JP6503923B2 - Polycarbonate diol and polyurethane using the same - Google Patents

Description

  The present invention relates to a polycarbonate diol useful as a raw material of a polycarbonate-based polyurethane and a polyurethane using the same.

  Conventionally, the raw material of the main soft segment part of polyurethane produced on an industrial scale is an ether type represented by polytetramethylene glycol, a polyester polyol type represented by adipate ester, and a polylactone type represented by polycaprolactone. Or polycarbonate type represented by polycarbonate diol (Non-Patent Document 1).

Among these, polyurethane using an ether type is excellent in hydrolysis resistance, flexibility and stretchability, but is said to be inferior in heat resistance and weather resistance. On the other hand, although polyurethane having polyester polyol type has improved heat resistance and weatherability, the hydrolysis resistance of the ester group is low and it can not be used depending on the application.
On the other hand, polyurethanes using the polylactone type are considered to be a grade that is superior in hydrolysis resistance as compared to polyurethanes using the polyester polyol type; I can not do it. Moreover, although it is also proposed to mix and use these polyester polyol type, ether type, and polylactone type as a raw material of a polyurethane, it has not been able to completely compensate each fault.

On the other hand, polyurethane using polycarbonate type represented by polycarbonate diol is regarded as the best durability grade in heat resistance and hydrolysis resistance, and durable film, artificial leather for automobiles, (water-based) paint, It is widely used as an adhesive.
However, polycarbonate diols which are widely marketed at present are polycarbonate diols mainly synthesized from 1,6-hexanediol, but since they are highly crystalline, they are cohesive of soft segments when made into polyurethane. In particular, applications have been limited due to problems such as high flexibility, poor flexibility, elongation, bending or elastic recovery at low temperatures. Furthermore, it is also pointed out that the artificial leather manufactured using this polyurethane as a raw material has a hard texture, and has a "feel" worse than natural leather.

In order to solve the above problems, polycarbonate diols of various structures have been proposed.
For example, there is a method of using 1,6-hexanediol and another dihydroxy compound as raw materials as a copolycarbonate diol, specifically, polycarbonates copolymerized using 1,6-hexanediol and 1,4-butanediol as raw materials Diol (Patent Document 1), Polycarbonate diol copolymerized using 1,6-hexanediol and 1,5-pentanediol as a raw material (Patent Document 2), copolymerized using 1,3-propanediol and another dihydroxy compound as a raw material An improved polycarbonate diol (Patent Document 3) has been proposed.

In addition, a method using a dihydroxy compound having a substituent in the main chain has been proposed as a powerful method for inhibiting the crystallinity of a dihydroxy compound-derived site, for example, 2-methyl-1,3-propanediol and other alkylenes. Polycarbonate diol copolymerized using glycol as a raw material (Patent Document 4), Polycarbonate diol copolymerized using 3-methyl-1,5-pentanediol and another alkylene diol as a raw material (Patent Document 5), Disubstituted by methyl group etc. The curable composition (patent document 6) using the polycarbonate diol which co-polymerized the C1-C8 diol and the C2-C12 diol which have the quaternary carbon atom which were carried out is mentioned.

In addition, polyurethanes using polycarbonate diols having long-chain diols such as 2-methyl-1,8-octanediol and 1,9-nonanediol as a raw material have been proposed. (Patent Document 7)
Furthermore, as a polycarbonate diol excellent in chemical resistance, low temperature properties and heat resistance, polycarbonate diols having an average carbon number of more than 6 have been proposed. (Patent Document 8)
Moreover, the flexibility, chemical resistance, etc. are improved by mixing and using polycarbonate diol which used C3-C6 diol as a raw material and polycarbonate diol which used C7-C12 diol as a raw material Polyurethanes have been proposed which use a polycarbonate diol. (Patent Documents 9 to 11)
Polycarbonate diol component containing 1,8-octanediol and 1,9-nonanediol which may be substituted with methyl group as raw materials, polyurethane containing polylactone diol component as essential component and leather-like composite sheet using the polyurethane (Patent Document 12)
Synthetic leather that can reduce environmental impact and is excellent in low-temperature flexibility, using a polyurethane resin consisting of polycarbonate diol using plant-derived diol and petroleum-derived diol having 4 to 20 carbon atoms as raw materials (Patent Document 13)

Unexamined-Japanese-Patent No. 5-51428 Unexamined-Japanese-Patent No. 2-289616 WO 2002/070584 pamphlet WO 2006/088152 pamphlet Japanese Patent Application Laid-Open No. 60-195117 JP, 2011-162646, A Japanese Examined Patent Publication No. 3-54967 JP 2000-95852 A Patent No. 04177318 Patent No. 04506754 JP 2008-106415 A Unexamined-Japanese-Patent No. 4-93316 JP, 2014-1475, A

"Basics and Applications of Polyurethanes" pp. 96-106 supervised by Katsuhisa Matsunaga, CMC Publishing Co., Ltd., November 2006

However, the polycarbonate diols described in these previously known techniques such as Patent Documents 1 to 3 have insufficient low temperature properties when used as polyurethane. The polycarbonate diols described in Patent Documents 4 to 6 and the like were inferior in chemical resistance and heat resistance when used as polyurethane. Furthermore, the polycarbonate diols described in Patent Document 7 and the like are inferior in chemical resistance and abrasion resistance when used as polyurethane. In addition, short-chain diols substantially used in polycarbonate diols such as Patent Documents 8 to 11 have 6 carbon atoms, and when they are polyurethane, they have poor chemical resistance. The polycarbonate diol used in Patent Document 12 is inferior in chemical resistance and heat resistance because the average carbon number of the raw material diol exceeds 6 and the polyester component is essential. The polycarbonate diol which consists of plant origin diol and petroleum origin diol currently indicated by patent document 13 was inferior to the chemical resistance, the low temperature characteristic, and the heat resistance balance.
An object of the present invention is to provide a polycarbonate diol as a raw material of polyurethane excellent in the balance of chemical resistance, low temperature characteristics, heat resistance and physical properties of touch which can not be reached by the above-mentioned prior art.

  As a result of intensive studies to solve the above problems, the present inventors have found that a structural unit derived from a compound represented by the following formula (A) and a structure derived from a compound represented by the following formula (B) Polycarbonate diol having a hydroxyl value of 20 mg-KOH / g or more and 450 mg-KOH / g or less, wherein the ratio of ether group to carbonate group of the polycarbonate diol is 5.0 mol% or less It has been found that the polycarbonate diol is a raw material of polyurethane having a good balance of chemical resistance, low temperature characteristics, heat resistance and touch feeling, and the present invention has been made.

That is, the gist of the present invention is as follows.
[1] A polycarbonate diol comprising a structural unit derived from a compound represented by the following formula (A) and a structural unit derived from a compound represented by the following formula (B), which is represented by the following formula (A) The molar ratio of the structural unit derived from the compound to the structural unit derived from the compound represented by the following formula (B) is 70:30 to 98: 2, and the hydroxyl value is 20 mg-KOH / g or more and 450 mg -A polycarbonate diol characterized in that the ratio of an ether group to a carbonate group of the polycarbonate diol is 5.0 mol% or less.

HO-R ¹ -OH (A)
HO-R ² -OH (B)
(In the above formula (A), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and in the above formula (B), R ² represents a substituted or unsubstituted carbon atom having 10)示 す represents a divalent alkylene group having a carbon number of 12. The carbon atom in the alkylene group of R ¹ and R ² is a primary carbon atom, a secondary carbon atom or a tertiary carbon atom.)

