various substituents and linking groups. It is preferable to introduce As the substituent, those containing an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a halogen atom are preferred, and those containing an oxygen atom or a nitrogen atom are particularly preferred. Among these, ether groups and carboxyl groups are preferred as substituents containing an oxygen atom from the viewpoint of improving affinity with water and dispersibility, and are suitable for use in water-based polyurethane dispersants. Amide groups and isocyanuric groups are particularly preferred as the nitrogen atom-containing substituents because they improve the compatibility between the polycarbonate polyol and the polyurethane and improve the transparency.

<Proportion of Structural Unit A and Structural Unit B>
The proportions of structural unit A and structural unit B in the polycarbonate polyol of the present invention depend on the proportions of cyclic carbonate X and polyol Y used as starting materials, respectively. If the ratio of the structural unit A is too small, the amount of the structural unit B becomes relatively large, and the molecular weight of the polycarbonate polyol cannot be increased to an appropriate amount. In addition, the amount of carbonate bonds may decrease, and the solvent resistance and mechanical strength may decrease. On the other hand, if the ratio of the structural unit B is too small, the effects of the substituents and the crosslinked structure of the structural unit B cannot be exhibited sufficiently.
The preferred ratio of structural unit A to structural unit B (hereinafter sometimes referred to as "(A):(B)") is (A):(B) = 2:1 to 500:1 in terms of molar ratio. is preferred, 5:1 to 200:1 is more preferred, and 10:1 to 100:1 is even more preferred.
The proportion of the structural unit A and the structural unit B in the polycarbonate polyol can be calculated from the charge ratio and conversion of the cyclic carbonate X and the polyol Y used as raw materials. In addition, similar values can also be obtained by NMR analysis or gas chromatography analysis of each dihydroxy compound obtained by hydrolysis with an alkali.

The polycarbonate polyol in the present invention particularly contains the structural unit A at a content ratio of 70 mol% or more with respect to 100% of the total molar amount of all structural units constituting the polycarbonate polyol, thereby improving solvent resistance and strength. The content of the structural unit A is more preferably 80 mol % or more, still more preferably 85 mol % or more, and particularly preferably 90 mol % or more.
On the other hand, in order to obtain various functions by the structural unit B, the content of the structural unit A is 99 mol% or less, particularly 98 mol%, relative to the total molar amount of 100% of all structural units constituting the polycarbonate polyol. The following are preferred.

The polycarbonate polyol of the present invention contains structural units other than the structural units A and B, and structural units in which the structural units A and B are changed due to transesterification or the like during the ring-opening polymerization during the production of the polycarbonate polyol. Although there are cases, the total structural units of the polycarbonate polyol of the present invention usually correspond to the sum of the structural unit A and the structural unit B.

<Number average molecular weight (Mn)>
The polycarbonate polyol of the present invention has a number average molecular weight (Mn) of 300 or more and 8,000 or less. The lower limit of the number average molecular weight (Mn) of the polycarbonate polyol of the present invention is preferably 350, more preferably 400. On the other hand, the upper limit is preferably 7,000, more preferably 6,000, even more preferably 5,000. If the Mn of the polycarbonate polyol is less than the above lower limit, sufficient flexibility may not be obtained when made into urethane. On the other hand, if the above upper limit is exceeded, the viscosity increases, which may impair the handling during polyurethane formation.
Here, the number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight, and can be usually determined by measurement by gel permeation chromatography (sometimes abbreviated as GPC). A specific measuring method is as described in the section of Examples below.

In addition, when the analysis by GPC is difficult, the number average molecular weight (Mn) calculated from the analysis by NMR or the number average molecular weight (Mn) obtained by calculation from the hydroxyl value may be used as well. . These measurement methods are also described in the Examples section below, but the number average molecular weight (Mn) of the polycarbonate polyol of the present invention measured by NMR is 200 or more for the same reason as above. It is preferably 300 or more, more preferably 350 or more, while it is preferably 8000 or less, more preferably 7000 or less, and further preferably 6000 or less. preferable.
Further, the number average molecular weight (Mn) obtained from the hydroxyl group is preferably 200 or more, more preferably 300 or more, further preferably 350 or more for the same reason as above, while 8000 It is preferably 7000 or less, more preferably 6000 or less.

The lower limit of the hydroxyl value of the polycarbonate polyol of the present invention determined by the method described in Examples section below is preferably 5 mgKOH/g, more preferably 10 mgKOH/g, still more preferably 15 mgKOH/g, and the upper limit is It is preferably 500 mgKOH/g, more preferably 450 mgKOH/g, still more preferably 400 mgKOH/g. If the hydroxyl value is less than the above lower limit, the viscosity becomes too high and handling may become difficult during polyurethane formation.

<Molecular weight distribution (D)>
The polycarbonate polyol in the present invention has a molecular weight distribution (D) of 1.7 or less. The molecular weight distribution (D) is calculated by weight average molecular weight/number average molecular weight (Mw/Mn). The molecular weight distribution (D) of the polycarbonate polyol of the present invention is preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.3 or less, particularly preferably 1.2 or less, and most preferably 1.2 or less. 1 or less. When the molecular weight distribution (D) is equal to or less than the above upper limit, the viscosity of the polycarbonate polyol is lowered and the handleability is excellent. In addition, since the molecular weight of the polyol in the polyurethane obtained by using this polycarbonate polyol is uniform, the crystallinity is enhanced, and the strength and elasticity of the polyurethane during expansion and contraction are improved. Moreover, heat resistance may improve. In addition, since the amount of low-molecular-weight substances is reduced and a uniform soft segment structure can be formed, mechanical durability such as sag resistance, impact resistance, and wear resistance may be improved. On the other hand, if the molecular weight distribution (D) is too low, the crystallinity of the polycarbonate polyol will improve, and handling may become difficult. In such cases, it may be better to adjust the molecular weight distribution (D) to an appropriate value. Here, the weight average molecular weight (Mw) is the weight average molecular weight in terms of polystyrene, and the number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene. A specific measuring method is as described in the section of Examples below. Generally commercially available polycarbonate diols are produced by transesterification of diol monomers and carbonate compounds (dialkyl carbonate, ethylene carbonate, diphenyl carbonate, etc.) and have a molecular weight distribution (D) of 2.0 or more.

Polycarbonate polyols with a molecular weight distribution (D) of more than 1.7 contain a wide range of low-molecular-weight substances to high-molecular-weight substances. There's a problem. Further, when a polycarbonate polyol having a wide molecular weight distribution is used to produce a polyurethane, a high molecular weight component precipitates during the urethane reaction, or becomes a cause of turbidity after the polyurethane is formed. On the other hand, the low-molecular-weight component becomes a volatile matter during processing and heating, and causes a decrease in thermal stability and coloration during use.

Although the technique for adjusting the molecular weight distribution (D) of the polycarbonate polyol to 1.7 or less is not particularly limited, it can be achieved, for example, by appropriately combining the following techniques.
A polycarbonate polyol is polymerized by ring-opening polymerization using a polyol Y as a starting point for polymerization and a cyclic carbonate X as raw materials.
By increasing the purity of the raw materials to be used, impurities that inhibit ring-opening polymerization and cause side reactions that widen the molecular weight distribution are removed.
By selecting an appropriate polymerization catalyst and manufacturing process (temperature, pressure, polymerization time, solvent, concentration, etc.), side reactions (transesterification and end-capping) that broaden the molecular weight distribution are suppressed before polymerization.
Post-treatments such as deactivation of the catalyst, removal of the catalyst, removal of residual monomers and impurities are carried out appropriately so that the molecular weight distribution of the obtained polycarbonate diol does not widen.
Purification steps (filtration, crystallization, distillation, liquid separation, etc.) are carried out so as to narrow the molecular weight distribution.

<Molecular weight distribution change rate (ΔD)>
The molecular weight distribution (D) of the polycarbonate polyol may increase due to the progress of the transesterification reaction due to heating or the like. Especially when a metal catalyst or the like involved in transesterification is contained, the tendency of the increase is remarkable. When the molecular weight distribution (D) of the polycarbonate polyol changes, the viscosity, melting point, and the like increase during storage and handling (dissolution, transfer, reaction, etc. under heating), resulting in poor handleability. In addition, there is a problem that the quality of the polyurethane obtained by the reaction under heating is not stable and the physical properties are deteriorated. For this reason, the molecular weight distribution (D) does not change under heating at about 100°C, which is a suitable temperature for storing and handling (dissolution, transfer, reaction, etc. under heating) of a highly viscous polycarbonate polyol. Small polycarbonate polyols are preferred.

In the present invention, regarding the degree of change in molecular weight distribution (D) due to heating, the rate of change in molecular weight distribution (ΔD) after heating at 100° C. for 12 hours calculated by the following formula is used as an index. This molecular weight change rate (ΔD) is characterized by being 0.20 or less.
Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

As a polycarbonate polyol having suitable thermal stability for stable storage and handling (dissolution, transfer, reaction, etc. under heating), the polycarbonate polyol in the present invention has this molecular weight distribution change rate ( ΔD) is 0.20 or less, preferably 0.18 or less, more preferably 0.15 or less, still more preferably 0.12 or less, and 0.10 or less. Especially preferred.
When the molecular weight distribution change rate (ΔD) exceeds 0.20, the viscosity of the polycarbonate polyol increases during storage or handling (dissolution, transfer, reaction, etc. under heating), or the polycarbonate polyol is used to produce polyurethane. During the production of , the molecular weight distribution widens, the mechanical strength and solvent resistance of the polyurethane are lowered, and high molecular weight components are formed, which may cause turbidity and coloration of the polyurethane.

A reduction in the rate of change in molecular weight distribution (ΔD) of the polycarbonate polyol can be achieved by making the resulting polycarbonate polyol product less susceptible to transesterification. The method is not particularly limited, but includes, for example, the following methods.
- When producing a polycarbonate polyol, use a polymerization catalyst that selectively acts only on the ring-opening polymerization of the cyclic carbonate X and does not act on the transesterification reaction of the product polycarbonate polyol. Examples of such a polymerization catalyst include, among the phosphorus compounds of the polymerization catalyst described later, particularly phosphorus compounds having an aromatic ring, sodium compounds described later, and the like.
- Reduce the amount of polymerization catalyst used in the production of polycarbonate polyol. Specifically, the total mass of the cyclic carbonate X and the polyol Y is 10,000 mass ppm or less, for example, 0.01 to 1,000 mass ppm, preferably 0.01 to 500 mass ppm.
- During the production of polycarbonate polyol, the conversion rate of cyclic carbonate is increased to reduce the residual amount in the polycarbonate polyol.
- The polymerization catalyst remaining in the produced polycarbonate polyol is deactivated with a catalyst deactivator, which will be described later.
- The polymerization catalyst remaining in the produced polycarbonate polyol is removed by crystallization, degassing, reprecipitation, washing, column chromatography, distillation, or the like.
- By-products, residual monomers, and residual solvents remaining in the produced polycarbonate polyol are removed by crystallization, degassing, reprecipitation, washing, column chromatography, distillation, and the like.
- By heating or cooling the produced polycarbonate polyol, the remaining polymerization catalyst is deactivated or precipitated and removed.
- A pH stabilizer, an acid or a base is added to the produced polycarbonate polyol to neutralize and deactivate the catalyst and impurities.
- Removing catalysts and impurities by centrifuging and filtering manufactured polycarbonate polyols.
Although each of these techniques can be effective alone, there are cases in which a greater effect can be obtained by combining multiple techniques.

<Percentage of terminal —R ₁ —OH groups>
In the polycarbonate polyol of the present invention, the ratio of —R ₁ —OH groups (wherein R ₁ is R ₁ in the formula (A)) among the molecular chain terminals of the polycarbonate polyol is It is preferably 80 mol % or more with respect to 100 mol %. If the proportion of -R ₁ -OH groups is 80 mol % or more, the reactivity during urethane polymerization is constant at many OH terminals, uniform polymerization proceeds, and a high-strength polyurethane with a narrow molecular weight distribution can be obtained. The --R ₁ --OH group ratio is more preferably 85 mol % or more, and still more preferably 90 mol % or more. The upper limit of the ratio of --R ₁ --OH groups is not particularly limited and may be 100 mol %.
In order to make the ratio of —R ₁ —OH groups equal to or higher than the above lower limit, for example, the following methods can be used.
By increasing the purity of the raw materials to be used, impurities that inhibit ring-opening polymerization and cause side reactions that widen the molecular weight distribution are removed.
By selecting an appropriate polymerization catalyst and manufacturing process (temperature, pressure, polymerization time, solvent, concentration, etc.), side reactions (transesterification and end-capping) that broaden the molecular weight distribution are suppressed before polymerization.
Post-treatments such as deactivation of the catalyst, removal of the catalyst, removal of residual monomers and impurities are carried out appropriately so that the molecular weight distribution of the obtained polycarbonate diol does not widen.

<Number of terminal hydroxyl groups per molecule>
The number of terminal hydroxyl groups per molecule of the polycarbonate polyol of the present invention is preferably 1.8 to 6.0. When the number of terminal hydroxyl groups per molecule is 1.8 or more, the molecular weight is sufficiently increased during polyurethane production, and a polyurethane having high strength and excellent solvent resistance can be obtained. On the other hand, if the number of terminal hydroxyl groups per molecule is 6.0 or less, the cross-linking reaction does not proceed excessively during polyurethane polymerization, suppressing the progress of gelation and viscosity increase, and the flexibility and flexibility of the obtained polyurethane. Impact resistance can be improved. From this point of view, the number of terminal hydroxyl groups per molecule of the polycarbonate polyol of the present invention is more preferably 1.80 to 5.0, still more preferably 1.90 to 4.0. For use as a particularly flexible polyurethane elastomer, it is most preferably 1.90 to 2.10, more preferably 1.95 to 2.05. Also, when used as high-strength polyurethane acrylate, polyurethane foam, or urethane coating, 2.0 to 4.0 is preferable.
The number of terminal hydroxyl groups per molecule of the polycarbonate polyol is determined by the method described in Examples below.

<Metal element/Phosphorus element content>
The polycarbonate polyol of the present invention usually contains a metal element and/or a phosphorus element derived from a polymerization catalyst during production.
When the metal compound and the phosphorus compound described below are used as the polymerization catalyst, the total content of the metal element and the phosphorus element in the polycarbonate polyol of the present invention is preferably 150 mass ppm or less, and preferably 120 mass ppm or less. More preferably, it is 100 mass ppm or less, and even more preferably 50 ppm or less. Although the lower limit of the total content of the metal elements and the phosphorus element is not particularly limited, it is usually 0.01 ppm by mass or more.