[2] The total of structural units derived from the compound represented by the formula (A) and structural units derived from the compound represented by the formula (B) in the total structural units of the polycarbonate diol is 50 mol The polycarbonate diol according to the above-mentioned [1], which is characterized in that it is% or more.
[3] The polycarbonate diol according to the above [1] or [2], wherein an average carbon number of a dihydroxy compound obtained by hydrolyzing the polycarbonate diol is 4 or more and 5.5 or less.

[4] The polycarbonate diol according to any one of the above [1] to [3], wherein the hydroxyl value is 20 mg-KOH / g or more and 60 mg-KOH / g or less.
[5] The above-mentioned [1] to [4], wherein the compound represented by the formula (A) is at least one compound selected from the group consisting of 1,3-propanediol and 1,4-butanediol The polycarbonate diol according to any one of the above.

[6] The above-mentioned compound represented by the above-mentioned formula (B) is at least one compound selected from the group consisting of 1,10-decanediol, 1,11-undecanediol and 1,12-dodecanediol The polycarbonate diol as described in any one of [1]-[5].
[7] The polycarbonate diol according to any one of the above [1] to [6], wherein at least one of the compound represented by the formula (A) and the compound represented by the formula (B) is derived from a plant .

[8] A polyurethane comprising the polycarbonate diol according to any one of the above [1] to [7].
[9] An artificial leather or a synthetic leather manufactured using the polyurethane described in the above [8].
[10] A paint or a coating agent produced using the polyurethane described in the above [8].

[11] An elastic fiber produced using the polyurethane described in the above [8].
[12] A water-based polyurethane paint produced by using the polyurethane according to the above [8].
[13] A pressure-sensitive adhesive or an adhesive produced using the polyurethane described in the above [8].

[14] An active energy ray-curable polymer composition comprising the polycarbonate diol according to any one of the above [1] to [7].
[15] A method for producing the polycarbonate diol according to any one of the above [1] to [7], which is a compound represented by the following formula (A) and a compound represented by the following formula (B) A method for producing a polycarbonate diol, which comprises polycondensing by transesterification using a carbonate compound.

HO-R ¹ -OH (A)
HO-R ² -OH (B)
(In the above formula (A), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and in the above formula (B), R ² represents a substituted or unsubstituted carbon atom having 10)示 す represents a divalent alkylene group having a carbon number of 12. The carbon atom in the alkylene group of R ¹ and R ² is a primary carbon atom, a secondary carbon atom or a tertiary carbon atom.)

  The polyurethane produced using the polycarbonate diol of the present invention is characterized by excellent balance of chemical resistance, low temperature characteristics, heat resistance and touch feeling, and is used for elastic fiber, synthetic or artificial leather, paint, high functional elastomer application It is suitable and extremely useful in industry.

Hereinafter, although the form of the present invention is explained in detail, the present invention is not limited to the following embodiments, and can be variously deformed and carried out within the limits of the gist.
Here, in the present specification, “mass%” and “weight%”, “mass ppm” and “weight ppm”, and “mass part” and “part by weight” are respectively synonymous. Moreover, when it only describes as "ppm", it shows the thing of "weight ppm."

[1. Polycarbonate diol]
The polycarbonate diol of the present invention is a polycarbonate diol including a structural unit derived from a compound represented by the following formula (A) and a structural unit derived from a compound represented by the following formula (B). The molar ratio of the structural unit derived from the compound represented by and the structural unit derived from the compound represented by the following formula (B) is 70:30 to 98: 2, and the carbonate diol of the polycarbonate diol is It is characterized by the hydroxyl value whose ratio of the ether group to group is 5.0 mol% or less is 20 mg-KOH / g or more and 450 mg-KOH / g or less.

HO-R ¹ -OH (A)
HO-R ² -OH (B)
(In the above formula (A), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and in the above formula (B), R ² represents 10 to 12 carbon atoms. It represents a substituted or unsubstituted divalent alkylene group, and the carbon atom in the alkylene group of R ¹ and R ² is a primary carbon atom, a secondary carbon atom or a tertiary carbon atom.
<1-1. Structural features>
The structural unit derived from the compound represented by said Formula (A) which concerns on this invention is represented by following formula (C), for example. Moreover, the structural unit derived from the compound represented by said Formula (B) is represented by following formula (D), for example.

(In the above formula (C), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms. The carbon atom in the alkylene group of R ¹ is a primary carbon atom, A secondary carbon atom or a tertiary carbon atom)

(In the above formula (D), R ² represents a substituted or unsubstituted divalent alkylene group having 10 to 12 carbon atoms. The carbon atom in the alkylene group of R ² is a primary carbon atom, A secondary carbon atom or a tertiary carbon atom)
In the formula (C), R ¹ may be either a one and more. Further in the formula (D), R ² may be either a one and more.

In the above formula (C), R ¹ is a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and the carbon atom in the alkylene group of R ¹ is a primary carbon atom or a secondary carbon atom Or a tertiary carbon atom, which is preferably a primary carbon atom or a secondary carbon atom because chemical resistance, low temperature properties and heat resistance are better, more preferably R ¹ is unsubstituted Is preferred.

In the formula (D), R ² is a substituted or unsubstituted divalent alkylene group having 10 to 12 carbon atoms, and the carbon atom in the alkylene group of R ² is a primary carbon atom or a secondary carbon atom Or a tertiary carbon atom, which is preferably a primary carbon atom or a secondary carbon atom because chemical resistance, low temperature properties and heat resistance are better, more preferably R ² is unsubstituted Is preferred.

Furthermore, in the above formula (C) and the formula (D), the following is calculated by the equation, the ratio is 10% or less to the total number of carbon atoms of R ¹ and R ² of the number of carbon atoms of the substituent in R ¹ and R ² Is preferred,
5% or less is more preferable, 3% or less is more preferable, 2% or less is particularly preferable, and 0% is most preferable.

  The polycarbonate diol of the present invention comprises a structural unit derived from the compound represented by the formula (A) and a structural unit derived from the compound represented by the formula (B). By containing a structural unit derived from the compound represented by the formula (A) and a structural unit derived from the compound represented by the formula (B), good chemical resistance and low temperature properties when converted to polyurethane can be obtained. You can get it. Furthermore, the ratio between the structural unit derived from the compound represented by the formula (A) and the structural unit derived from the compound represented by the formula (B) (hereinafter referred to as “(A): (B)” (A): (B) = 70:30 to 98: 2 is preferable, 75: 25 to 97: 3 is more preferable, 80: 20 to 95: 5 is more preferable, 80) : 20 to 90: 10 is most preferable. If the content ratio of the structural unit derived from the compound represented by the formula (A) is too large, the low temperature properties of the polyurethane may not be sufficient. If the content ratio of the structural unit derived from the compound represented by the formula (A) is too small, the chemical resistance of the polyurethane may not be sufficient.

  Furthermore, when the average carbon number of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol is 4 or more and 5.5 or less, it is possible to obtain good chemical resistance, heat resistance and abrasion resistance when made into polyurethane. it can. The upper limit of the average carbon number is preferably 5.3, more preferably 5.2, and still more preferably 5.1. The lower limit of the average carbon number is preferably 4.3, more preferably 4.5, and still more preferably 4.7. Below the lower limit, low temperature properties may be insufficient, and when the upper limit is exceeded, chemical resistance, heat resistance, and abrasion resistance may be insufficient.

  The average carbon number of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol in the present invention is determined from the result of gas chromatography analysis of the dihydroxy compound obtained by hydrolyzing the polycarbonate diol by heating in the presence of an alkali. be able to. Specifically, it is calculated from the carbon number of the dihydroxy compound obtained by hydrolyzing polycarbonate diol and the molar ratio of the dihydroxy compound to the total dihydroxy compound.

  The ratio of the total of the structural unit derived from the compound represented by the formula (A) and the structural unit derived from the compound represented by the formula (B) to the total structural units of the polycarbonate diol is chemical resistance, low temperature In terms of the balance of physical properties of the properties, it is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 95 mol% or more.

The polycarbonate diol of the present invention is a copolymer if it contains a structural unit derived from the compound represented by the formula (A) and a structural unit derived from the compound represented by the formula (B) Although it may be a mixture of different polycarbonate diols, it is preferably a copolymer because the low temperature characteristics and the flexibility become good. In the case of a copolymer, a block copolymer or a random copolymer may be used, but a polycarbonate diol of a random copolymer is preferable because the low temperature characteristics and the flexibility become good.

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

<1-2. Dihydroxy compound>
The compound represented by the above formula (A) which is a dihydroxy compound which is a raw material of the polycarbonate diol of the present invention is 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1, 4- butanediol etc. are mentioned. Among them, 1,3-propanediol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable, because the polyurethane is excellent in the balance between the chemical resistance and the low temperature characteristics. The compound represented by the formula (A) may be one kind or plural kinds.

  Examples of the compound represented by the formula (B) include 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like. Among them, 1,10-decanediol and 1,12-dodecanediol are preferable, and 1,10-decanediol is more preferable, because of excellent balance of chemical resistance and low temperature characteristics when used as polyurethane. The compound represented by the formula (B) may be one kind or plural kinds.

  In the production of the polycarbonate diol of the present invention, as long as the effects of the present invention are not impaired, a dihydroxy compound other than the compound represented by the formula (A) and the compound represented by the formula (B) (other dihydroxy compounds May be used). Specific examples thereof include linear dihydroxy compounds, dihydroxy compounds having an ether group, dihydroxy compounds having a branched chain, and dihydroxy compounds having a cyclic group. However, when other dihydroxy compounds are used, the proportion of structural units derived from other dihydroxy compounds is preferably 50 mol% or less with respect to the total structural units of polycarbonate diol in order to obtain the effects of the present invention effectively. 30 mol% or less is more preferable, 20 mol% or less is more preferable, and 10 mol% or less is the most preferable. If the proportion of structural units derived from other dihydroxy compounds is high, the balance of chemical resistance and low temperature properties may be impaired.

It is preferable that the compound represented by said Formula (A) is plant-derived from a viewpoint of environmental load reduction. As a compound represented by said Formula (A) applicable as plant origin, a 1, 3- propanediol, a 1, 4- butanediol etc. are mentioned.
It is preferable that the compound represented by said Formula (B) is plant-derived from a viewpoint of environmental load reduction. As a compound represented by said Formula (B) applicable as plant origin, 1,10-decanediol, 1,11-undecanediol, 1,12- dodecanediol etc. are mentioned.

  As a plant-derived dihydroxy compound, for example, in the case of 1,4-butanediol, succinic acid, succinic acid anhydride, succinic acid ester, maleic acid, maleic acid anhydride, maleic acid ester, tetrahydrofuran and γ obtained by a fermentation method -1,4-butanediol may be produced by chemical synthesis from butyrolactone etc., or 1,4-butanediol may be produced directly by fermentation, or 1,3-butadiene obtained by fermentation May be used to produce 1,4-butanediol. Among them, a method of directly producing 1,4-butanediol by a fermentation method and a method of hydrogenating succinic acid with a reduction catalyst to obtain 1,4-butanediol are efficient and preferable.

In the case of 1,3-propanediol, after 3-hydroxypropionaldehyde is produced from glycerol, glucose or other saccharides by fermentation, it is further converted to 1,3-propanediol, or fermented from glucose or other saccharides It is obtained by direct production of 1,3-propanediol by the method.
1,10-decanediol can be synthesized by synthesizing sebacic acid from castor oil by alkali melting and hydrogenating it directly or after the esterification reaction.

<1-3. Carbonate compound>
The carbonate compound (sometimes referred to as "carbonic diester") that can be used for producing the polycarbonate diol of the present invention is not limited as long as the effects of the present invention are not impaired, but dialkyl carbonate, diaryl carbonate, or alkylene carbonate may be mentioned. Be Among these, diaryl carbonate is preferable from the viewpoint of reactivity.

  Specific examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate and the like, with diphenyl carbonate being preferred.

<1-4. Transesterification catalyst>
The polycarbonate diol of the present invention can be produced by polycondensation of a compound represented by the above formula (A), a compound represented by the above formula (B) and a carbonate compound by transesterification.

  In the case of producing the polycarbonate diol of the present invention, a transesterification catalyst (hereinafter sometimes referred to as a catalyst) can be used as needed to accelerate the polymerization. In that case, if too much catalyst remains in the obtained polycarbonate diol, the reaction may be inhibited or the reaction may be excessively accelerated when producing polyurethane using the polycarbonate diol.

For this reason, the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less as the content in terms of catalyst metal.
As the transesterification catalyst, any compound generally regarded as having transesterification ability can be used without limitation.

Examples of transesterification catalysts include compounds of Group 1 metals of periodic table such as lithium, sodium, potassium, rubidium and cesium; compounds of group 2 metals of periodic table such as magnesium, calcium, strontium and barium; titanium, zirconium Compounds of periodic table group 4 metals such as; compounds of periodic table group 5 metals such as hafnium; compounds of periodic table group 9 metals such as cobalt; compounds of periodic table group 12 metals such as zinc; aluminum etc. Compounds of periodic table group 13 metals; compounds of periodic table group 14 metals such as germanium, tin and lead; compounds of periodic table group 15 metals such as antimony and bismuth; lanthanum, cerium, europium, ytterbium etc. lanthanide based metals And the like. Among these, from the viewpoint of increasing the transesterification reaction rate, a compound of a periodic table group 1 metal, a periodic table group 2 metal compound, a periodic table group 4 metal compound, a periodic table group 5 metal compound, Preferred are compounds of periodic table group 9 metals, compounds of periodic table group 12 metals, compounds of periodic table group 13 metals, compounds of periodic table group 14 metals, compounds of periodic table group 1 metals, periodic table group Compounds of Group 2 metals are more preferred, and compounds of Group 2 metals of the periodic table are even more preferred. Among the compounds of Group 1 metal of the periodic table, compounds of lithium, potassium and sodium are preferable, compounds of lithium and sodium are more preferable, and compounds of sodium are more preferable. Among the compounds of periodic table group 2 metals, compounds of magnesium, calcium and barium are preferable, compounds of calcium and magnesium are more preferable, and compounds of magnesium are more preferable. These metal compounds are mainly used as hydroxides, salts and the like. Examples of salts when used as salts include halide salts such as chloride, bromide and iodide; carboxylates such as acetate, formate and benzoate; methanesulfonic acid, toluenesulfonic acid, trifluoro Sulfonic acid salts such as sodium methanesulfonic acid; Phosphorus-containing salts such as phosphoric acid salts, hydrogen phosphates and dihydrogen phosphates; and acetylacetonate salts. The catalytic metal can also be used as an alkoxide such as methoxide or ethoxide.