Further, when only the later-described phosphorus compound is used as the polymerization catalyst, the phosphorus element content in the polycarbonate polyol in the present invention is preferably 0.01 to 150 ppm by mass, more preferably 0.01 to 100 ppm by mass. is more preferable, and 0.01 to 50 ppm by mass is even more preferable.

Further, when only the metal compound described later, preferably a sodium compound, is used as the polymerization catalyst, the content of metal elements such as sodium in the polycarbonate polyol in the present invention is preferably 0.01 to 150 ppm by mass. It is more preferably 0.01 to 100 ppm by mass, even more preferably 0.01 to 50 ppm by mass.

If the content of any element in the polycarbonate polyol is more than the above upper limit, the polycarbonate polyol of the present invention may not have a molecular weight distribution change rate (ΔD) of 0.20 or less. In addition, it causes coloring of the polycarbonate polyol, and causes problems due to poor polymerization or accelerated polymerization during the urethane reaction.
On the other hand, in order to reduce the content of these elements, the operations for purifying the raw material, reducing the amount of the catalyst used, and deactivating and/or removing the residual catalyst become complicated, which impairs productivity. , is not preferable in terms of cost.

In order to make the content of the metal element and/or the phosphorus element in the polycarbonate polyol within the above range, the amount of the catalyst during the production of the polycarbonate polyol may be adjusted, or the produced polycarbonate polyol may be subjected to the deactivation and/or deactivation of the catalyst as described above. A process for removal may be performed.

<Coloring of Polycarbonate Polyol>
Coloration of polycarbonate polyol can be evaluated by APHA value in accordance with JIS K0071-1 (1998). The APHA value of the polycarbonate polyol of the present invention is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. If the APHA value exceeds 50, the color tone of the polyurethane obtained from the polycarbonate polyol as a raw material may be deteriorated, and the commercial value may be lowered, or the heat stability may be deteriorated. The APHA value of polycarbonate polyol is measured by the method described in the section below. Coloration can be reduced by appropriately selecting a catalyst, a polymerization method, a purification method, and the like, which will be described later.

<Residual monomers, etc.>
Cyclic carbonate X and polyol Y used as raw material monomers during production may remain in the polycarbonate polyol. The amount of the raw material monomers remaining in the polycarbonate polyol is not limited, but is preferably as small as possible. be. In particular, the content of the cyclic carbonate X represented by the following formula (1) in the polycarbonate polyol in the present invention is preferably 1% by mass or less with respect to 100% of the total mass of the polycarbonate polyol, and is preferably 0.5%. It is more preferably 0.3% by mass or less, further preferably 0.1% by mass or less. If the content of monomers such as cyclic carbonate X in the polycarbonate polyol is too high, the reaction during polyurethane formation may be inhibited, and the rate of change in molecular weight distribution (ΔD) may increase due to further reaction with the polycarbonate polyol during heating. . On the other hand, the lower limit is not particularly limited, but is preferably 0.1% by mass, more preferably 0.01% by mass, and still more preferably 0% by mass.
The content of the cyclic carbonate in the polycarbonate polyol is analyzed by H-NMR by converting the ratio of the peak of the cyclic carbonate used and the various structural units of the polymer into mass %. In some cases, analytical means such as GC and HPLC may also be used. The lower limit of the analytical value is 0.01% by mass. In order to reduce the amount of residual cyclic carbonate, the reaction conditions such as catalyst, temperature, and time should be optimized to improve the conversion rate of cyclic carbonate. There is a method such as removing in the operation such as.

(In the formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.)

The cyclic carbonate X represented by the formula (1) will be described in detail in the section <Cyclic carbonate X>, but the cyclic carbonate X is preferably represented by the following formula (1A).

(In formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.)

<Ingredients derived from plants>
As described below, the polycarbonate polyol in the present invention is preferably produced using a plant-derived raw material, that is, a plant-derived cyclic carbonate X or polyol Y, from the viewpoint of reducing environmental load.

[Method for producing polycarbonate polyol]
The method for producing the polycarbonate polyol of the present invention is not particularly limited, but it is preferably produced by carrying out ring-opening polymerization using a cyclic carbonate X and a polyol Y as an initiator as raw materials. In this case, in order to efficiently proceed the ring-opening polymerization, it is preferable to carry out the reaction with stirring at an appropriate reaction temperature using a normal polymerization catalyst.

For example, the polycarbonate polyol in the present invention is produced by ring-opening polymerization of a cyclic carbonate X represented by the following formula (1) using polyol Y as an initiator in the presence of a polymerization catalyst.

(In the formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.)

<Cyclic carbonate X>
The cyclic carbonate X is a compound having a carbon chain of a cyclic skeleton represented by the above formula (1) and a carbonate group, and is preferably represented by the following formula (1A) in terms of reactivity (ring-opening polymerizability) and availability. is a cyclic carbonate represented.

(In the formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.)

Particularly preferred cyclic carbonates X having high reactivity include linear diol-derived cyclic carbonates (trimethylene carbonate, tetramethylene carbonate, pentamethylene carbonate, hexamethylene carbonate, etc.), diol-derived cyclic carbonates having side chain substituents ( 2-methylpropanediol, neopentyl glycol, 2-butyl-2-ethylpropanediol, etc. as raw materials), carbonates synthesized from raw materials having two methylol groups (trimethylolpropane, pentaerythritol and Those using ether derivatives thereof, those using dimethylolpropionic acid, dimethylolbutanoic acid and ester derivatives thereof), specifically (2-methyl-2-carboxymethyl -trimethylene carbonate (cas: 507471-78-5), 2-methyl-2-benzyloxycarbonyl-trimethylene carbonate (cas: 247142-68-3), with other ester substituents differing, 2-methyl -2-benzyloxycarbonyl-trimethylene carbonate (cas: 247142-68-3), 2-methyl-2-methyloxycarbonyl-trimethylene carbonate (cas: 184697-04-9), 2-methyl-2-propenyl oxycarbonyl-trimethylene carbonate (cas: 1373439-22-5), 2-methyl-2-methoxyethoxyethyloxycarbonyl-trimethylene carbonate (cas: 1006903-36-1), 5-methyl-5-(2, 5,8,11-tetraoxadodecyl)-1,3-dioxa-2-one (cas: 1365611-65-9), etc. (Here, the 2-position of "2-" means The substitution positions of R _a and R _b in (1A) are shown.)
Moreover, these cyclic carbonates may form cyclic oligocarbonates such as dimers and trimers, which may be used for polymerization. For example, in the case of linear carbonates having 4 or more carbon atoms such as cyclobisbutylene carbonate (cas: 87719-16-2) and cyclobishexamethylene carbonate (cas: 82613-63-6), the monomer Since it forms a macrocyclic structure that is more stable than the cyclic carbonate, it has high thermal stability, is easy to handle and synthesize, and is easy to control polymerization.
Among these, the cyclic carbonate represented by the above formula (1A) is preferable because it is easy to handle and synthesize and has high reactivity. Most preferred.

When a cyclic carbonate having a carboxylic acid group, an ester group, an ether group, a hydroxyl group, a thiol group, a sulfonyl group, a phosphonyl group, or the like is used as a side chain substituent, water dispersibility, adhesiveness, dyeability, biocompatibility, etc. are used. In some cases, they are excellent in terms of compatibility, biodegradability, and low adhesiveness in vivo, and in some cases, they can be utilized as substituents used in cross-linking reactions. In particular, if there is a structural unit derived from polyethylene glycol ether such as diethylene glycol ether or triethylene glycol ether, it is excellent in biocompatibility, biodegradability, hydrophilicity, and low adhesiveness in the body, so it is useful for medical materials, hydrophilic materials, and Useful for biodegradable materials. Cyclic carbonates having ionic substituents or highly polar substituents such as carboxylic acid groups, ether groups, hydroxyl groups, thiol groups, amino groups, amide groups, sulfonyl groups, sulfonylamide groups, and phosphonyl groups as side chain substituents When used, it has excellent ion conductivity such as lithium ion, electrical conductivity, and solubility of ionic compounds. When used in battery materials and electronic materials, it is useful as an electrolyte, electrode, solvent, additive, etc. .

In the production of the polycarbonate polyol of the present invention, only one type of such cyclic carbonates X may be used, or two or more types may be used in any combination and ratio.

<Polyol Y>
Polyol Y used as an initiator is a polyol having 3 or more carbon atoms and having two or more hydroxyl groups, and is represented by the following formula (2).
HO—R ₂ —OH (2)
(In formula (2), R ₂ has the same definition as R ₂ in formula (B) above.)

Specific examples of diols among polyol Y include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, Linear terminal dihydroxy compounds such as 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 1,20-eicosanediol dihydroxy compounds having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol and polytetramethylene glycol; thioether diols such as bishydroxyethylthioether; 2-ethyl-1,6-hexanediol, 2-methyl- 1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (hereinafter abbreviated as neopentyl glycol ), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, etc. 2,2-dialkyl-substituted 1,3-propanediols (where the number of carbon atoms in the alkyl group is 15 or less); 2,2,4,4-tetramethyl-1,5-pentanediol, 2,2,9, Tetraalkyl-substituted alkylenediols such as 9-tetramethyl-1,10-decanediol; 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro [ 5.5] Dihydroxy compounds containing a cyclic group such as undecane; 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3 -propanediol, 2,2-dimethoxy-1,3-propanediol, bis(2-hydroxy-1,1-dimethylethyl)ether, bis(2-hydroxy-1,1-dimethylethyl)thioether, 2,2 ,4,4-tetramethyl-3-cyano-1,5-pentanediol and other branched dihydroxy compounds; 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2′-bis(4-hydroxycyclohexyl)propane, 1,4- Dihydroxyethylcyclohexane, isosorbide, spiroglycol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidene dicyclohexanol, 4,4'-isopropylidene bis(2,2'-hydroxyethoxycyclohexane), etc. in the molecule; 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl) Dihydroxy compounds having an aromatic ring such as fluorene; Nitrogen-containing dihydroxy compounds such as diethanolamine and N-methyl-diethanolamine; Sulfur-containing dihydroxy compounds such as bis(hydroxyethyl) sulfide; 2,2-bis(4-hydroxyphenyl) Propane [=bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis (4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2, 4′-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4- hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4′-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4′- Aromas such as dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene group bisphenols; and the like.
Examples of oligomer type diols include polyether polyols (polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PTMG), etc.), polyester polyols (butylene adipate diol, polycaprolactone polyol, , polyglycolic acid-derived polyols, polylactide-derived polyols, etc.), polycarbonate polyols (1,6-hexanediol, 1,4-butanediol, 1,10-decanediol, isosorbide, those composed of diols such as PTMG ), polyolefin polyol (polybutadiene polyol, hydrogenated polybutadiene polyol (e.g. Nippon Soda Co., Ltd. GI1000), etc.), silicone polyol (both ends carbinol-modified polydimethylsiloxane (e.g. Shin-Etsu Chemical KF6000), etc.), perfluorodiol (e.g. Solvay Fluorolink E10-H manufactured by Co., Ltd.).

As triols, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexane Chain triols such as triol, tris(hydroxymethyl)amine, tris(hydroxyethyl)amine, tris(hydroxypropyl)amine; tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxymethyl) isocyanurate, cyclo cyclic triols such as dodecanetrimethanol, 1,3,5-benzenetrimethanol, and 1,3,5-cyclohexanetrimethanol;

Examples of polyols having four or more hydroxyl groups include pentaerythritol, diglycerol, triglycerol, polyglycerol, bis(trimethylolpropane), sugars such as glucose, and sugar derivatives such as sorbitol.

Among these polyols Y, from the viewpoint of heat resistance and strength, those having preferably 3 to 50 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms are preferred. . As for the shape of the diol compound, linear diols are preferable from the viewpoint of flexibility, and those having a cyclic structure are preferable from the viewpoint of mechanical strength.

In addition, the aforementioned oligomer type polyol is preferable in order to allow the polyurethane to exhibit functions such as flexibility and rubber elasticity. In addition, the polycarbonate polyol in the present invention obtained using an oligomer-type polyol (for example, silicone polyol, olefin polyol, etc., which are usually incompatible with polycarbonate diols) as a raw material has improved compatibility with the oligomer-type polyol as a raw material. . It may function as a compatibilizer when using a plurality of polyols, and may improve the reactivity during polyurethane synthesis and improve the strength and transparency of the resulting polyurethane. In addition, water solubility, water dispersibility, biocompatibility, and biodegradability can be imparted by using biocompatible and biodegradable oligomer polyols (polylactic acid, polyglycolic acid, polycaprolactone, polyethylene glycol, etc.). In some cases, it can be used for medical materials, etc.

Moreover, in order to utilize it as a polyol having a cross-linking function, it is preferable to utilize the aforementioned polyol having three or more hydroxyl groups.
As polyols having three or more hydroxyl groups, glycerol, trimethylolpropane, pentaerythritol, and the like are preferable from the availability of raw materials. In order to prevent the formation of cyclic by-products and synthesize a highly pure radial polyol, it is preferable that the distance between the hydroxyl groups in the initiator polyol Y (the number of atoms between hydroxyl groups) is long. Triols are sometimes preferred.

For producing the polycarbonate polyol of the present invention, only one of these polyols Y may be used, or two or more of them may be used in any combination and ratio.

<Polymerization catalyst>
When producing the polycarbonate polyol of the present invention, a polymerization catalyst (hereinafter sometimes referred to as a catalyst) can be used as necessary to promote polymerization. In that case, if too much catalyst remains in the polycarbonate polyol obtained, the reaction may be inhibited or accelerated excessively in the production of polyurethane using the polycarbonate polyol. Moreover, the thermal stability of the polycarbonate polyol may be improved or lowered.

For this reason, the amount of the catalyst remaining in the polycarbonate polyol is not particularly limited, but the content in terms of atoms to be the catalyst is preferably 10000 mass ppm or less, more preferably 5000 mass ppm or less, and still more preferably 1000 mass ppm or less. be. The preferred contents of the catalyst-derived metal element and phosphorus element in the polycarbonate polyol of the present invention are as described above.

As the catalyst, any compound can be used without limitation as long as it is generally considered to have an effect of promoting ring-opening polymerization.

Examples of catalysts include acid compounds such as sulfuric acid, hydrochloric acid, boric acid, and phosphoric acid.
Examples of base compounds include inorganic base compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; aliphatic amines such as triethylamine and tributylamine; and cyclic amines such as pyridine, dimethylaminopyridine, 1,5, 7-triazabicyclo[4.4.0]dec-5-ene (TBD), diazabicycloundecene (DBU), and amino acids such as glycine and lysine and their derivatives.
As phosphorus compounds, dimethyl phosphate, diethyl phosphate, diisopropyl phosphate, di-n-butyl phosphate, diisobutyl phosphate, di-n-ethylhexyl phosphate, dilauryl phosphate, dioleyl phosphate, distearyl phosphate, Diphenyl phosphate, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, mono-n-butyl phosphate, monoisobutyl phosphate, mono-n-ethylhexyl phosphate, monolauryl phosphate, monooleyl phosphate, mono phosphate stearyl, monophenyl phosphate, 3,3′-bis[3,5-bis(trifluoromethyl)phenyl]-1,1′-binaphthyl-2,2′-diyl phosphate, thiophosphate, methylthiophosphate, Ethylthiophosphate, dimethylthiophosphate, diethylthiophosphate, N,N'-bis[(trifluoromethyl)methyl]diphenylphosphoroamide and the like.

Further, the metal compound serving as a catalyst includes compounds of Group 1 metals of the periodic table such as lithium, sodium, potassium, rubidium and cesium; compounds of Group 2 metals of the periodic table such as magnesium, calcium, strontium and barium; titanium, Compounds of Group 4 metals of the periodic table such as 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; Group 13 metal compounds of the periodic table; compounds of group 14 metals of the periodic table such as germanium, tin and lead; compounds of group 15 metals of the periodic table such as antimony and bismuth; Examples include metal compounds. Among these, periodic table group 1 metal compounds, periodic table group 2 metal compounds, periodic table group 4 metal compounds, periodic table group 5 metal compounds, periodic table group 9 metal compounds, period Compounds of Group 12 metals of the periodic table, compounds of Group 13 metals of the periodic table, and compounds of metals of Group 14 of the periodic table are preferred, and compounds of Group 1 metals of the periodic table and compounds of Group 2 metals of the periodic table are more preferred. More preferred are compounds of the Group 1 metals of the Table. Among the compounds of Group 1 metals of the periodic table, lithium, potassium and sodium compounds are preferred, lithium and sodium compounds are more preferred, and sodium compounds are even more preferred. Among the compounds of lithium, potassium and sodium, fatty acids such as acetates, pivalates and benzoates with weak basicity are considered from the viewpoint of the reactivity of the ring-opening polymerization and the effect on the thermal stability of the resulting polycarbonate polyols. Group carboxylates and aromatic carboxylates are preferred, and acetate, ie sodium acetate, is most preferred from the viewpoint of availability.

Among these, phosphorus compounds are preferable in that side reactions such as transesterification between polymers are less likely to occur than with metal catalysts, and a polymer with a narrow molecular weight distribution can be obtained. It is also preferable in terms of obtaining a highly thermally stable polycarbonate polyol with little broadening of the molecular weight distribution during heating, since there is little effect of causing a transesterification reaction on the obtained polycarbonate polyol. When other phosphorus compounds and metal catalysts are contained at the same time, the phosphorus compounds and metal catalysts may interact with each other to inactivate the phosphorus compounds and metal catalysts respectively. In particular, phosphorus compounds include dimethyl phosphate, diethyl phosphate, diisopropyl phosphate, di-n-butyl phosphate, diisobutyl phosphate, di-n-ethylhexyl phosphate, dilauryl phosphate, dioleyl phosphate, and distearyl phosphate. , diphenyl phosphate, di(4-nitrophenyl) phosphate, and dinaphthyl phosphate are preferable from the viewpoint of reactivity. Aromatic phosphate diesters such as phenyl) and dinaphthyl phosphate are more preferred, and diphenyl phosphate is most preferred from the standpoint of availability.

Only one of these catalysts may be used, or two or more thereof may be used in any combination and ratio.

From the viewpoint of the effect of activating the polymerization reaction by using a catalyst, the suppression of side reactions that broaden the molecular weight distribution, and the reduction of the amount of residual catalyst, especially when using a catalyst containing elemental phosphorus as a catalyst, the cyclic carbonate X and the polyol Y It is preferable to use 0.01 to 1000 mass ppm as the amount of phosphorus element, that is, the amount used in terms of phosphorus element, more preferably 0.01 to 800 mass ppm, with respect to the total mass of 0.01 to 500 It is more preferable to use mass ppm.

<Dihydroxy compound other than polyol Y>
In the production of the polycarbonate polyol of the present invention, a dihydroxy compound (sometimes referred to as another dihydroxy compound) other than the initiator polyol Y may be used as long as it does not impair the effects of the present invention. Specific examples include straight-chain dihydroxy compounds, ether group-containing dihydroxy compounds, branched-chain dihydroxy compounds, and dihydroxy compounds containing an alicyclic structure. However, when other dihydroxy compounds are used, in order to effectively obtain the effects of the present invention, the ratio of structural units derived from other dihydroxy compounds to the total structural units of the polycarbonate polyol is more preferably 30 mol% or less. , is more preferably 20 mol % or less, and most preferably 10 mol % or less.

<Materials derived from plants>
The cyclic carbonate X used in the present invention is preferably derived from plants from the viewpoint of reducing environmental impact.
The plant-derived cyclic carbonate X is obtained from plant-derived polyols such as plant-derived 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and glycerol. Cyclic carbonates are mentioned. Further, it is more preferable that the raw material of the carbonate group portion is also plant-derived or carbon dioxide.
Also, polyol Y, which is an initiator, is preferably derived from plants from the viewpoint of reducing environmental load. As the plant-derived polyol Y, all plant-derived polyols listed in the section of polyol Y can be applied. 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13 -tridecanediol, 1,12-octadecanediol, 1,20-eicosanediol, glycerol, pentaerythritol, isosorbide, polytetramethylene ether glycol, polycols derived from sugars such as glucose, and the like are preferred.

<Reaction temperature>
The reaction temperature during the ring-opening polymerization reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, but the lower limit is usually 0°C, preferably 20°C, more preferably 60°C. The upper limit of the reaction temperature is usually 200°C, preferably 150°C, more preferably 140°C, even more preferably 120°C, particularly preferably 100°C. If the reaction temperature is lower than the above lower limit, the polymerization reaction may not proceed at a practical rate, the raw materials may not dissolve, or the mixing may be insufficient. On the other hand, if the reaction temperature exceeds the above upper limit, quality problems such as widening of the molecular weight distribution (D) of the resulting polycarbonate polyol, coloration, and deterioration of turbidity may occur.

<Reaction pressure>
The ring-opening polymerization is carried out under normal pressure if the reaction proceeds without problems. However, when the reaction becomes more efficient under reduced pressure or increased pressure, the reaction may be carried out under reduced pressure or increased pressure while extracting the product. In some cases, residual monomers, by-products, and catalysts are removed under reduced pressure simultaneously with the reaction.

<Reaction time>
The time required for the ring-opening polymerization reaction to obtain the polycarbonate polyol of the present invention varies greatly depending on the cyclic carbonate X and polyol Y used, the type and amount of catalyst used, and cannot be generally defined. The reaction time required to reach the molecular weight is 50 hours or less, preferably 20 hours or less, more preferably 10 hours or less. Further, if the heating is continued after the completion of the polymerization, the molecular weight distribution (D) of the polycarbonate polyol may widen. In order to solve the problem, the reaction may be stopped by cooling immediately after the reaction is completed, performing purification such as crystallization or liquid separation, or adding a catalyst deactivator, which will be described later.

<Solvent for ring-opening polymerization>
When producing the polycarbonate polyol of the present invention, it is preferable to carry out polymerization without using a solvent as much as possible from the viewpoint of reactivity and productivity. Even when a solvent is used, it is preferable that the amount used is small. Specifically, it is preferably 50 parts by mass or less, more preferably 10 parts by mass or less based on 100 parts of the total mass of the cyclic carbonate X and the polyol Y. , 5 parts by mass or less is most preferable, and the ring-opening polymerization may be carried out without using a solvent.

When a solvent is used, preferable solvents include ketone solvents such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and toluene and xylene. amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide and N-methylpyrrolidone; and sulfoxide solvents such as dimethylsulfoxide. These solvents may be used alone or as a mixed solvent of two or more. Particularly preferred solvents are toluene, methyl ethyl ketone, ethyl acetate and the like. When an appropriate amount of these solvents is used, the compatibility between the cyclic carbonate X and the polyol Y is improved, and a uniform reaction becomes possible. A polycarbonate polyol with improved reactivity or a narrow molecular weight distribution (D) may be obtained. However, if too much solvent is used, the concentration of the catalyst may decrease, the polymerization rate may decrease, or the reaction time may become longer to broaden the molecular weight distribution. In addition, an increase in the amount of solvent lowers the productivity during the polymerization reaction and purification.

<Purification of Polycarbonate Polyol>
As described above, when a catalyst is used in the polymerization reaction, the catalyst usually remains in the polycarbonate polyol obtained, and the residual catalyst reduces the thermal stability of the polycarbonate polyol and makes it difficult to control the polyurethane formation reaction. may not be possible.
Purification methods for removing the residual catalyst in the polycarbonate polyol include reprecipitation, distillation, column chromatography, solvent extraction, and the like. In particular, reprecipitation is preferable from the viewpoint of removal efficiency when using a catalyst that dissolves in an organic solvent. In the case of a water-soluble catalyst, washing with water (which may contain acid or base) is preferred.

<Catalyst deactivator>
As described above, in order to suppress the influence of the catalyst remaining in the polycarbonate polyol, a phosphorus-based compound, an amine compound, or the like (hereinafter referred to as a catalyst deactivator) is added in an approximately equimolar amount to the catalyst used, and the catalyst is is preferably inactivated. Furthermore, after adding the catalyst deactivator, the transesterification catalyst can be efficiently deactivated by heat treatment or the like.

The catalyst deactivator has a structure suitable for deactivating the catalyst, and the contained element, acid/base, etc. are not particularly limited. If the compound described above for the polymerization catalyst is acidic, a catalyst deactivator of a basic compound may be effective, and if the polymerization catalyst is basic, a catalyst deactivator of an acidic compound may be effective.

Examples of catalyst deactivators include phosphorus-containing compounds such as inorganic phosphoric acid such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and phosphorous acid. Examples thereof include organic phosphates such as triphenyl and diphenyl phosphate. These phosphorus-containing compounds may be effective as metal polymerization catalysts. Examples of nitrogen-containing compounds include triethylamine, diethylamine, n-butylamine, aniline, pyridine and imidazole. A nitrogen-containing compound may be effective as a deactivator for a phosphate diester used as a polymerization catalyst.
One of these catalyst deactivators may be used alone, or two or more thereof may be used in combination.

The amount of the catalyst deactivator used is not particularly limited, but may be approximately equimolar to the catalyst used. Specifically, the upper limit is preferably 5 mol per 1 mol of the polymerization catalyst used. , more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol. If the catalyst deactivator is used in an amount less than this, the deactivation of the polymerization catalyst in the reaction product may not be sufficient, and the thermal stability of the resulting polycarbonate polyol may decrease. Moreover, when used as a raw material for polyurethane production, it may not be possible to stabilize the reactivity of the polycarbonate polyol with respect to isocyanate groups. Also, if a catalyst deactivator exceeding this range is used, the obtained polycarbonate polyol may be colored.

[Polyurethane]
Polycarbonate polyols of the invention can be used to produce polyurethanes of the invention.
The method for producing the polyurethane of the present invention using the polycarbonate polyol of the present invention employs known polyurethane-forming reaction conditions for producing ordinary polyurethanes.

For example, the polyurethane of the present invention can be produced by reacting the polycarbonate polyol of the present invention with a polyisocyanate and a chain extender at a temperature ranging from room temperature to 200°C.
Alternatively, the polycarbonate polyol of the present invention may first be reacted with an excess amount of polyisocyanate to produce a prepolymer having isocyanate groups at its terminals, and then a chain extender may be used to increase the degree of polymerization to produce the polyurethane of the present invention. can be done.

<Polyisocyanate>
The polyisocyanate used to produce the polyurethane of the present invention using the polycarbonate polyol of the present invention includes various known aliphatic, alicyclic or aromatic polyisocyanate compounds.
For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer diisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group. Aliphatic diisocyanates; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 1,3-bis Alicyclic diisocyanates such as (isocyanatomethyl)cyclohexane; 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl Aromatic diisocyanates such as -4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate and m-tetramethylxylylene diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

Among these, 4,4′-diphenylmethane diisocyanate (hereinafter sometimes referred to as MDI), hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred.

<Chain extender>
The chain extender used in producing the polyurethane of the present invention is a low-molecular-weight compound having at least two active hydrogens that react with isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later, and is usually a polyol. 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, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2 ,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, dimer diol, and other branched diols diols having an ether group such as diethylene glycol and propylene glycol; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane; xylylene glycol; Diols having aromatic groups such as 1,4-dihydroxyethylbenzene and 4,4′-methylenebis(hydroxyethylbenzene); Polyols such as glycerin, trimethylolpropane and pentaerythritol; N-methylethanolamine and N-ethylethanol hydroxyamines such as amine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxy ethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4′-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tri polyamines such as diamine, 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 (hereinafter sometimes referred to as 14BD) and 1,5-pentane are preferred because the resulting polyurethane has a good balance of physical properties and is industrially available in large quantities at low cost. Diol, 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 are 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>.

<Chain terminating agent>
When producing the polyurethane of the present invention, a chain terminating agent having one active hydrogen group can be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane.
These chain terminators include aliphatic monools 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.

<Catalyst>
Amine-based catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine or tins such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanate in the polyurethane-forming reaction when producing the polyurethane of the present invention. Known urethane polymerization catalysts typified by 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.

<Polyol other than the polycarbonate polyol of the present invention>
In the polyurethane-forming reaction when producing the polyurethane of the present invention, the polycarbonate polyol of the present invention may be used in combination with other polyols, if desired. Here, the polyol other than the polycarbonate polyol of the present invention is not particularly limited as long as it is used in ordinary polyurethane production, and examples thereof include polyether polyols, polyester polyols, and polycarbonate polyols other than the polycarbonate polyol of the present invention. be done. Here, with respect to the total weight of the polycarbonate polyol of the present invention and other polyols. The mass ratio of the polycarbonate polyol of the present invention is preferably 70% or more, more preferably 90% or more. If the mass ratio of the polycarbonate polyol of the present invention is small, the advantages of the polycarbonate polyol of the present invention, such as the small molecular weight distribution (D) and excellent handleability, may be impaired.