  Among these, preferably, acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halides and alkoxides of at least one metal selected from Group 2 metals of the periodic table are used, More preferably, acetates, carbonates and hydroxides of Group 2 metals are used, more preferably magnesium, calcium acetates and carbonates and hydroxides are used, and particularly preferably magnesium and calcium. Acetate is used, most preferably magnesium acetate is used.

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

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

  The molecular chain ends of the polycarbonate diol of the present invention are the number of ends derived from the compound represented by the formula (A) and the number of ends derived from the compound represented by the formula (B) with respect to the total number of ends. The proportion of the total number is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, particularly preferably 97 mol% or more, and most preferably 99 mol% or more. By setting it in the above-mentioned range, it becomes easy to obtain a desired molecular weight when made into polyurethane, and it becomes possible to become a raw material of polyurethane excellent in the balance of chemical resistance and low temperature characteristics.

  The ratio of the number of end groups derived from the carbonate compound at the molecular chain end of polycarbonate diol is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol%, with respect to the total number of terminals. The content is particularly preferably 1 mol% or less.

<1-6. Ratio of ether group to carbonate group>
The molecular chain of the polycarbonate diol of the present invention is mainly a structure having a carbonate group. However, in the case of a polycarbonate diol obtained by the reaction of a dihydroxy compound and a carbonate compound, an ether group may be contained in the molecular chain. The polycarbonate diols according to the invention are characterized in that they contain ether groups, the proportion of ether groups being a specific proportion. The ether group may be incorporated into the molecular chain of the polycarbonate diol by by-producing an ether group from a dihydroxy compound used as a raw material, an alcohol by-produced from a carbonate compound, a polymethylene oxide or the like. Since the polycarbonate diol containing a large amount of ether groups may deteriorate the weather resistance and heat resistance, the proportion of ether groups should be small. In the polycarbonate diol of the present invention, the ratio of ether group to polycarbonate group is 5.0 mol% or less, preferably 3.0 mol% or less, more preferably 2.0 mol% or less, still more preferably 1.0 It is preferable that it is mol% or less, especially 0.5 mol% or less. In order to reduce the ether group content in the polycarbonate diol molecular chain, it is preferable to lower the reaction temperature in the polycondensation reaction of the dihydroxy compound and the carbonate compound.

<1-7. Hydroxyl value>
The lower limit of the hydroxyl value of the polycarbonate diol of the present invention is 20 mg KOH / g, preferably 25 mg KOH / g, more preferably 30 mg KOH / g, further preferably 35 mg KOH / g. In addition, the upper limit is 450 mg-KOH / g, preferably 230 mg-KOH / g, more preferably 150 mg-KOH / g, still more preferably 120 mg-KOH / g, still more preferably 75 mg-KOH / g, particularly preferably 60 mg -KOH / g, most preferably 45 mg KOH / g. If the hydroxyl value is less than the above lower limit, the viscosity may be too high, and handling during polyurethane formation may be difficult. When the above upper limit is exceeded, physical properties such as flexibility and low temperature properties may be insufficient when polyurethane is used.

<1-8. Molecular weight / molecular weight distribution>
The lower limit of the number average molecular weight (Mn) determined from the hydroxyl value of the polycarbonate diol of the present invention is preferably 250, more preferably 300, still more preferably 400. On the other hand, the upper limit is preferably 5,000, more preferably 4,000, and still more preferably 3,000. When the Mn of the polycarbonate diol is less than the above lower limit, sufficient flexibility may not be obtained when it is urethane. On the other hand, if the above upper limit is exceeded, the viscosity may be increased, which may impair the handling during the polyurethane formation.

  The weight average molecular weight / number average molecular weight (Mw / Mn), which is the molecular weight distribution of the polycarbonate diol of the present invention, is not particularly limited, but the lower limit is preferably 1.5, more preferably 1.8. The upper limit is preferably 3.5, more preferably 3.0. If the molecular weight distribution exceeds the above range, the physical properties of the polyurethane produced using this polycarbonate diol tend to be hard at low temperatures, the elongation decreases, etc., and it is attempted to produce a polycarbonate diol having a molecular weight distribution below the above range. Then, sophisticated purification operations such as removal of oligomers may be required.

  The weight average molecular weight is a weight average molecular weight in terms of polystyrene, and the number average molecular weight is a number average molecular weight in terms of polystyrene. The weight average molecular weight can be determined usually by gel permeation chromatography (sometimes abbreviated as GPC).

<1-9. Use ratio of raw materials>
The amount of the carbonate compound to be used in the production of the polycarbonate diol of the present invention is not particularly limited, but the lower limit is preferably 0.35, more preferably 0.50, more preferably a molar ratio to a total of 1 mol of dihydroxy compounds. Is 0.60, and the upper limit is preferably 1.00, more preferably 0.98, still more preferably 0.97. If the amount of the carbonate compound used exceeds the above upper limit, the proportion of terminal groups of the obtained polycarbonate diol which is not a hydroxyl group may increase or the molecular weight may not fall within a predetermined range. There is a case.

<1-10. Catalyst deactivator>
As described above, when a catalyst is used in the polymerization reaction, the catalyst usually remains in the obtained polycarbonate diol, and the remaining catalyst causes heating of the polycarbonate diol to cause increase in molecular weight, composition change, color tone deterioration, etc. In some cases, the polyurethane formation reaction can not be controlled. In order to suppress the influence of the remaining catalyst, it is preferable to inactivate the transesterification catalyst by adding, for example, a phosphorus compound or the like in an approximately equimolar amount to the transesterification catalyst used. Furthermore, after the addition, the transesterification catalyst can be efficiently inactivated by heat treatment or the like as described later. As the phosphorus-based compound, phosphoric acid and phosphorous acid are preferable, and phosphoric acid is more preferable, because the effect is large even if the amount is small.

As a phosphorus compound used for inactivation of a transesterification catalyst, For example, Inorganic phosphoric acids, such as phosphoric acid and phosphorous acid, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, Organic phosphoric acid esters such as triphenyl phosphate and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.
The amount of the phosphorus-based compound used is not particularly limited, but as described above, it may be approximately equimolar to the transesterification catalyst used, and specifically, to 1 mol of the transesterification catalyst used The upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.6 mol, more preferably 0.8 mol, still more preferably 1.0 mol. When using a smaller amount of phosphorus-based compound, heating the polycarbonate diol causes increase in molecular weight, composition change, color tone deterioration, etc. of the polycarbonate diol, and inactivation of the transesterification catalyst is not sufficient. When the polycarbonate diol is used, for example, as a raw material for polyurethane production, the reactivity to the isocyanate group of the polycarbonate diol may not be sufficiently reduced. In addition, when a phosphorus compound exceeding this range is used, the obtained polycarbonate diol is colored, or when the polycarbonate diol is used as a raw material for polyurethane, the polyurethane is easily hydrolyzed, and further, the phosphorus compound bleeds out. There is a possibility of

Inactivation of the transesterification catalyst by adding a phosphorus-based compound can be carried out even at room temperature, but heat treatment is more efficient. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 180 ° C., more preferably 150 ° C., still more preferably 120 ° C., still more preferably 100 ° C., and the lower limit is preferably 50 ° C., more preferably Preferably it is 60 ° C, more preferably 70 ° C. If the temperature is lower than this, inactivation of the transesterification catalyst may be time-consuming and inefficient, and the degree of inactivation may be insufficient. On the other hand, at temperatures exceeding 180 ° C., the obtained polycarbonate diol may be colored.
The reaction time with the phosphorus compound is not particularly limited, but is usually 0.1 to 5 hours.

<1-11. Residual monomers etc>
When an aromatic carbonic diester such as diphenyl carbonate is used as a raw material, phenols by-produce during the production of polycarbonate diol. Since phenols are monofunctional compounds, they may be an inhibitor in the production of polyurethane, and urethane bonds formed by phenols have a weak bonding force, so they are thermally treated in the subsequent steps, etc. It may dissociate, and isocyanate and phenols may be regenerated to cause problems. In addition, since phenols are also irritating substances, the remaining amount of phenols in polycarbonate diol is preferably smaller. Specifically, the weight ratio to the polycarbonate diol is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, and preferably 100 ppm or less. In order to reduce phenols in the polycarbonate diol, as described later, the pressure of the polymerization reaction of the polycarbonate diol is a high vacuum of 1 kPa or less as an absolute pressure, or thin film distillation may be performed after the polymerization of the polycarbonate diol. It is valid.

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

  In the polycarbonate diol, the dihydroxy compound used at the time of manufacture may remain. The residual amount of the dihydroxy compound in the polycarbonate diol is not limited, but is preferably small, and is preferably 1% by weight or less, more preferably 0.1% by weight or less, as a weight ratio to the polycarbonate diol. Is less than 0.05% by weight. When the residual amount of the dihydroxy compound in the polycarbonate diol is large, the molecular length of the soft segment part in forming the polyurethane may be insufficient, and a desired physical property may not be obtained.

  The polycarbonate diol may contain a cyclic carbonate (cyclic oligomer) by-produced in the production. For example, when 1,3-propanediol is used as the compound represented by the above formula (A), 1,3-dioxane-2-one or a compound in which two or more molecules thereof form a cyclic carbonate, etc. It may be formed and contained in polycarbonate diol. Since these compounds may cause side reactions in the polyurethane formation reaction and cause turbidity, the pressure of the polymerization reaction of polycarbonate diol is set to a high vacuum of 1 kPa or less as an absolute pressure, or synthesis of polycarbonate diol is performed. It is preferable to carry out thin film distillation etc. later and to remove as much as possible. The content of these cyclic carbonates contained in the polycarbonate diol is not limited, but is preferably 3% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less as a weight ratio to the polycarbonate diol .

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

For example, the polyurethane of the present invention can be produced by reacting the polycarbonate diol of the present invention with a polyisocyanate and a chain extender in the range of ordinary temperature to 200 ° C.
In addition, the polycarbonate diol of the present invention is first reacted with an excess of polyisocyanate to produce a prepolymer having an isocyanate group at the end, and the chain extender is used to increase the polymerization degree to produce the polyurethane of the present invention. Can do.

<2-1. Polyisocyanate>
The polyisocyanate used for producing a polyurethane using the polycarbonate diol of the present invention includes various known polyisocyanate compounds of aliphatic, alicyclic or aromatic.
For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer isocyanate obtained by converting carboxyl group of dimer acid to isocyanate group, etc. 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 diisocyanate Alicyclic diisocyanates such as (isocyanatomethyl) cyclohexane; xylylene diisocyanate; 4,4'-diphenyldiy Cyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4 ' -Dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylenepolyphenylisocyanate, phenylene diisocyanate and m-tetramethylene And aromatic diisocyanates such as xylylene diisocyanate. One of these may be used alone, or two or more may be used in combination.

  Among these, it is preferable to have a balance of physical properties of the obtained polyurethane and to be able to obtain a large amount at low cost industrially, 4,4′-diphenylmethane diisocyanate (hereinafter sometimes referred to as MDI), hexamethylene diisocyanate, Preference is given to 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate.

2-2. Chain extender>
The chain extender used when 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 described later, Usually, polyols and polyamines can be mentioned.

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

These chain extenders may be used alone or in combination of two or more.
Among these, 1,4-butanediol (hereinafter sometimes referred to as 1,4 BD), 1,5 in that the balance of the physical properties of the obtained polyurethane is preferable, and that a large amount can be obtained at low cost industrially. -Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, Preferred are 1,3-diaminopropane, isophorone diamine and 4,4'-diaminodicyclohexylmethane.

  Moreover, the chain extender in the case of manufacturing the prepolymer which has a hydroxyl group mentioned later is a low molecular weight compound which has at least two isocyanate groups, and, specifically, it is <2-1. Polyisocyanate] and the like.

<2-3. Chain stopper>
In the production of the polyurethane of the present invention, a chain stopper having one active hydrogen group can be used, if necessary, for the purpose of controlling the molecular weight of the resulting polyurethane.
Aliphatic monools such as methanol having one hydroxyl group, ethanol, propanol, butanol and hexanol, diethylamine having one amino group, dibutylamine, n-butylamine, monoethanolamine and diethanolamine And aliphatic monoamines such as morpholine.
One of these may be used alone, or two or more may be used in combination.

<2-4. Catalyst>
In the polyurethane formation reaction in producing the polyurethane of the present invention, amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine or trimethyltin laurate, tin such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate It is also possible to use a known urethane polymerization catalyst typified by a compound of the type, and an organic metal salt such as a titanium compound. A urethane polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

<2-5. Polyol other than polycarbonate diol of the present invention>
In the polyurethane formation reaction in producing the polyurethane of the present invention, the polycarbonate diol of the present invention may be used in combination with other polyols as needed. Here, the polyol other than the polycarbonate diol of the present invention is not particularly limited as long as it is used in normal polyurethane production, and for example, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol other than the present invention can give. For example, when used in combination with a polyether-based polyol, it can be a polyurethane with further improved low temperature characteristics which is a feature of the polycarbonate diol of the present invention. Here, with respect to the combined weight of the polycarbonate diol of the present invention and the other polyol. 70% or more is preferable and, as for the weight ratio of polycarbonate diol of this invention, 90% or more is more preferable. When the proportion by weight of the polycarbonate diol of the present invention is small, the balance between the chemical resistance, the low temperature characteristics and the heat resistance, which is a feature of the present invention, may be lost.

In the present invention, the above-mentioned polycarbonate diol of the present invention can be modified and used for the production of polyurethane. The polycarbonate diol is modified by adding an epoxy compound such as ethylene oxide, propylene oxide or butylene oxide to polycarbonate diol to introduce an ether group, or using polycarbonate diol as a cyclic lactone such as ε-caprolactone, adipic acid or succinic acid There are methods of introducing an ester group by reaction with dicarboxylic acid compounds such as sebacic acid and terephthalic acid, and ester compounds thereof. In the case of ether modification, the viscosity of polycarbonate diol is lowered by modification with ethylene oxide, propylene oxide or the like, which is preferable from the viewpoint of handleability and the like. In particular, in the polycarbonate diol of the present invention, by modifying ethylene oxide or propylene oxide, the crystallinity of the polycarbonate diol is reduced and the flexibility at low temperature is improved, and in the case of ethylene oxide modification, it is manufactured using ethylene oxide modified polycarbonate diol. In order to increase the water absorbability and moisture permeability of the polyurethane, the performance as an artificial leather, a synthetic leather, etc. may be improved. However, when the addition amount of ethylene oxide or propylene oxide increases, various physical properties such as mechanical strength, heat resistance, chemical resistance, etc. of the polyurethane produced using the modified polycarbonate diol decrease, so the addition amount to the polycarbonate diol is 5 50 to 50% by weight is suitable, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. Moreover, in the method of introduce | transducing an ester group, the viscosity of a polycarbonate diol falls by modification | denaturation by (epsilon) -caprolactone, and it is preferable from the reasons of a handleability etc. The addition amount of ε-caprolactone to polycarbonate diol is preferably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. When the addition amount of ε-caprolactone exceeds 50% by weight, the hydrolysis resistance, chemical resistance and the like of the polyurethane produced using the modified polycarbonate diol are lowered.