<Solvent>
A solvent may be used in the polyurethane-forming reaction when producing the polyurethane of the present invention.
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.

Among these, preferred organic solvents are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide.

Aqueous dispersion polyurethane can also be produced from a polyurethane composition containing the polycarbonate polyol of the present invention, polydiisocyanate, and the chain extender.

<Polyurethane manufacturing method>
As a method for producing the polyurethane of the present invention using the above-mentioned reaction reagents, production methods generally used experimentally or industrially can be used.
Examples thereof include a method of collectively mixing and reacting the polycarbonate polyol of the present invention, other polyols, polyisocyanate and chain extender (hereinafter sometimes referred to as "one-step method"), and A method of reacting a polycarbonate polyol, other polyol and polyisocyanate to prepare a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with a chain extender (hereinafter sometimes referred to as a “two-step method”). Yes), etc.

In the two-step method, the polycarbonate polyol of the present invention and other polyols are preliminarily reacted with one or more equivalents of polyisocyanate to prepare isocyanate intermediates at both ends corresponding to the soft segment of the polyurethane. It is. 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 it is useful when it is necessary to ensure phase separation between the soft segment and the hard segment. is useful.

<Single step method>
The one-step method, which is also called a one-shot method, is a method in which the polycarbonate polyol 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 polyol of the present invention and other polyols, the number of hydroxyl groups and the number of amino groups of the chain extender is set to 1 equivalent. When the is 2.0 equivalents, more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

If the amount of polyisocyanate used is too large, unreacted isocyanate groups will cause a side reaction, and the viscosity of the resulting polyurethane will tend to be too high, making it difficult to handle or impairing flexibility. 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.
In addition, the amount of the chain extender used is not particularly limited. is 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 equivalents, and further Preferably 1.5 equivalents, particularly preferably 1.1 equivalents. 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. The retention performance may not be obtained, or the heat resistance may deteriorate.

<Two step method>
The two-step method, also called a prepolymer method, mainly includes the following methods.
(a) The polycarbonate polyol of the present invention and other polyols and excess polyisocyanate are added in advance in an amount having a reaction equivalent ratio of polyisocyanate/(polycarbonate polyol of the present invention and other polyols) exceeding 1 to 10. A method of producing a polyurethane by reacting at a temperature of 0 or less to produce a prepolymer having an isocyanate group at the molecular chain end and then adding a chain extender to the prepolymer (b) Preliminary polyisocyanate, excess polycarbonate polyol and A polyol other than the above is reacted at a reaction equivalent ratio of polyisocyanate/(polycarbonate polyol of the present invention and other polyols) of 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 it 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, the polyisocyanate, the polycarbonate polyol of the present invention, and other polyols are directly reacted to synthesize a prepolymer, which is directly used for the 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, the polyisocyanate, the polycarbonate polyol of the present invention, and other polyols are reacted, and then the chain extension reaction is carried out.

In the case of method (1), the chain extension reaction is carried out by dissolving the chain extender in a solvent, or dissolving the prepolymer and the chain extender in the solvent at the same time, to obtain the polyurethane in a form coexisting with the solvent. This is very important.
The amount of polyisocyanate used in the two-step method (a) is not particularly limited. The lower limit is preferably more than 1.0 equivalents, more preferably 1.2 equivalents, still more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, still more preferably It is in the range of 3.0 equivalents.

If the amount of isocyanate used is too large, the excessive isocyanate groups tend to cause side reactions, making it difficult to achieve the desired physical properties of the polyurethane. Although the amount of the chain extender to be used is not particularly limited, the lower limit is preferably 0.1 equivalent, more preferably 0.1 equivalent, with respect to one equivalent of isocyanate groups contained in the prepolymer. It is 5 equivalents, more preferably 0.8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, 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 addition, the amount of polyisocyanate to be used when preparing a prepolymer having a terminal hydroxyl group in the two-step method (b) is not particularly limited, but the amount of the total hydroxyl groups of the polycarbonate polyol of the present invention and other polyols is 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. In some cases, it may decrease, or the handling 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 polyol of the present invention and other polyols used in the prepolymer is 1 equivalent, the equivalent of the isocyanate group used in the prepolymer is As the total equivalent added, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalents, more preferably 0.99 equivalents. , 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 reaction progresses too slowly, and the solubility of the raw materials and polymer may be low, which may lengthen the production time. . 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. You may use the above together. Examples of stabilizers include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, tris(dinonylphenyl)phosphite, Compounds such as phyto may be mentioned, and one kind may be used alone, or two or more kinds may be used in combination. If the chain extender is highly reactive such as a short-chain aliphatic amine, the reaction may be carried out without adding a catalyst.

<Water-based polyurethane emulsion>
It is also possible to produce aqueous polyurethane emulsions using the polycarbonate polyols of the present invention. In particular, polycarbonate polyols having polar groups such as carboxyl groups, ether groups, and amide groups have high water dispersibility and are particularly useful for this application.
In that case, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is added in reacting a polyol, including the polycarbonate polyols of the present invention, with an excess of polyisocyanate to produce a prepolymer. A prepolymer is formed by mixing, and an aqueous polyurethane emulsion 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.

As used herein, the hydrophilic functional group of compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups is, for example, a carboxylic acid group or a sulfonic acid group, neutralized with an alkaline group. 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 emulsion, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups should be adjusted to increase the dispersibility in water. It is preferably 1% by mass, more preferably 5% by mass, still more preferably 10% by mass, based on the total mass of polycarbonate polyol and other polyols. On the other hand, if too much is added, the properties of the polycarbonate polyol of the present invention may not be maintained, so the upper limit is preferably 50% by mass, more preferably 40% by mass, and still more preferably 30% by mass.

When producing an aqueous polyurethane emulsion, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone in the prepolymer 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 manufacturing an aqueous emulsion.

When the polycarbonate polyol of the present invention is used as a raw material to produce an aqueous polyurethane emulsion without solvent, the upper limit of the number average molecular weight obtained from the hydroxyl value of the polycarbonate polyol of the present invention is preferably 5,000, more preferably 4,500, and still more preferably. 4000. Also, the lower limit is preferably 300, more preferably 500, still more preferably 800. If the number average molecular weight obtained from the hydroxyl value exceeds 5000 or is smaller than 300, emulsification may become difficult.

Higher fatty acid, resin acid, acidic fatty alcohol, sulfate, higher alkyl sulfonate, higher alkyl sulfonate, alkylaryl sulfonate, sulfonated castor oil, sulfosuccinate, etc. Cationic surfactants such as anionic 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 or the like in combination, which is represented by a known reaction product with .

In addition, when making a water-based polyurethane emulsion, water is mechanically mixed under high shear in the presence of an emulsifier with an organic solvent solution of the prepolymer, if necessary, without the neutralization and chlorination step, to produce the emulsion. You can also
The water-based polyurethane emulsion 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 emulsions include, for example, coating agents, water-based paints, adhesives, synthetic leathers, and artificial leathers. In particular, the water-based polyurethane emulsion produced using the polycarbonate polyol of the present invention has a structural unit derived from the compound represented by the formula (B) in the polycarbonate polyol, and thus is flexible and a coating agent. As such, it can be used more effectively than conventional water-based polyurethane emulsions using polycarbonate polyols.

<Additive>
Polyurethanes of the present invention produced using the polycarbonate polyols of the present invention contain heat stabilizers, light stabilizers, colorants, fillers, stabilizers, UV absorbers, antioxidants, antiblocking agents, flame retardants, anti-aging agents. Various additives such as inhibitors and inorganic fillers can be added and mixed within limits that do not impair the properties of the polyurethane of the present invention.

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. are 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.
Regarding the amount of these additives added, the lower limit is preferably 0.01% by mass, more preferably 0.05% by mass, still more preferably 0.1% by mass, and the upper limit is preferably 10% by mass, as a mass ratio to polyurethane. % by mass, more preferably 5% by mass, still more preferably 1% by mass. 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.

<Evaluation of physical properties of polyurethane>
Various physical properties of the polyurethane of the present invention can be evaluated by preparing sheet-like or film-like moldings having various thicknesses, if necessary.

<Sheet-like polyurethane molding>
A sheet-like polyurethane molded article can be obtained from the polyurethane of the present invention by hot compression molding. For example, it can be molded into a sheet having a thickness of 2 mm by the following method.
After placing the PET release film and the cured polyurethane on a compression molding mold (15 cm×8 cm×2 mm thickness), the PET release film and the mold are placed in that order. After installing these on the stage of a preheated heating press (manufactured by Toyo Seiki Seisakusho, product name “Mini Test Press”), the stage of the heating press is brought into contact and pressurized (pressure: 0.5 MPa x temperature: 218 to 225°C x time: 2 minutes). After that, the pressure setting of the heating press is gradually increased to 13 MPa for 2 minutes to complete the molding. Lower the pressure of the heating press, take out the mold, set it in a cooling press (manufactured by Toyo Seiki Seisakusho, product name "Mini Test Press") that has been cooled by running cooling water in advance, and cool (pressure 10 MPa x time 2 minutes) to obtain a sheet-like polyurethane molding.
By changing the size of the mold to be used, it is possible to produce sheet-like polyurethane moldings having different thicknesses and sizes.

<Polyurethane film/polyurethane plate>
When a film is produced using the polyurethane of the present invention, the lower limit of the film thickness is preferably 10 μm, more preferably 20 μm, and still more preferably 30 μm, and the upper limit is preferably 1000 μm, more preferably 500 μm, and even more preferably. is 100 μm.
If the film is too thick, there is a tendency that sufficient moisture permeability cannot be obtained. Polyurethane films can also be evaluated for physical properties in the same manner as for polyurethane moldings.
A polyurethane film can be obtained, for example, by the following method.
The polyurethane solution was applied onto a fluororesin sheet (fluorocarbon tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 9.5 mil applicator, and then heated at 60°C for 1 hour, followed by 0.5 at 100°C. Allow time to dry. After further drying at 100° C. under vacuum for 0.5 hour and at 80° C. for 15 hours, the film is allowed to stand at constant temperature and humidity at 23° C. and 55% RH for 12 hours or more to obtain a polyurethane film.

<Molecular weight>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use, and is not particularly limited. It is more preferably from 10,000 to 300,000, further preferably from 80,000 to 150,000. If Mw is less than the above lower limit, sufficient strength and hardness may not be obtained.

<Chemical resistance>
For the polyurethane of the present invention, the rate of change (%) in the mass of the polyurethane film after being immersed in the chemical with respect to the mass of the polyurethane film before being immersed in the chemical is 5% or less, for example, when evaluated by the method described below. It is preferably 3% or less, more preferably 1% or less. Moreover, it is preferable that there is no change in the shape and color of the appearance and that the film does not dissolve. The polyurethane film is prepared by the method described later. If this mass change rate exceeds the above upper limit, desired chemical resistance may not be obtained.

<Oleic acid resistance>
The polyurethane of the present invention can be evaluated, for example, by the method described below as a rate of change (%) in the mass 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 as a chemical. However, it is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, particularly preferably 5% or less, and most preferably 3% or less.
If this mass change rate exceeds the above upper limit, sufficient oleic acid resistance may not be obtained.

<Ethanol resistance>
For the polyurethane of the present invention, the rate of change (%) in the mass of the polyurethane test piece after being immersed in oleic acid with respect to the weight of the polyurethane test piece before being immersed in ethanol as a chemical is evaluated, for example, by the method described below. , is preferably 10% or less, more preferably 8% or less, still more preferably 6% or less, and particularly preferably 4% or less. If this mass change rate exceeds the above upper limit, sufficient ethanol resistance may not be obtained.

<Evaluation method for chemical resistance, oleic acid resistance, and ethanol resistance>
The polyurethane solution was applied onto a fluororesin sheet (fluorocarbon tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 9.5 mil applicator, and then heated at 60°C for 1 hour, followed by 0.5 at 100°C. Allow time to dry. Furthermore, after drying for 0.5 hours in a vacuum state of 100 ° C. and 15 hours at 80 ° C., it was left to stand under a constant temperature and humidity of 23 ° C. and 55% RH for 12 hours or more, and a 3 cm × 3 cm test was performed from the obtained film. After cutting out a piece and measuring the mass of the test piece with a precision balance, it is placed in a glass petri dish with an inner diameter of 10 cmφ containing 50 ml of the test chemical or solvent and immersed at room temperature of about 23° C. for 1 hour. After the test, the test piece is taken out and lightly wiped with a paper wiper, and the mass is measured to calculate the mass increase ratio from before the test.

<Tensile breaking elongation, breaking strength>
The polyurethane of the present invention can be evaluated for tensile elongation at break and breaking strength by the following methods. A punching machine is used to punch out a polyurethane sheet-like molded body (2 mm thick sheet) into a dumbbell-shaped No. 3 shape, and a tensile tester (AGS-10kNX, manufactured by Shimadzu Corporation) and an elongation system (DSES-1000, manufactured by Shimadzu Corporation) are used. A tensile test was performed using a gauge length of 20 mm, a tensile speed of 200 mm, n = 3, a room temperature of 23 ° C., and a humidity of 55%. The modulus (called elongation at break or elongation at break) can be measured. The lower limit of the breaking elongation measured by this method is preferably 100%, more preferably 200%, more preferably 300%, and the upper limit is preferably 900%, more preferably 800%, more preferably 700%. . If the tensile 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 chemical resistance may not be obtained. The lower limit of the breaking strength measured by this method is preferably 10 MPa, more preferably 20 MPa, still more preferably 30 MPa, and the upper limit is preferably 80 MPa or less, more preferably 60 MPa or less, still more preferably 50 MPa or less. If the tensile strength at break is less than the above lower limit, the chemical resistance and mechanical strength 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.

<Young's modulus>
Using the polycarbonate polyol of the present invention, MDI and 1,4-BD, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is The Young's modulus at 23° C. of 80,000 to 210,000 polyurethane (hereinafter sometimes referred to as "specific polyurethane") measured by the same method as the tensile elongation at break is preferably 0.02 or more, and more It is preferably 0.04 or more, more preferably 0.06 or more. It is also preferably 2 or less, more preferably 1 or less, still more preferably 0.5 or less. If the Young's modulus is too low, chemical resistance may be insufficient. If the Young's modulus is too high, flexibility may be insufficient, and handling properties such as workability may be impaired. Furthermore, the Young's modulus of the specific polyurethane measured by the same method as the tensile elongation at break is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.03 or more, except that the temperature is -10°C. , particularly preferably 0.05 or more. It is also preferably 2 or less, more preferably 1 or less, even more preferably 0.5 or less, and particularly preferably 0.3 or less. If the Young's modulus at -10°C is less than the above lower limit, chemical resistance may be insufficient. If the Young's modulus at −10° C. exceeds the above upper limit, the flexibility at low temperatures may be insufficient, or the handling properties such as workability may be impaired.