<2-6. Solvent>
A solvent may be used for the polyurethane formation reaction in 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; tetrahydrofuran and dioxane Ether solvents; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents may be used alone or in combination of two or more.

Among these, preferred organic solvents are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide and the like.
In addition, polyurethanes of water dispersions can also be produced from polyurethane compositions containing the polycarbonate diol of the present invention, polydiisocyanate, and the chain extender described above.

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

  The two-step method is carried out by preparing the double-ended isocyanate intermediate of the portion corresponding to the soft segment of polyurethane by reacting the polycarbonate diol of the present invention and the other polyol in advance with one equivalent or more of polyisocyanate. It is a thing. Thus, once preparing the prepolymer and then reacting it with a chain extender, it may be easier to adjust the molecular weight of the soft segment, and it is necessary to ensure phase separation between the soft segment and the hard segment. Is useful.

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

If the amount of polyisocyanate used is too large, the unreacted isocyanate group causes a side reaction, and the viscosity of the resulting polyurethane tends to be too high to be difficult to handle or the flexibility is impaired, If it is too much, the molecular weight of the polyurethane may not be sufficiently large, and there is a tendency that sufficient polyurethane strength can not be obtained.
The amount of chain extender used is not particularly limited, but the lower limit is preferably 1 when the number of total hydroxyl groups of the polycarbonate diol of the present invention and other polyols minus the number of isocyanate groups of polyisocyanate is 1 equivalent. Is preferably 0.7 equivalents, more preferably 0.8 equivalents, still more preferably 0.9 equivalents, particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, furthermore Preferably, it is 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 solvents and difficult to process, and if too small, the resulting polyurethane is too soft to have sufficient strength, hardness, elastic recovery performance and elasticity. The holding performance may not be obtained or the heat resistance may deteriorate.

<2-9. Two-step method>
The two-stage method is also referred to as a prepolymer method and mainly includes the following methods.
(A) The amount by which the reaction equivalent ratio of the polycarbonate / (polycarbonate diol of the present invention and the polyol other than the present invention) exceeds 1 from the polycarbonate diol of the present invention and the other polyol and the excess polyisocyanate beforehand. Method of producing a polyurethane by reacting at 0 or less to produce a prepolymer having an isocyanate group at the molecular chain end and then adding a chain extender thereto (b) Pre-polyisocyanate, excess polycarbonate diol and the like The reaction is carried out at a reaction equivalent ratio of polyisocyanate / (polycarbonate diol of the present invention and other polyols) of at least 0.1 to less than 1.0 to produce a prepolymer having a hydroxyl group at the molecular chain end. Followed by a terminal isocyanate as chain extender Method for producing a polyurethane polyisocyanate preparative groups reacted.

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

In the case of the method of (1), polyurethane is obtained in the form of coexistence with a solvent by dissolving the chain extender in a solvent or simultaneously dissolving the prepolymer and the chain extender in a solvent for chain extension reaction. This is very important.
The amount of polyisocyanate used in the two-stage method (a) is not particularly limited, but the lower limit is preferable as the number of isocyanate groups when the number of total hydroxyl groups of polycarbonate diol and the other polyols is one equivalent. Is an amount of more than 1.0 equivalent, 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, more preferably 3.0 It is a range of equivalents.

If the amount of isocyanate used is too large, excess isocyanate groups tend to cause side reactions to make it difficult to reach the desired physical properties of the polyurethane. The sex may be low.
The use amount of the chain extender is not particularly limited, but the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0 with respect to the number 1 equivalent of isocyanate groups contained in the prepolymer. The upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, still more preferably 2.0 equivalents.

When the above-mentioned chain extension reaction is carried out, a monofunctional organic amine or alcohol may be allowed to coexist for the purpose of adjusting the molecular weight.
The amount of polyisocyanate used in preparing the prepolymer having a hydroxyl group at the end in the method of the two-step method (b) is not particularly limited, but the number of total hydroxyl groups of polycarbonate diol and other polyols is 1 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 the number of isocyanate groups when they are equivalent. It is 0.98 equivalent, more preferably 0.97 equivalent.

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

When the above-mentioned chain extension reaction is carried out, a monofunctional organic amine or alcohol may be allowed to coexist for the purpose of adjusting the molecular weight.
The chain extension reaction is usually carried out at 0 ° C. to 250 ° C. The temperature varies depending on the amount of solvent, the reactivity of the raw materials used, the reaction equipment and the like, and is not particularly limited. If the temperature is too low, the reaction may proceed too slowly, or the solubility of the raw materials and polymers may be low, which may increase the production time. If the temperature is too high, side reactions and decomposition of the resulting polyurethane may occur. . The chain extension reaction may be performed while degassing under reduced pressure.

Moreover, a catalyst, a stabilizer, etc. can also be added to chain extension reaction as needed.
Examples of the catalyst include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one type may be used alone, or two types may be used. The above may be used in combination. As a stabilizer, for example, 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N, N'-di-2-naphthyl-1,4-phenylenediamine, tris (dinonylphenyl) phos Compounds such as Phyto may be mentioned, and one type may be used alone, or two or more types may be used in combination. When the chain extender is one having high reactivity such as a short chain aliphatic amine, it may be carried out without adding a catalyst.

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

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

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

  When 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 is lower than that of the present invention in order to increase the water dispersibility. It is preferably 1% by weight, more preferably 5% by weight, still more preferably 10% by weight, based on the total weight of the polycarbonate diol and the other polyol. On the other hand, the upper limit is preferably 50% by weight, more preferably 40% by weight, and still more preferably 30% by weight, since the properties of the polycarbonate diol of the present invention may not be maintained if too much is added. It is.

In the case of producing an aqueous polyurethane emulsion, it may be reacted in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone in the prepolymer step, or may be reacted without a solvent. Moreover, when using a solvent, it is preferable to distill off a solvent by distillation after producing an aqueous emulsion.
The upper limit of the number average molecular weight determined from the hydroxyl value of the polycarbonate diol is preferably 5,000, more preferably 4500, still more preferably 4,000, when producing an aqueous polyurethane emulsion without solvent using the polycarbonate diol of the present invention as a raw material . The lower limit is preferably 300, more preferably 500, and still more preferably 800. When the number average molecular weight determined from the hydroxyl value exceeds 5,000 or is smaller than 300, emulsification may be difficult.

  In addition, for synthesis or storage of aqueous polyurethane emulsions, anionic interfaces represented by higher fatty acids, resin acids, acid fatty alcohols, sulfuric esters, higher alkyl sulfonates, alkyl aryl sulfonates, castor oil sulfonated, sulfosuccinic esters and the like Well-known reaction of cationic surfactant such as activator, primary amine salt, secondary amine salt, tertiary amine salt, quaternary amine salt, pyridinium salt or ethylene oxide with long chain fatty alcohol or phenols The emulsion stability may be maintained by using a nonionic surfactant represented by a product in combination.

In addition, when forming an aqueous polyurethane emulsion, the emulsion is produced by mechanically mixing water with the organic solvent solution of the prepolymer in the presence of an emulsifier under high shear, if necessary, without the neutralization and chlorination step. You can also do it.
The water-based polyurethane emulsion thus produced can be used in various applications. In particular, chemical raw materials with low environmental impact are required recently, and it is possible to replace conventional products for the purpose of not using organic solvents.