Here, the Young's modulus is the stress value when the elongation is 1% as the slope of the stress value at the initial elongation, and is specifically measured by the method described in the Examples section below. .
The HS content % can be calculated by the following formula.

Each term in the above formula is a numerical value related to the raw materials used in the production of urethane.

<100% modulus, 300% modulus>
The 100% modulus and 300% modulus of the polyurethane of the present invention are measured by the same method as the breaking elongation measurement.
The lower limit of the 100% modulus of the polyurethane of the present invention at room temperature of 23° C. and humidity of 55% is preferably 1 MPa or more, more preferably 3 MPa or more, still more preferably 5 MPa or more, and the upper limit is preferably 30 MPa or less, more preferably 20 MPa. Below, more preferably 15 MPa or less. If the 100% modulus is less than the above lower limit, chemical resistance and mechanical strength may be insufficient, and if it exceeds the above upper limit, flexibility tends to be insufficient, and handling properties such as workability tend to be impaired.
Furthermore, the lower limit of the 100% modulus at -10°C of the polyurethane of the present invention is preferably 1 MPa or higher, more preferably 3 MPa or higher, and still more preferably 5 MPa or higher, and the upper limit is preferably 30 MPa or lower, more preferably 20 MPa or lower. More preferably, it is 15 MPa or less. If the 100% modulus at −10° C. exceeds the above upper limit, the flexibility at low temperatures may be insufficient, and handling properties such as workability may be impaired.
Furthermore, the lower limit of the 300% modulus value of the polyurethane of the present invention measured in the same manner is preferably 10 MPa or more, more preferably 15 MPa or more, and still more preferably 20 MPa or more. The upper limit is preferably 80 MPa or less, more preferably 60 MPa or less. If the 300% modulus is less than the above lower limit, chemical resistance and mechanical strength may be insufficient, and if it exceeds the above upper limit, flexibility tends to be insufficient, and handling properties such as workability tend to be impaired.

<Low temperature characteristics>
The polyurethane of the present invention has good low-temperature properties, and the low-temperature properties in this patent can be evaluated by elongation at break, Young's modulus, and 100% modulus in a tensile test at a low temperature such as -10°C. More specifically, it means flexibility at low temperatures, impact resistance, bending resistance, and durability.

<Heat resistance>
The polyurethane of the present invention has high heat resistance because it is made from polycarbonate diol, which has a high ratio of carbonate bonds in the molecule and has high heat resistance. The heat resistance can be evaluated by the following method.
A urethane film with a width of 100 mm, a length of 100 mm, and a thickness of about 50 to 100 μm is heated in a gear oven at a temperature of 120° C. for 400 hours. Mw), the lower limit is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, particularly preferably 85% or more, and the upper limit is preferably 120% or less, more preferably 110%. 105% or less, more preferably 105% or less.

<Glass transition temperature>
The polycarbonate polyol of the present invention, MDI, and 1,4-BD are used to produce a one-step method with an HS content of 12% to 13%, and the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is 8. The lower limit of the glass transition temperature (Tg) of the specific polyurethane of 10,000 to 210,000 is preferably -50°C, more preferably -40°C, still more preferably -30°C, and the upper limit is preferably 50°C, more preferably 30°C. °C, more preferably 20 °C. If the Tg is less than the above lower limit, the heat resistance and chemical resistance may not be sufficient, and if it exceeds the above upper limit, the low temperature properties may be insufficient. Note that Tg corresponds to the tan δ peak temperature in the viscoelasticity measurement described later.

<Hardness>
The hardness of polyurethane (sometimes referred to as hardness) is measured by the following method.
A 3-cm-square piece was cut from a 2-mm-thick polyurethane sheet-like molding, and three sheets were stacked to obtain a test piece (n=5). Using an Asker rubber altimeter ISO-A (manufactured by Kobunshi Keiki Co., Ltd.), the hardness is measured after 15 seconds of contact, and the hardness (Shore A hardness) is obtained from the median value. For use as a high-strength polyurethane elastomer, the lower limit is preferably A30 or more, more preferably A50 or more, and even more preferably A70 or more. The upper limit is preferably A95 or less, more preferably A90 or less.

<Compression set>
Polycarbonate diol having a narrow molecular weight distribution is used as the soft segment in the polyurethane of the present invention, so that the soft segment has a uniform molecular weight. Highly durable polyurethane with excellent shock absorption and vibration absorption. Compression set is evaluated by the following method.
In compliance with JIS K-6262, a punching machine is used to punch a polyurethane sheet-like molding (2 mm thick sheet) into φ13 mm, and three stacked test pieces are prepared as n=3 test pieces. The height at this time is measured using a thickness gauge. A test piece is placed on a lower compression plate (Dumbell Co., Ltd.), and compressed and fixed with a spacer (4.72 mm, Dumbbell Co., Ltd.), an upper compression plate, and a hexagon socket head bolt. This is placed in a circulating constant temperature bath and temperature-controlled at 70° C. for 24 hours. After that, it is taken out from the constant temperature bath, the compression plate is quickly released, and the test piece is allowed to stand on a wooden stand at 23° C. for 30 minutes. Compression permanent strain is calculated from the height of the test piece after standing. The compression set (%) measured by this method is preferably 90% or less, more preferably 80% or less, even more preferably 70% or less, and even more preferably 60% or less.

<Measurement of viscoelasticity of polyurethane (tan δ peak value, tan δ peak temperature, tan δ half width>
The viscoelasticity of polyurethane can be measured as follows.
A polyurethane sheet-like molding (1 mm thick sheet) is prepared by the above method and used for viscoelasticity evaluation. Using DVA-200 (manufactured by IT Keisoku Control Co., Ltd.), test piece dimensions 4 × 20 × 0.1 mm, strain 0.1%, frequency 10 Hz, tensile mode, heating rate 3 ° C./min, temperature range - Dynamic viscoelasticity is measured under conditions of 100 to 200°C. Create a (Log E' (Pa) / temperature (° C.) graph, (tan δ / temperature (° C.)) graph from the viscoelasticity measurement results, from which tan δ (loss tangent) peak value, tan δ peak temperature, tan δ half value The width can be calculated.In polyurethane, the higher the tan δ peak value, the better the sag resistance, wear resistance, shock absorption, and vibration absorption.The tan δ peak value is preferably 0.5 or more. , is more preferably 0.6 or more, more preferably 0.7 or more, and the tan δ peak temperature represents the glass transition temperature described above.

<Application>
The polyurethane of the present invention has excellent thermal stability and handleability during polymerization, an excellent balance between strength and flexibility, excellent chemical resistance, and abrasion resistance and vibration absorption as a resin. Widely used in foams, elastomers, elastic fibers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, active energy ray-curable resin compositions, etc. can.

In particular, when the polyurethane of the present invention is used for applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc., it has excellent chemical resistance and low temperature properties. Because of its balance, it is highly durable in areas where it comes into contact with human skin, or where cosmetic chemicals or alcohol for disinfection are used. A good characteristic of being strong can be imparted. It is also suitable for use as an intermediate coating for automotive exteriors, which requires flexibility at even lower temperatures.

The polyurethanes of the invention can be used in 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.

The polyurethanes of the invention 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, tire chain substitutes, and the like. It can also be used for keyboard films, films for automobiles, curled cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leather, dipping products, adhesives, etc.

The polyurethane elastomers of the present invention can also be foamed polyurethane elastomers or polyurethane foams. The method of foaming or forming a polyurethane elastomer may be, for example, chemical foaming using water or mechanical foaming such as mechanical flossing. Similarly, slabs, flexible foams obtained by molding, and the like can be mentioned.
Specific uses of foamed polyurethane elastomers or polyurethane foams include heat insulating materials and vibration damping materials for electronic equipment and construction, automobile seats, automobile ceiling cushions, bedding such as mattresses, insoles, midsoles and shoe soles.

The polyurethane of the present invention can also be applied as a solvent-based two-component paint, and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sporting goods. In addition, the polyurethane of the present invention, which can also be used for automobile repair as tar epoxy urethane, is a moisture-curable one-component paint, a blocked isocyanate-based solvent paint, an alkyd resin paint, a urethane-modified synthetic resin paint, an ultraviolet-curable paint, and a water-based paint. It can be used as a component of urethane paints, for example, plastic bumper paints, strippable paints, magnetic tape coating agents, floor tiles, flooring materials, paper, overprint varnishes such as wood grain printing films, wood varnishes, high It can be applied to processing coil coats, optical fiber protective coatings, solder resists, top coats for metal printing, base coats for vapor deposition, white coats for food cans, etc.

The polyurethane of the present invention can also be applied as an adhesive to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc. It can also be used as a component of low-temperature adhesives and hot melts. The polyurethane of the present invention 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 foams, and glass fiber sizing. etc. can be used

The polyurethane of the present invention can be used as a component of a fiber processing agent for shrink-proofing, wrinkle-proofing, water-repellent finishing, and the like.
When the polyurethane of the present invention is used as an 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 the elastic fiber is obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250°C or lower, more preferably 200°C or higher and 235°C or lower.

The polyurethane elastic fiber of the present invention can be used as it is as a bare yarn, or can be coated with other fibers and used as a covered yarn. 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. Further, the polyurethane elastic fiber of the present invention may contain a dyeing type disperse dye.

The polyurethane of the present invention can be used as a sealant and caulking for concrete walls, induced joints, around sashes, wall-type PC joints, ALC joints, board joints, composite glass sealants, heat-insulating sash sealants, automotive sealants, and the like. .
The polyurethane of the present invention 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, and surgical gloves. , artificial kidney potting materials, etc.

By modifying the terminal of the polyurethane of the present invention, it can be used as a raw material for UV curable coatings, electron beam curable coatings, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, and the like. can.

<Urethane (meth)acrylate oligomer>
A urethane (meth)acrylate oligomer can be produced by subjecting the polycarbonate polyol of the present invention to an addition reaction between a polyisocyanate and a droxyalkyl (meth)acrylate. 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 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 the same as the amount of hydroxyalkyl (meth)acrylate, the polycarbonate polyol of the present invention, and other raw material compounds used as necessary. Usually 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and usually 70, based on the total amount of compounds containing a functional group that reacts with isocyanate such as polyol and chain extender. It should be 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.

In this case, the amount of the polycarbonate polyol of the present invention used is preferably 25 mol% or more, more preferably 50 mol% or more, still more preferably, based on the total amount of the polycarbonate polyol of the present invention and other polyols used. is 70 mol % or more. When the amount of the polycarbonate polyol of the present invention used is larger than the above lower limit, the resulting cured product tends to have good hardness and stain resistance, which is preferable.

In addition, the amount of the polycarbonate polyol of the present invention used is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably, based on the total amount of the polycarbonate polyol of the present invention and other polyols used. is 50% by mass or more, particularly preferably 70% by mass or more. When the amount of the polycarbonate polyol of the present invention used is larger than the above lower limit, the viscosity of the resulting composition is lowered, the workability is improved, and the mechanical strength, hardness and abrasion resistance of the resulting cured product are improved. Favorable as a trend.

Furthermore, when a chain extender is used, the amount of the polycarbonate polyol of the present invention and other polyols used is 70% with respect to the total amount of the compound used in combination with the polycarbonate polyol of the present invention, other polyols, and the chain extender. It is preferably 80 mol % or more, more preferably 90 mol % or more, and particularly preferably 95 mol % or more. If the amount of polyol is larger than the above 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 usually 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 mass or more with respect to the total amount of the reaction system, and is preferably 40% by mass. % or more is more preferable. In addition, the upper limit of this total content is 100 mass %. When the total content of the urethane (meth)acrylate-based oligomer and its raw material compounds is 20% by mass or more, the reaction rate tends to increase and the production efficiency tends to improve, 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 or less, preferably 500 ppm or less, and a lower limit of usually 10 ppm or more, preferably 30 ppm or more, with respect to the total content of the urethane (meth)acrylate oligomer and its raw material compounds to be produced. Used.

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 or less, preferably 1000 ppm or less, particularly preferably 500 ppm or less, and the lower limit is usually It is used at 50 ppm or more, preferably 100 ppm or more.

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.

<Active energy ray-curable polymer composition>
The active energy ray-curable polymer composition containing the urethane (meth)acrylate oligomer described above (hereinafter sometimes referred to as "the active energy ray-curable polymer composition of the present invention") is described below. do.
The active energy ray-curable polymer composition of the present invention preferably has a molecular weight between calculated network crosslink points 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 calculated molecular weight between network crosslinks of the composition is 1000+500=1500.

From the above, it can be seen that for a mixture of moles of monofunctional compound MA of molecular weight WA, moles of fB-functional compound MB of molecular weight WB, and moles of fC-functional compound MC of molecular weight WC, the calculated molecular weight between network crosslink points of the composition is can be expressed by the following formula.

The calculated molecular weight between network crosslink points of the active energy ray-curable polymer composition of the present invention calculated in this manner is preferably 500 or more, more preferably 800 or more, and 1,000 or more. 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 , 3,000 or less.

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 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.

The active energy ray-curable polymer composition of the present invention 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 of the present invention, the content of the urethane (meth)acrylate-based oligomer is 40% by mass or more with respect to the total amount of the active energy ray-reactive components including the urethane (meth)acrylate-based oligomer. and more preferably 60% by mass or more. In addition, the upper limit of this content is 100 mass %. When the content of the urethane (meth)acrylate-based oligomer is 40% by mass 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 of the present invention, the content of the urethane (meth)acrylate oligomer is preferably large in terms of elongation and film-forming properties. In terms of points, the smaller the number, the better. From this point of view, the content of the urethane (meth)acrylate oligomer is preferably 50% by mass 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 mass or more. In addition, the upper limit of the content of the urethane (meth)acrylate oligomer is 100% by mass, and the content is preferably 100% by mass or less.

In addition, in the active energy ray-curable polymer composition of the present invention, the total content of the active energy ray-reactive components including the urethane (meth)acrylate-based oligomer affects the curing speed and surface curability of the composition. From the viewpoint of being excellent and leaving no tack, it is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the composition. , more preferably 95% by mass or more. In addition, the upper limit of this content is 100 mass %.

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 of the present invention, the content of the active energy ray-reactive monomer is determined from the viewpoint of adjusting the viscosity of the composition and adjusting physical properties such as hardness and elongation of the resulting cured product. It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of the composition. .

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 of the present invention, the content of the active-energy-ray-reactive oligomer should be , is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass 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 radical photopolymerization 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 photocationic polymerization initiator is used together with the photoradical polymerization initiator described above. 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 of the present invention is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray-reactive components. It is more preferably 5 parts by mass or less. When the content of the photopolymerization initiator is 10 parts by mass or less, it is preferable because deterioration of the mechanical strength due to decomposition products of the initiator hardly occurs.

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 of the present invention, the content of the photosensitizer is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray-reactive components. , 5 parts by mass or less. When the content of the photosensitizer is 10 parts by mass or less, the mechanical strength is less likely to decrease due to the decrease in 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, mica, talc, kaolin, metal oxides, metal fibers, iron, lead, and metal powders. fillers such as; carbon fibers, carbon black, graphite, carbon nanotubes, carbon materials such as fullerenes such as C60 (fillers and carbon materials may be collectively referred to as "inorganic components"); antioxidant 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 of the present invention, the content of the additive is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray-reactive components. It is more preferably not more than parts by mass. When the content of the additive is 10 parts by mass or less, the mechanical strength is less likely to decrease due to the decrease in crosslink density, which is preferable.

The solvent is used for the purpose of adjusting the viscosity of the active energy ray-curable polymer composition of the present invention, depending on, for example, the coating method for forming the coating film of the active energy ray-curable polymer composition of the present invention. can be used. A solvent may be used individually by 1 type, and may be used in mixture of 2 or more types. As the solvent, any known solvent can be used as long as the effects of the present invention 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 mass with respect to 100 parts by mass of the solid content of the active energy ray-curable polymer composition.

There are no particular limitations on the method of adding optional components such as the above-described additives to the active energy ray-curable polymer composition of the present invention, and conventionally known mixing and dispersing methods can be used. 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 of the present invention can be appropriately adjusted according to the application, mode of use, etc. of the composition. Therefore, the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is preferably 10 mPa s or more, more preferably 100 mPa s or more. It is preferably 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 urethane (meth)acrylate oligomer of the present invention, the types of the above optional components, their blending ratios, and the like.

Examples of coating methods for the active energy ray-curable polymer composition of the present invention 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, and a reverse roll coater method. , a lip coater method, a die coater method, a slot die coater method, an air knife coater method, a dip coater method and the like can be applied, and among them, a bar coater method and a gravure coater method are preferable.

<Cured film and laminate>
The active energy ray-curable polymer composition of the present invention 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. 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 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.
The 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 on the outside thereof. It's okay to be 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 is applied, such as a method of applying an upper layer and curing with active energy rays again, 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 it is possible, from the viewpoint of enhancing the 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 shapes such as metal plates. goods.

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, the active energy ray-curable polymer composition of the present invention has flexibility, breaking elongation, mechanical strength, and stain resistance that can follow deformation during three-dimensional processing, considering the molecular weight between the calculated network crosslink points. A cured film having both properties and hardness can be obtained.
In addition, the active energy ray-curable polymer composition of the present invention 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, still more preferably 100% or more, and 120% or more. It is particularly preferred to have

Such a cured film and laminate can be used as a paint substitute film, and can be effectively applied to, for example, interior and exterior building materials, automobiles, home electric appliances, and other various members.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.
Below, the evaluation method of each physical property value is as follows.

[Evaluation method]
<Quantitative determination of residual amount and conversion rate of monomer>
Dissolve polycarbonate diol in CDCl ₃ , measure 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.), identify the starting monomer (cyclic carbonate, initiator diol) from the signal position of each component, and integrate Each content was calculated from the values. The detection limit at that time is 0.01% by mass as the mass of the raw material monomer with respect to the mass of the entire sample. The cyclic carbonate content was also calculated by this method.

<Measurement of molecular weight>
Analysis of weight average molecular weight and number average molecular weight was performed by ¹ H-NMR and GPC. They are described as Mn (NMR), Mw (GPC), and Mn (GPC), respectively.
Measurement method by ¹ H-NMR: Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured, and the number average was calculated from the conversion rate of the raw material monomer and the molecular weight of the initiator. The molecular weight Mn (NMR) was estimated.
Measurement method by GPC: The polystyrene-equivalent weight average molecular weight (Mw), the polystyrene-equivalent weight average molecular weight Mw (GPC), and the number average molecular weight Mn (GPC) were determined by GPC measurement under the following conditions.
Apparatus: HLC-8220 manufactured by Tosoh Corporation
Column: TSKgel Super HZM-N
(4.6mm I.D. x 15cmL x 4 pieces)
Reference column: TSKgel Super H-RC
(6.0mm ID x 15cmL x 1 piece)
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0 mL/min
Column temperature: 40°C
RI detector: RI (device HLC-8220 built-in)

<Calculation of molecular weight distribution (D)>
The molecular weight distribution (D) was calculated by weight average molecular weight Mw (GPC)/number average molecular weight Mn (GPC) measured by GPC.
The value of (D) of the corresponding sample was used for D and D1 used in the calculation of the molecular weight distribution change rate (ΔD). The rate of change in molecular weight distribution (ΔD) after heating at 100° C. for 12 hours, which will be described later in Examples, is calculated by the following formula.
Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

<Measurement of amount of inorganic component contained>
0.2 g of polycarbonate diol was precisely weighed into a Kjeldahl flask and subjected to wet decomposition using concentrated sulfuric acid and concentrated nitric acid. After cooling to room temperature, pure water was added to a constant volume, and the solution was measured with ICP-MS ELEMENT 2 (manufactured by Thermo Fisher Scientific) to determine the content of elements contained in the polycarbonate diol (mass ppm). Phosphorus and sodium contents were calculated using values calibrated from standard solutions of phosphorus and sodium therein. Other inorganic elements can also be measured in a similar manner. When using an inorganic component that does not volatilize or decompose under the reaction conditions, the inorganic component concentration (ppm) is the ratio of the inorganic component amount (g) such as the catalyst used for charging to the yield (g) of the polycarbonate diol. Equivalent to.

<Composition Analysis and Terminal Structure Analysis of Polycarbonate Diol>
Polycarbonate diol was dissolved in CDCl ₃ , 400 MHz ¹ H-NMR (ECZ-400 manufactured by JEOL Ltd.) was measured, and from the signal position of each component, the structure derived from each raw material monomer (cyclic carbonate, initiator diol). The unit was identified and each content (mol%) was calculated from the integrated value. Similarly, in the terminal structure, each content (mol %) was calculated from the integrated value. Structures that can be detected as terminal structures other than terminal hydroxyl groups are alkyl carbonate terminals (for example, in the case of methyl carbonate), phenyl carbonate terminals, carboxyl groups, ester groups, and aldehyde groups, and the detection limit is the molar amount of the entire sample. It is 0.01 mol % as the molar amount of the raw material monomer with respect to

<Number of terminal hydroxyl groups per molecule of polycarbonate polyol>
The value obtained by subtracting the number of terminal structures other than the terminal hydroxyl groups of the obtained polycarbonate polyol from the number of hydroxyl groups per molecule of the starting initiator polyol (for example, 2 for diols and 3 for triols) is 1 of the polycarbonate polyol. The number of terminal hydroxyl groups per molecule.

<Hydroxyl value>
The hydroxyl value of the polycarbonate diol was measured by a method using an isocyanate reagent according to ASTM E1899-16.
Furthermore, the number average molecular weight (Mn) was obtained from the measured hydroxyl value by the following formula (I).
Number average molecular weight = 2 × 56.1 / (hydroxyl value × 10 ^-3 ) (I)

<Measurement of melt viscosity>
After the polycarbonate diol was heated to 60° C. and melted, the melt viscosity was measured at 60° C. using an E-type viscometer (DV-II+Pro manufactured by BROOKFIELD, cone: CPE-52). The melt viscosity at 60° C. of polycarbonate diol having a molecular weight of 3000 is 30000 mPa.s. s or less, 25000 mPa.s or less. s or less, 20000 mPa.s or less. It is preferable in the order below s. Furthermore, 15000 mPa. s or less, or even 10000 mPa.s or less. s or less. The melt viscosity at 60° C. of polycarbonate diol having a molecular weight of 2000 is 20000 mPa.s. s or less, 15000 mPa.s or less. s or less, 10000 mPa.s or less. s or less, 8000 mPa.s or less. s or less, 6000 mPa.s or less. It is preferable in the order below s. If the melt viscosity is high, the handleability of the polycarbonate diol is lowered, and sufficient handleability may not be obtained during storage, transfer, and urethane polymerization. In addition, if the viscosity increases due to long-term heating during storage or transfer, it may cause troubles such as clogging of the transfer or polymerization apparatus, impossibility of extraction, and impossibility of stirring.

<Measurement of APHA value>
It was measured in accordance with JIS K0071-1 (1998) by comparing polycarbonate polyol with a standard solution in a colorimetric tube. A color standard solution of 1000 degrees (1 mgPt/mL) (manufactured by Kishida Chemical Co., Ltd.) was used as a reagent.

[raw materials used]
The abbreviations and manufacturers of the raw materials used are listed below. The following ingredients were used unless otherwise specified.
Trimethylene carbonate (TMC) Tokyo Chemical Industry Co., Ltd. 1,10-Decanediol (DD) Tokyo Chemical Industry Co., Ltd. (derived from plant material)
1,3-propanediol (1,3PD) manufactured by DuPont (derived from plant material)
Diphenyl phosphate (DPP) Tokyo Chemical Industry Co., Ltd. Sodium acetate (AcONa) Tokyo Chemical Industry Co., Ltd. Tin octylate (Sn (Oct) ₂ ) Tokyo Chemical Industry Co., Ltd. Isosorbide (ISB) Tokyo Chemical Industry Co., Ltd. (plant-derived product )
Dimethylolpropionic acid (DMPA) Tokyo Chemical Industry Co., Ltd. Cyclododecane trimethanol (CDTM) Mitsubishi Chemical Corporation Tris(2-hydroxyethyl) isocyanurate (ICTE) Tokyo Chemical Industry Co., Ltd. 1,3,5-Benzene trimethanol ( PhTM) Tokyo Chemical Industry Co., Ltd. Trimethylolpropane (TMP) Tokyo Chemical Industry Co., Ltd.

The following two cyclic carbonate compounds were synthesized by the method described in Journal of the American Chemical Society (2007), 129(22), 6994-6995 (Goodwin, Andrew P. et al).
2-methyl-2-carboxymethyl-trimethylene carbonate (cas: 507471-78-5) (TMC-Me-COOH)
2-methyl-2-benzyloxycarbonyl-trimethylene carbonate (cas: 247142-68-3) (TMC-Me-COOBn)

The following cyclic carbonate compounds are described in Polymer Vol. 37, No. 19, 1996, p. 4383.
Cyclobishexamethylene carbonate (1,3,10,12-Tetraoxacyclooctadecane-2,11-dione cas: 82613-63-6) (HMC-D)
The following cyclic carbonate compounds are described in Macromolecules 2012, Vol. 45, No. 6, p2668.
5-methyl-5-(2,5,8,11-tetraoxadodecyl)-1,3-dioxa-2-one (1) (cas: 1365611-65-9) (TOTMC)

[Production and Analysis of Polycarbonate Diol I]
<Example 1-1>
A 100 mL glass reaction vessel was charged with trimethylene carbonate (20 g, 0.20 mol, 30 eq.), 1,10-decanediol (1.14 g, 6.5 mmol, 1.0 eq.), diphenyl phosphate (49 mg, 200 μmol, 0 03 eq. of phosphorus atom (Mw: 31) equivalent to 300 ppm) was added, and polymerization was carried out at 100° C. for 5 hours using a mechanical stirring device under a nitrogen stream to obtain a crude polycarbonate diol. The resulting reaction solution was dissolved in about 20 mL of methylene chloride and added dropwise to 100 mL of ice-cooled methanol. When the obtained liquid was stirred, a highly viscous liquid precipitated, and then methanol was removed to obtain a highly viscous liquid. The polycarbonate diol obtained by repeating this reprecipitation operation twice was dried with an evaporator.
The obtained polycarbonate diol is referred to as "PCD1-1".

The conversion of the PCD1-1 reaction, Mn (NMR), Mn (GPC), molecular weight distribution (D), and catalyst-derived phosphorus content were measured, and the results are shown in Table 1.
The molar ratio of structural unit A (derived from TMC) and structural unit B (derived from DD) in this PCD1-1 was measured by ¹ H-NMR and found to be 97:3. Also, the viscosity at 60° C. was 18000 mPa·s.
When the terminal structure and ratio were confirmed by ¹ H-NMR, terminal groups other than hydroxyl groups were not observed. The number of terminal hydroxyl groups per molecule of polycarbonate polyol is equivalent to 2.0. When the ratio of terminal hydroxyl groups was confirmed, terminal hydroxyl groups derived from trimethylene carbonate accounted for 99 mol % or more of all terminals. When the content of trimethylene carbonate was confirmed by ¹ H-NMR, no trimethylene carbonate peak was observed.

<Example 1-2>
The amount of diphenyl phosphate used in Example 1-1 was reduced to 1/10, and the same reaction as in Example 1-1 was carried out.
Trimethylene carbonate (20 g, 196 mmol, 30 eq.), 1,10-decanediol (1.14 g, 6.5 mmol, 1.0 eq.) and diphenyl phosphate (4.9 mg, 200 μmol, 0.003 eq.) were added to a test tube. , equivalent to 30 ppm as phosphorus atoms) was added, and polymerization was carried out at 100° C. under a nitrogen stream using a mechanical stirring device. The polycarbonate diol obtained after 24 hours was withdrawn at room temperature.
This polycarbonate diol is referred to as "PCD1-2".
This PCD1-2 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

<Example 1-3>
Trimethylene carbonate (471 g, 4.61 mol, 17.9 eq.) and 1,10-decanediol (45 g, 0.25 mol, 1.0 eq.) were added to a 1 L separable flask and completely melted at 80°C. and diphenyl phosphoric acid (1.3 g, 5.2 mmol, 0.03 eq.) were added and polymerized at 80° C. for 6 hours under a nitrogen stream using a mechanical stirrer to obtain a crude polycarbonate diol. The resulting reaction solution was dissolved in 500 g of methylene chloride and added dropwise to 2 L of methanol while stirring. After the dropwise addition was completed, the mixture was allowed to stand, and a highly viscous liquid precipitated. After that, the methanol was removed to obtain a highly viscous liquid. This operation was repeated three times to obtain a polycarbonate diol.
This polycarbonate diol is referred to as "PCD1-3".
This PCD1-3 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

The molar ratio of structural unit A (derived from TMC) and structural unit B (derived from DD) in this PCD1-3 was measured by ¹ H-NMR and found to be 95:5. Moreover, the viscosity at 60° C. was 4200 mPa·s. When the hydroxyl value was measured, it was 61.7 mgKOH/g, which corresponds to a molecular weight of 1819 converted from the hydroxyl value. When coloration was confirmed, APHA was 20.
When the terminal structure and ratio were confirmed by ¹ H-NMR, terminal groups derived from alkyl terminals were not observed, and all were terminal hydroxyl groups, and the number of terminal hydroxyl groups per molecule was 2.0. When the ratio of terminal hydroxyl groups derived was confirmed by ¹ H-NMR, terminal hydroxyl groups derived from trimethylene carbonate accounted for 99 mol % or more of all the terminals. Also, no trimethylene carbonate peak was observed.