  As a specific application of the water-based polyurethane emulsion, for example, application to a coating agent, a water-based paint, an adhesive, a synthetic leather, and an artificial leather is suitable. In particular, the aqueous polyurethane emulsion produced using the polycarbonate diol of the present invention is flexible because it has a structural unit derived from the compound represented by the formula (B) in the polycarbonate diol. It is possible to use effectively as compared with the water-based polyurethane emulsion which used the conventional polycarbonate diol as etc.

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

  Compounds usable as heat stabilizers include aliphatic and aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates and dialkyls Phosphorus compounds such as pentaerythritol diphosphite and dialkyl bisphenol A diphosphite; phenolic derivatives, particularly hindered phenol compounds; thioethers, dithioacids, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates, etc. Compounds containing sulfur; tin-based compounds such as tin malate and dibutyltin monoxide can be used.

Specific examples of the hindered phenol compound include Irganox 1010 (trade name: made by BASF Japan Ltd.), Irganox 1520 (trade name: made by BASF Japan Ltd.), Irganox 245 (trade name: made by BASF Japan Ltd.) and the like.
As a phosphorus compound, PEP-36, PEP-24G, HP-10 (all are brand names: made by ADEKA Corporation) Irgafos 168 (brand name: made by BASF Japan Ltd.) etc. are mentioned.

Specific examples of the compound containing sulfur include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).
Examples of light stabilizers include benzotriazole compounds, benzophenone compounds, etc. Specifically, “TINUVIN 622LD”, “TINUVIN 765” (above, manufactured by Ciba Specialty Chemicals Inc.), “SANOL LS-2626” “SANOL LS-765” (manufactured by Sankyo Co., Ltd.) and the like can be used.

As an example of an ultraviolet absorber, "TINUVIN 328", "TINUVIN 234" (above, Ciba specialty chemicals KK made) etc. are mentioned.
As colorants, dyes such as direct dyes, acid dyes, basic dyes, metal complex dyes, etc .; carbon black, titanium oxide, zinc oxide, iron oxide, inorganic pigments such as mica; and coupling azo type, condensation azo type, Organic pigments such as anthraquinone type, thioindigo type, dioxazone type, and phthalocyanine type can be mentioned.

Examples of the inorganic filler include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, white clay and the like.
Examples of flame retardants include addition and reaction type flame retardants of phosphorus 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 in combination of two or more in any combination and ratio.
The addition amount of these additives is preferably 0.01% by weight, more preferably 0.05% by weight, still more preferably 0.1% by weight, and the upper limit is preferably 10, as a weight ratio to the polyurethane. % By weight, more preferably 5% by weight, still more preferably 1% by weight. If the additive amount is too small, the effect of the additive can not be sufficiently obtained. If the additive amount is too large, it may precipitate in the polyurethane or generate turbidity.

<2-12. Polyurethane film / polyurethane board>
When producing a film using the polyurethane of the present invention, the thickness of the film preferably has a lower limit of preferably 10 μm, more preferably 20 μm, still more preferably 30 μm, and an upper limit of preferably 1000 μm, more preferably 500 μm, more preferably Is 100 μm.
When the thickness of the film is too thick, sufficient moisture permeability tends to not be obtained, and when it is too thin, pinholes tend to occur, and the film tends to be easily blocked and difficult to handle.

<2-13. Molecular weight>
The molecular weight of the polyurethane of the present invention is appropriately adjusted according to the application, and is not particularly limited, but preferably 50,000 to 500,000 as the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC, It is more preferable that it is ten thousand to three hundred thousand. When Mw is smaller than the above lower limit, sufficient strength and hardness may not be obtained, and when it is larger than the above upper limit, there is a tendency that the handling property such as processability is impaired.

<2-14. Chemical resistance>
The polyurethane of the present invention has a change (%) in the weight of the polyurethane test piece after immersion in the drug relative to the weight of the polyurethane test piece before immersion in the medicine, for example, in the evaluation described in the section of Examples described later 40% or less is preferable, 30% or less is more preferable, and 20% or less is more preferable.
If the weight change rate exceeds the above upper limit, desired chemical resistance may not be obtained.

<2-15. Olein resistant>
The polyurethane of the present invention is, for example, a rate of change in the weight of the polyurethane test piece after immersion in oleic acid relative to the weight of the polyurethane test piece before immersion in oleic acid in the evaluation by the method described in the section of Examples described later. (%) Is preferably 80% or less, more preferably 60% or less, further preferably 50% or less, particularly preferably 45% or less, and most preferably 40% or less.
When the weight change rate exceeds the above upper limit, sufficient oleic acid resistance may not be obtained.

<2-16. Ethanol resistance>
The polyurethane of the present invention is, for example, a rate of change (%) in the weight of the polyurethane test piece after immersion in ethanol relative to the weight of the polyurethane test piece before immersion in ethanol in the evaluation by the method described in the section of Examples described later. 25% or less is preferable, 23% or less is more preferable, 21% or less is more preferable, 20% or less is particularly preferable, and 19% or less is most preferable.
If the weight change rate exceeds the above upper limit, sufficient ethanol resistance may not be obtained.

<2-17. Tensile elongation at break>
The polyurethane of the present invention is measured at a temperature of 23 ° C. and a relative humidity of 50% at a distance between chucks of 50 mm, at a tensile speed of 500 mm / min, against a strip-shaped sample of 10 mm wide and 100 mm long and 50 to 100 μm thick The lower limit of the tensile elongation at break is preferably 50%, more preferably 100%, still more preferably 150%, and the upper limit is preferably 900%, more preferably 850%, still more preferably 800%. If the tensile elongation at break is less than the above lower limit, there is a tendency that the handling property such as processability is impaired, and if the above upper limit is exceeded, sufficient chemical resistance may not be obtained.

<2-18. Young's modulus>
The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 140,000, which was produced by the one-step method using 12% to 13% HS content% using the polycarbonate diol of the present invention and MDI and 1,4BD. The Young's modulus at 23 ° C. measured by the same method as the above tensile elongation at break measurement of a polyurethane of 210,000 (hereinafter sometimes referred to as “specific polyurethane”) is preferably 0.02 or more, more preferably It is 0.04 or more, more preferably 0.06 or more. Moreover, preferably it is 2 or less, More preferably, it is 1 or less, More preferably, it is 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, the flexibility may be insufficient or the handling properties such as processability may be impaired. Furthermore, the Young's modulus measured by the same method as the above tensile elongation at break measurement except that the specific polyurethane is at −10 ° C. is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more And particularly preferably 0.05 or more. Also preferably, it is 2 or less, more preferably 1 or less, still 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. When 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 processability may be impaired.

Here, Young's modulus is the value of stress at an elongation of 1% as the slope of the stress value at the initial elongation, and specifically, it is measured by the method described in the section of Examples described later. .
The HS (hard segment) content% can be calculated by the following equation. HS content (% by weight) = [polyisocyanate preparation weight (g) + chain extender preparation weight (g) + hardness adjuster (g)] ÷ [polyisocyanate preparation weight (g) + polycarbonate diol preparation weight (g) + Other polyol preparation weight (g) + chain extender preparation weight (g) + hardness adjuster (g))
Each term of the above-mentioned formula is a numerical value concerning the raw material used at the time of urethane manufacture.