<Example 1-4>
Trimethylene carbonate (10.5 g, 0.10 mol, 17.9 eq.), 1,10-decanediol (1.0 g, 5.7 mmol, 1.0 eq.), sodium acetate (42 mg, 513 μmol, 0.09 eq.) was added, and polymerization was carried out at 80° C. for 5 hours using a mechanical stirring device under a nitrogen stream to obtain a crude polycarbonate diol. The resulting reaction solution was dissolved in about 20 mL of toluene, and separated and washed three times with 20 mL of desalted water. The obtained polycarbonate diol was dried with an evaporator. When coloration was confirmed, APHA was 25.
This polycarbonate diol is referred to as "PCD1-4".
This PCD1-4 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

<Comparative Example 1-1>
Using the same molar amount of tin octylate (81 mg, 200 μmol, 0.03 eq. corresponding to 1149 ppm as Sn (Mw 118.7)) as a catalyst in the same manner as in Example 1-1, polycarbonate was prepared in the same manner as in Example 1-1. A diol was produced.
The obtained polycarbonate diol is referred to as "PCD-H1-1".
This PCD-H1-1 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

<Comparative Example 1-2>
A polycarbonate diol was produced under the same conditions as in Example 1-2, except that the reaction temperature was changed to 140°C.
The obtained polycarbonate diol is referred to as "PCD-H1-2".
This PCD-H1-2 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

<Comparative Example 1-3>
A polycarbonate diol having the same composition and molecular weight as in Example 1-1 was produced by the following transesterification reaction using 1,3-propanediol, 1,10-decanediol and diphenyl carbonate.
A 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator was charged with 1,3-propanediol (1168.1 g), 1,10-decanediol (82.7 g), diphenyl carbonate (3249 .2 g) and an aqueous solution of magnesium acetate tetrahydrate (7.2 mL, concentration: 8.4 g/L) were added, and the atmosphere was replaced with nitrogen gas. 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. Next, the pressure was lowered to 9.3 kPa over 90 minutes, and further lowered to 0.7 kPa over 30 minutes to continue the reaction, and then the temperature was raised to 170° C. to remove phenol and unreacted dihydroxy compounds out of the system. while reacting for 60 minutes to obtain a polycarbonate diol-containing composition. After that, a 0.85% by mass phosphoric acid aqueous solution (2.8 mL) was added to deactivate the magnesium acetate, and the mixture was distilled under the same conditions for 3 hours to obtain a polycarbonate diol.
The obtained polycarbonate diol is referred to as "PCD-H1-3".
This PCD-H1-3 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.
The molar ratio of structural unit A (derived from 1,3PD) and structural unit B (derived from DD) in this PCD-H1-3 was measured by ¹ H-NMR and found to be 96:4. Moreover, the viscosity at 60° C. was 40000 mPa·s.

<Comparative Example 1-4>
A polycarbonate diol having the same composition and molecular weight as those of Examples 1-3 was produced by the following transesterification reaction using 1,3-propanediol, 1,10-decanediol and diphenyl carbonate.
A 1 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator was charged with 1,3-propanediol (295.5 g), 1,10-decanediol (20.9 g), diphenyl carbonate (798 .9 g) and an aqueous solution of magnesium acetate tetrahydrate (2.0 mL, concentration: 8.4 g/L) were added, and the atmosphere was replaced with nitrogen gas. 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. Next, the pressure was lowered to 9.3 kPa over 90 minutes, and further lowered to 0.7 kPa over 30 minutes to continue the reaction, and then the temperature was raised to 170° C. to remove phenol and unreacted dihydroxy compounds out of the system. while reacting for 60 minutes to obtain a polycarbonate diol-containing composition. After that, a 0.85% by mass phosphoric acid aqueous solution (0.8 mL) was added to deactivate the magnesium acetate, and the mixture was distilled under the same conditions for 3 hours to obtain a polycarbonate diol.
The obtained polycarbonate diol is referred to as "PCD-H1-4".
This PCD-H1-4 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.
The molar ratio of structural unit A (derived from 1,3PD) and structural unit B (derived from DD) in this PCD-H1-4 was measured by ¹ H-NMR and found to be 95:5. Also, the viscosity at 60° C. was 9700 mPa·s. When the hydroxyl value was measured, it was 60.8 mgKOH/g, which corresponds to a molecular weight of 1845 converted from the hydroxyl value. When the terminal structure and proportion were confirmed by ¹ H-NMR, terminal phenoxy groups were present in a proportion of 0.05% of all terminal groups.

<Comparative Example 1-5>
Polymerization using diphenyl phosphoric acid was carried out under the same conditions as in Example 1-3 to obtain a crude polycarbonate diol, which was then converted to polycarbonate diol without performing the subsequent reprecipitation operation.
The obtained polycarbonate diol is designated as "PCD-H1-5".
This PCD-H1-5 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

<Comparative Example 1-6>
Polymerization using sodium acetate was carried out under the same conditions as in Example 1-4 to obtain a crude polycarbonate diol, which was then converted to polycarbonate diol without performing liquid separation and washing.
This polycarbonate diol is referred to as "PCD-H1-6".
This PCD-H1-6 was analyzed in the same manner as in Example 1-1, and the results are shown in Table 1.

The following Table 2 shows the structural unit A:structural unit B molar ratio of the polycarbonate diols obtained in Examples 1-1, 1-3, Comparative Examples 1-3 and 1-4 (in Table 2, "A:B"), molecular weight and molecular weight distribution (D), and viscosity at 60°C.

<Discussion>
As can be seen from the comparison between Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4, a narrow molecular weight distribution can be obtained by conducting ring-opening polymerization at an appropriate reaction temperature using a specific catalyst and catalyst amount. A polycarbonate diol was obtained.
From the comparison of Example 1-1 with Comparative Example 1-3 and Example 1-3 with Comparative Example 1-4, the viscosity of the polycarbonate diol with a narrow molecular weight distribution was lower than that of the polycarbonate diol having the same composition and molecular weight. .

[Measurement of molecular weight distribution change rate (ΔD)]
The polycarbonate diols obtained in the above Examples and Comparative Examples were heated at 100° C. for 12 hours to confirm changes in molecular weight distribution (D).
The molecular weight distribution change rate (ΔD) after heating at 100° C. for 12 hours is calculated by the following formula.
Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

<Example 2-1>
PCD1-1 (2 g) obtained in Example 1-1 was placed in a glass bottle and heated in an oven at 100° C. for 12 hours to examine the rate of change in molecular weight distribution (ΔD).

<Example 2-2>
PCD1-34 (2 g) obtained in Example 1-3 was placed in a glass bottle and heated in an oven at 100° C. for 12 hours to examine the rate of change in molecular weight distribution (ΔD).

<Example 2-3>
PCD1-4 (2 g) obtained in Example 1-4 was placed in a glass bottle and heated in an oven at 100° C. for 12 hours to examine the rate of change in molecular weight distribution (ΔD).

<Example 2-4>
PCD1-4 (2 g) obtained in Example 1-4 was further washed with water three times. After that, it was placed in a glass bottle and heated in an oven at 100° C. for 12 hours, and the rate of change in molecular weight distribution (ΔD) was examined.

<Comparative Example 2-1>
PCD1-1 obtained in Example 1-1 (2 g, containing P: 47 ppm) and diphenyl phosphate (4.9 mg, 20 μmol, equivalent to P: 300 ppm) were placed in a glass bottle and dissolved, and then placed in an oven at 100 ° C. for 12 hours. After heating, the rate of change in molecular weight distribution (ΔD) was examined.

<Comparative Example 2-2>
PCD1-1 obtained in Example 1-1 (2 g, containing P: 47 ppm) and diphenyl phosphate (49 mg, 200 μmol, corresponding to P: 3000 ppm) were placed in a glass bottle and dissolved, and then placed in an oven at 100 ° C. for 12 hours. After heating, the rate of change in molecular weight distribution (ΔD) was examined.

<Comparative Example 2-3>
PCD-H1-5 obtained in Comparative Example 1-5 was placed in a glass bottle and heated in an oven at 100° C. for 12 hours to examine the rate of change in molecular weight distribution (ΔD).

<Comparative Example 2-4>
PCD-H1-6 obtained in Comparative Example 1-6 was placed in a glass bottle and heated in an oven at 100° C. for 12 hours to examine the rate of change in molecular weight distribution (ΔD).

The measurement results of the molecular weight distribution rate of change (ΔD) of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4 are summarized in Table 3 below together with catalyst species and catalyst amounts.

<Discussion>
From the results of Examples 2-1 to 2-4, the polycarbonate diols of the present invention had a small rate of change (ΔD) in molecular weight distribution under heating and were stable under heating.
On the other hand, as shown in Comparative Examples 2-1 to 2-4, when a large amount of compounds containing elements such as P and Na were contained, the molecular weight distribution was broadened during heating, resulting in poor thermal stability.

[Production and Analysis of Polycarbonate Diol II]
Polycarbonate diols were produced using different initiator diols and cyclic carbonates, and the resulting polycarbonate diols were subjected to ¹ H-NMR and MALDI-MASS analyses, confirming that the target polycarbonate diol structure was obtained.

<Example 3-1>
1,10-Decanediol, which is the initiator diol in Example 1-1, was changed to isosorbide (ISB) and polymerization was carried out in the same manner to obtain a polycarbonate diol.
The obtained polycarbonate diol is referred to as "PCD3-1".

<Example 3-2>
1,10-Decanediol, which is the initiator diol in Example 1-1, was changed to dimethylolpropionic acid (DMPA) and polymerization was carried out in the same manner to obtain a polycarbonate diol.
The obtained polycarbonate diol is referred to as "PCD3-2".

<Example 3-3>
Polycarbonate diol was synthesized in the same manner as in Example 1-1 using trimethylene carbonate synthesized from plant-derived 1,3-propanediol as a starting material. The conversion rate at this time was 99.5%.
The obtained polycarbonate diol is designated as "PCD3-3".

<Example 3-4>
initiator diol 1,10-decanediol (1 eq.), trimethylene carbonate (30 eq.) and 2-methyl-2-carboxymethyl-trimethylene carbonate (TMC-Me-COOH) (15 eq.) as cyclic carbonates, Using diphenyl phosphate (0.03 eq.) as a catalyst, the same operation as in Example 1-1 was performed to obtain a polycarbonate diol.
The obtained polycarbonate diol is referred to as "PCD3-4".
Analysis by ¹ H-NMR and MALDI-MASS confirmed that theoretical amounts of terminal hydroxyl groups and carboxyl groups remained in the polycarbonate polyol, and that a polycarbonate polyol with a corresponding structure was obtained. ¹ H-NMR analysis revealed that the ratio of structural units derived from TMC and TMC-Me-COOH in the obtained polycarbonate polyol was 33.4:16.6.

<Example 3-5>
Initiator diol 1,10-decanediol (1 eq.), trimethylene carbonate (30 eq.) and 2-methyl-2-benzyloxycarbonyl-trimethylene carbonate (TMC-Me-COOBn) (15 eq.) as cyclic carbonates. ), and using diphenyl phosphate (0.03 eq.) as a catalyst, a polycarbonate diol was obtained in the same manner as in Example 1-1.
The obtained polycarbonate diol is designated as "PCD3-5".
Analysis by ¹ H-NMR and MALDI-MASS confirmed that theoretical amounts of terminal hydroxyl groups and benzyloxycarbonyl groups remained in the polycarbonate polyol, and that a polycarbonate polyol with a corresponding structure was obtained.
¹ H-NMR analysis revealed that the ratio of structural units derived from TMC and TMC-Me-COOBn in the obtained polycarbonate polyol was 23.4:13.1.

<Example 3-6>
Initiator diol 1,4-butanediol (1 eq.), Cyclobishexamethylene carbonate (1,3,10,12-Tetraoxacyclooctadecane-2,11-dione cas: 82613-63-6) (HMC- D) (6.6 eq.), using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) (0.1 eq.) as catalyst, Example 1-4 A polycarbonate diol was obtained by performing the same operation.
The obtained polycarbonate diol is designated as "PCD3-6".

<Example 3-7>
1,10-Decanediol of the initiator diol was changed to 5.0 g of hydrogenated polybutadiene polyol (GI1000 manufactured by Nippon Soda Co., Ltd.), and 5.0 g of trimethylene carbonate, 40 mg of sodium acetate, and 10 mL of toluene were used. -4 was performed to obtain a polycarbonate diol. At the start of the reaction, the mixture was separated into two phases, but the resulting polycarbonate diol was uniform without separation.
The obtained polycarbonate diol is designated as "PCD3-7".

<Example 3-8>
1,10-Decanediol of the initiator diol was changed to 5.0 g of polytetramethylene ether glycol (PTMG1000 manufactured by Mitsubishi Chemical Corporation), and 5.0 g of trimethylene carbonate, 40 mg of sodium acetate, and 10 mL of toluene were used. A polycarbonate diol was obtained by performing the same operation as in 1-4. At the start of the reaction, the mixture was separated into two phases, but the resulting polycarbonate diol was uniform without separation.
The obtained polycarbonate diol is designated as "PCD3-8".

<Example 3-9>
1,10-decanediol of the initiator diol was changed to 5.0 g of silicone diol (carbinol-modified dimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd. KF6000), trimethylene carbonate 5.0 g, sodium acetate 40 mg, toluene 10 mL, A polycarbonate diol was obtained by performing the same operation as in Example 1-4. At the start of the reaction, the mixture was separated into two phases, but the resulting polycarbonate diol was uniform without separation.
The obtained polycarbonate diol is designated as "PCD3-9".

<Example 3-10>
1,3-propanediol (1,3PD) (2.48 g, 1 eq.) as the initiator diol, 5-methyl-5-(2,5,8,11-tetraoxadodecyl)-1 as the cyclic carbonate, 3-Dioxa-2-one (1) (cas: 1365611-65-9) (TOTMC) (86.2 g, 9.0 eq.) using diphenyl phosphate (0.16 g, 0.02 eq.) as a catalyst and reacted for 130 hours in the same manner as in Example 1-1.
The resulting polycarbonate diol composition was dissolved in a mixture of hexane and acetone, and purified by column chromatography while changing the developing solvent from the mixture of hexane and acetone to a mixture of dichloromethane and methanol.
The obtained polycarbonate diol is designated as "PCD3-10".
The phosphorus atom content of PCD3-10 was analyzed and found to be 8 ppm. Further, when the hydroxyl value of PCD3-10 was measured, it was 64.1 mgKOH/g, which corresponds to a molecular weight of 1748 converted from the hydroxyl value.

The results of Examples 3-1 to 3-10 are summarized in Table 4 below.

[Production and Analysis of Polycarbonate Polyol III]
Polyol Y was changed to a triol having three hydroxyl groups each having various substituents shown below, and a polycarbonate polyol was produced and analyzed at the catalyst amount, reaction temperature, and reaction time shown in Table 5. Analysis by ¹ H-NMR and MALDI-MASS confirmed that theoretical amounts of terminal hydroxyl groups and benzyloxycarbonyl groups remained in the polycarbonate polyol, and that a polycarbonate polyol with a corresponding structure was obtained.

<Example 4-1>
Cyclododecane trimethanol (CDTM) was used. The obtained polycarbonate polyol is referred to as "PCD4-1".
<Example 4-2>
Tris(2-hydroxyethyl) isocyanurate (ICTE) was used. The obtained polycarbonate polyol is referred to as "PCD4-2".
<Example 4-3>
1,3,5-Benzenetrimethanol (PhTM) was used. The obtained polycarbonate polyol is referred to as "PCD4-3".
<Example 4-4>
Trimethylolpropane (TMP) was used. The obtained polycarbonate polyol is referred to as "PCD4-4".

The conversion rate, Mn (GPC), and molecular weight distribution (D) of the polycarbonate polyols obtained in Examples 4-1 to 4-4 were measured, and the results are shown in Table 5.

[Synthesis and Evaluation of Polyurethane]
Using the obtained polycarbonate diol, a polyurethane was synthesized and its physical properties were evaluated.

<Example 5-1>
PCD1-3 obtained in Example 1-3 was used to synthesize a polyurethane by the synthesis method described later, and the physical properties thereof were evaluated as described later.
<PCD1-3>
Molecular weight distribution (D): 1.08
Molar ratio of structural unit A to structural unit B in polycarbonate diol: 95:5
Hydroxyl value: 61.7mgKOH/g
Number average molecular weight determined from hydroxyl value: 1819
Viscosity at 60°C 4200mPa s

<Comparative Example 5-1>
Polyurethane was synthesized in the same manner as in Example 5-1 using PCD-H1-4 having a wide molecular weight distribution synthesized by the transesterification method obtained in Comparative Example 1-4, and its physical properties were evaluated.
<PCD-H1-4>
Molecular weight distribution (D): 2.04
Molar ratio of structural unit A to structural unit B in polycarbonate diol: 95:5
Hydroxyl value: 60.8mgKOH/g
Number average molecular weight determined from hydroxyl value: 1845
Viscosity at 60°C: 9700 mPa s

<Synthesis of Polyurethane>
247.7 g of PCD1-3 and 102.3 g of 4,4'-diphenylmethane diisocyanate (MDI), which had been heated and melted at 100° C., were placed in a 1-liter tin plate reactor and allowed to react for 30 minutes to obtain a prepolymer. After that, 22.8 g of 1,4-butanediol (BG) was added, stirred for 50 seconds, poured into a mold separately temperature-controlled at 100° C., and cured. (Preparation molar ratio: MDI/BG/PCD=3/2/1, NCO/OH ratio=1.05) After that, post-curing was performed at 100° C. for 1 hour to obtain a polyurethane cured product.

<Physical property evaluation>
(compression molding)
After placing the PET release film and the cured polyurethane on a compression molding mold (15 cm×8 cm×2 mm thickness), the PET release film and the mold were placed in that order. These were placed on the stage of a preheated heating press (manufactured by Toyo Seiki Seisakusho, product name "Mini Test Press"), and then brought into contact with the stage of the heating press to pressurize (pressure: 0. 5 MPa x temperature: 218-225°C x time: 2 minutes). After that, the pressure setting of the heating press was gradually increased, and the molding was completed by heating at 13 MPa for 2 minutes. Lower the pressure of the heating press, take out the mold, set it in a cooling press (manufactured by Toyo Seiki Seisakusho, product name "Mini Test Press") that has been cooled by running cooling water in advance, and cool (pressure 10 MPa x time 2 minutes) to obtain a sheet-like polyurethane molding. The physical properties of the polyurethane molded article were evaluated as follows, and the results are shown in Table 6. For the viscoelasticity measurement, a 1-mm-thick sheet prepared by the same method was used using a 1-mm-thick mold.

(Weight average molecular weight (Mw) of polyurethane)
Polyurethane was dissolved in dimethylacetamide to prepare a dimethylacetamide solution having a concentration of 0.14% by mass. GPC device [manufactured by Tosoh Corporation, product name “HLC-8220” (column: TSKGEL
GMHXL-L, 2)], the dimethylacetamide solution was injected, and the weight average molecular weight (Mw) of the polyurethane was measured in terms of standard polystyrene.

(Hardness (after 15 seconds))
Polyurethane moldings were cut into 3-cm squares, and 3-ply pieces were used as test pieces (n=5). Using an Asker rubber altimeter ISO-A type (manufactured by Kobunshi Keiki Co., Ltd.), the hardness was measured after 15 seconds of contact, and the hardness was obtained from the median value.

(100% modulus, 300% modulus)
A punching machine was used to punch a polyurethane molding (2 mm thick sheet) into a No. 3 dumbbell shape. Using a tensile tester (AGS-10kNX, manufactured by Shimadzu Corporation) and an extensometer (DSES-1000, manufactured by Shimadzu Corporation), a tensile test was performed with a gauge length of 20 mm, a tensile speed of 200 mm, and n = 3. The stress at 100% or 300% was determined respectively. The median of these values was defined as 100% modulus or 300% modulus, respectively.

(Tensile strength/elongation at break)
A tensile test was performed using the same test piece and test conditions as in the 100% modulus/300% modulus measurement, and the stress at break (referred to as tensile strength) and elongation (referred to as elongation at break) were measured.

(Compression set)
According to JIS K-6262, a punching machine was used to punch a polyurethane molded body (2 mm thick sheet) into φ13 mm, and three sheets were laminated to prepare n=3 test pieces. The height at this time was measured using a thickness gauge. The test piece was placed on a lower compression plate (Dumbell Co., Ltd.), and compressed and fixed with a spacer (4.72 mm, Dumbbell Co., Ltd.), an upper compression plate, and a hexagon socket head bolt. This was placed in a circulating constant temperature bath controlled at 70° C. and heated for 24 hours. Then, it was taken out from the constant temperature bath, the compression plate was quickly released, and the test piece was allowed to stand on a wooden stand at 23°C for 30 minutes. The height of the test piece after standing was measured with a thickness gauge, the compression set was calculated for each, and the median value of n3 was used as a representative value.

(Polyurethane viscoelasticity measurement (tan δ peak value, tan δ peak temperature, tan δ half width)
A 1 mm-thick sheet-like polyurethane molded article was obtained by changing only the mold for the compression molding, and the viscoelasticity was measured.
Using DVA-200 (manufactured by IT Keisoku Co., Ltd.), test piece size 4 × 20 × 1 mm, strain 0.1%, frequency 10 Hz, tensile mode, heating rate 3 ° C./min, temperature range -100 to Dynamic viscoelasticity was measured at 200°C.

The analytical values of the resulting polyurethane are summarized in Table 6 below.
Moreover, the measurement results of viscoelasticity are shown in FIG. 1 (Log E′ (Pa)/temperature (° C.) graph and FIG. 2 (tan δ/temperature (° C.)).

<Discussion>
In Example 5-1, since the viscosity of the polycarbonate polyol used was low, the viscosity of the liquid during the production of the polyurethane was lowered, which facilitated charging, stirring, transfer, etc., and improved handleability. Polycarbonate diol was previously melted at 100° C. and kept warm to produce polyurethane. The polyurethane molded article obtained in Example 5-1 is a polyurethane having high mechanical strength and excellent tensile strength and elongation at break, which are characteristics of polycarbonate polyol.
From a comparison between Example 5-1 and Comparative Example 5-1, the polycarbonate polyol having a narrow molecular weight distribution had a low compression set and a high restoring property (resistance to settling) against compression deformation of polyurethane. In addition, it has a high value of tan δ (loss tangent) in viscoelasticity measurement, and is excellent in shock absorption and abrasion resistance when used as an elastomer.

Claims (24)

A composition containing a polycarbonate polyol,
A polycarbonate polyol composition in which the polycarbonate polyol satisfies the following conditions (1) to (4).
(1) containing a structural unit A represented by the following formula (A); (2) having a number average molecular weight (Mn) of 300 or more and 8,000 or less; Calculated molecular weight distribution change rate (ΔD) after heating at 100 ° C. for 12 hours is 0.20 or less Molecular weight distribution change rate (ΔD) = (D1-D) / D
D: Molecular weight distribution of polycarbonate polyol D1: Molecular weight distribution of the polycarbonate polyol after heating at 100° C. for 12 hours

(In the formula (A), R ₁ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms.) The polycarbonate polyol composition according to claim 1, wherein the polycarbonate polyol further contains a structural unit B represented by the following formula (B).

(In the formula (B), R ₂ represents an alkylene group having 3 or more carbon atoms which may have a side chain substituent, and within the above carbon number range, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and at least one selected from the group consisting of halogen atoms, or may have a substituent containing these atoms, provided that R ₂ is different from R ₁ in the formula (A).) 2. The polycarbonate polyol composition according to claim 1, wherein the proportion of -R ₁ -OH groups in the molecular chain ends of the polycarbonate polyol is 80 mol% or more with respect to 100% of the total molar amount of all terminal groups. . 2. The polycarbonate polyol composition according to claim 1, wherein the number of terminal hydroxyl groups per molecule of said polycarbonate polyol is 1.8 to 6.0. 2. The polycarbonate polyol composition according to claim 1, wherein the total content of metal elements and phosphorus elements in the composition is 150 mass ppm or less. 2. The polycarbonate polyol composition according to claim 1, wherein the elemental phosphorus content in the composition is 0.01 to 150 mass ppm. 2. The polycarbonate polyol composition according to claim 1, wherein the elemental sodium content in the composition is 0.01 to 150 mass ppm. 2. The polycarbonate polyol composition according to claim 1, comprising a phosphorus compound having an aromatic ring. 2. The polycarbonate polyol composition according to claim 1, wherein the content of the cyclic carbonate X represented by the following formula (1) in the composition is 1% by mass or less with respect to 100% of the total mass of the composition. .

(In Formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.) The polycarbonate polyol composition according to claim 9, wherein the cyclic carbonate X is represented by the following formula (1A).

(In formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.) 2. The polycarbonate polyol composition according to claim 1, wherein the content of the structural unit A in the polycarbonate polyol is 70 mol% or more with respect to 100% of the total molar amount of all structural units constituting the polycarbonate polyol. . 2. The polycarbonate polyol composition according to claim 1, wherein the polycarbonate polyol is produced using a plant-derived raw material. The polycarbonate polyol composition according to any one of claims 1 to 12, comprising a step of ring-opening polymerization of a cyclic carbonate X represented by the following formula (1) in the presence of a polymerization catalyst using polyol Y as an initiator. A method of making things.

(In Formula (1), X ₁ to X ₄ are each independently an alkyl group having 1 to 20 carbon atoms or a hydrogen atom, and the alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.Z is a carbon number 1 that may have a side chain substituent -20 alkylene group, at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms within the above carbon number range may have.) The method for producing a polycarbonate polyol composition according to claim 13, wherein the cyclic carbonate X is represented by the following formula (1A).

(In formula (1A), R _a and R _b each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. The alkyl group is an oxygen atom, a sulfur atom, or a nitrogen atom within the above-described carbon number range. , at least one selected from the group consisting of silicon atoms and halogen atoms, or may have a substituent containing these atoms.) 15. The method for producing a polycarbonate polyol composition according to claim 14, wherein the cyclic carbonate X is trimethylene carbonate. The polyol Y may have at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and a halogen atom, or a substituent containing these atoms, having 2 to 2 carbon atoms. 14. The method for producing a polycarbonate polyol composition according to claim 13, which is a diol compound or triol compound of No. 50. The method for producing a polycarbonate polyol composition according to claim 13, wherein the polyol Y is at least one oligomer polyol selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and silicone polyols. 14. The method for producing a polycarbonate polyol composition according to claim 13, comprising a step of deactivating and/or removing the polymerization catalyst after the ring-opening polymerization. According to claim 13, wherein the ring-opening polymerization is performed by using the polymerization catalyst containing elemental phosphorus in an elemental amount of phosphorus of 0.01 to 1000 ppm by mass with respect to the total mass of the cyclic carbonate X and the polyol Y. A process for making the described polycarbonate polyol composition. 14. Production of the polycarbonate polyol composition according to claim 13, wherein the ring-opening polymerization is carried out using a solvent of 50 parts by mass or less with respect to 100 parts by mass of the total mass of the cyclic carbonate X and the polyol Y, or without using a solvent. Method. A polyurethane obtained using the polycarbonate polyol composition according to any one of claims 1 to 12. 22. The polyurethane of Claim 21 made using a polyisocyanate, a chain extender and said polycarbonate polyol composition. A method for producing polyurethane using the polycarbonate polyol composition according to any one of claims 1 to 12. Obtaining a polycarbonate polyol composition by the method for producing a polycarbonate polyol composition according to any one of claims 13 to 20, and producing a polyurethane using the obtained polycarbonate polyol composition, A method for producing polyurethane.

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