<2-19.100% modulus>
The polyurethane of the present invention has a width of 10 mm when 2 equivalents of 4,4'-dicyclohexylmethane diisocyanate is reacted with the polycarbonate diol of the present invention and chain extension reaction is carried out with isophorone diamine to obtain polyurethane by a two-stage method. The lower limit of 100% modulus measured at a temperature of 23 ° C and a relative humidity of 50% at a distance between chucks of 50 mm and a tensile speed of 500 mm / min is preferable for strip-like samples of 100 mm in length and about 50 to 100 μm in thickness. It is 0.1 MPa or more, more preferably 0.5 MPa or more, further preferably 1 MPa or more, and the upper limit is preferably 20 MPa or less, more preferably 10 MPa or less, further preferably 6 MPa or less. If the 100% modulus is less than the above lower limit, the chemical resistance may not be sufficient. If the above upper limit is exceeded, the flexibility tends to be insufficient or the handling property such as processability tends to be impaired. Furthermore, the 100% modulus at −10 ° C. of the specific polyurethane is preferably 0.5 or more, more preferably 1.0 or more, further preferably 1.5 or more, particularly preferably 2.0 or more. Also preferably, it is 13.0 or less, more preferably 12.5 or less, still more preferably 12.0 or less, particularly preferably 11.5 or less, and most preferably 10.0 or less. If the 100% modulus at -10 ° C is less than the above lower limit, chemical resistance may be insufficient. If the 100% modulus at -10 ° C exceeds the above upper limit, the flexibility at low temperature may be insufficient or the handling property such as processability may be impaired.

<2-20. Low temperature characteristics>
The polyurethane of the present invention has good low temperature properties, but the low temperature properties in this patent can be evaluated by the tensile elongation at break, Young's modulus, 100% modulus in a tensile test at a low temperature such as -10. Further, specifically, it refers to flexibility at low temperatures, impact resistance, flex resistance, and durability.

<2-21. Heat resistance>
The polyurethane of the present invention is heated at a temperature of 120 ° C. for 400 hours in a gear oven for a urethane film having a width of 100 mm, a length of 100 mm and a thickness of about 50 to 100 μm. The lower limit is preferably 15% or more, more preferably 20% or more, still more preferably 30% or more, particularly preferably 45% or more, and the upper limit is preferably 120% or less, based on the weight average molecular weight (Mw) described above. More preferably, it is 110% or less, more preferably 105% or less.

<2-22. Glass transition temperature>
The equivalent of 4,4'-dicyclohexylmethane diisocyanate is reacted with the polycarbonate diol of the present invention, and chain extension reaction is carried out with isophorone diamine to obtain a polyurethane by a two-step method. The lower limit of the glass transition temperature (Tg) of the specific polyurethane having a weight average molecular weight (Mw) of 130,000 to 210,000 is preferably -50 ° C, more preferably -45 ° C, still more preferably -40 ° C, and the upper limit is preferably Is -20.degree. C., more preferably -25.degree. C., still more preferably -30.degree. If the Tg is less than the above lower limit, the chemical resistance may not be sufficient, and if the above upper limit is exceeded, the low temperature properties may not be sufficient.

<2-23. Applications>
The polyurethane of the present invention is excellent in chemical resistance and has good low temperature properties, so foams, elastomers, elastic fibers, paints, fibers, adhesives, adhesives, floorings, sealants, medical materials, artificial leather, It can be widely used in synthetic leather, coating agents, water-based polyurethane paints, active energy ray-curable resin compositions and the like.

  In particular, when the polyurethane of the present invention is used in applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, floorings, paints, and coating agents, good chemical resistance and low temperature properties are obtained. Because it has balance, it has high durability in areas where human skin is touched or cosmetics and antiseptic alcohol are used, and it has sufficient flexibility at low temperatures, and it also has physical impact. Good characteristics of strong can be imparted. In addition, it is also suitable for a mid coat of the exterior of an automobile where flexibility at more severe low temperatures is required.

The polyurethanes of the present invention can be used in cast polyurethane elastomers. Specific applications thereof include rolls such as rolling rolls, papermaking rolls, office equipment, rolls such as pretension rolls, forklifts, solid tires such as automobile vehicles neutram, carriages, carts etc., conveyor belt idlers and guides as industrial products, etc. Rolls, pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liners, pump impellers, cyclone cones, cyclone liners, etc. In addition, it can be used as a belt for office automation equipment, a paper feed roll, a cleaning blade for copying, a snow plow, a toothed belt, a surf roller, and the like.

  The polyurethanes of the invention are also applicable for use as thermoplastic elastomers. For example, it can be used for tubes, hoses, spiral tubes, fire hoses and the like in pneumatic devices, coating devices, analytical devices, physicochemical devices, metering pumps, water treatment devices, industrial robots, etc. used in the food and medical fields. In addition, as belts such as round belts, V-belts and flat belts, they are used in various transmission mechanisms, spinning machines, packing machines, printing machines and the like. Further, it can be used for heel tops and soles of footwear, couplings, packing, pole joints, bushes, gears, rolls and other equipment parts, sports goods, leisure goods, watch belts and the like. Furthermore, examples of automobile parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, tire chain substitutes and the like. Further, it can be used for films such as keyboard films, films for automobiles, curl cords, cable sheaths, bellows, transport belts, flexible containers, binders, synthetic leathers, dipping products, adhesives and the like.

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

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

The polyurethane of the present invention can be used as a component of a fiber processing agent for shrinkproofing, mildewproofing, water repellent finishing and the like.
The method of fiberization in the case of using the polyurethane of the present invention as an elastic fiber can be carried out without particular limitation as long as it can be spun. For example, it is possible to employ a melt spinning method in which, once pelletized, it is melted and directly spun through a spinneret. When elastic fibers are obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250 ° C. or less, more preferably 200 ° C. or more and 235 ° C. or less.

  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 coated yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton and polyester fibers. Among them, polyester fibers are preferably used in the present invention. In addition, 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 caulking for concrete-embedded walls, induced joints, sash surroundings, wall-type PC joints, ALC joints, board joints, composite glass sealants, heat insulation sash sealants, automotive sealants, etc. .
The polyurethane of the present invention can be used as a medical material, and can be used as a blood compatible material such as a tube, a catheter, an artificial heart, an artificial blood vessel, an artificial valve, etc., and a catheter, a tube, a bag, a surgical glove as a disposable material. It can be used for artificial kidney potting materials etc.
The polyurethane of the present invention may be used as a raw material for a UV curable coating, an electron beam curable coating, a photosensitive resin composition for flexographic printing plate, a photocurable optical fiber coating composition, etc. by modifying the terminal. it can.

<2-24. Urethane (Meth) Acrylate Oligomer>
Also, urethane (meth) acrylate based oligomers can be produced by addition reaction of polyisocyanate and hydroxyalkyl (meth) acrylate using the polycarbonate diol of the present invention. When using a polyol which is another raw material compound, a chain extender and the like in combination, the urethane (meth) acrylate based oligomer can be produced by addition reaction of these other raw material compounds with polyisocyanate. .

Further, the preparation ratio of each raw material compound at that time is substantially equal to or the same as the composition of the target urethane (meth) acrylate oligomer.
The amount of all isocyanate groups and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups in the urethane (meth) acrylate based oligomer are usually theoretically equimolar.

When producing a urethane (meth) acrylate-based oligomer, the amount of hydroxyalkyl (meth) acrylate used is a polyol which is a hydroxyalkyl (meth) acrylate, a polycarbonate diol, and other raw material compounds used as needed, and It is usually 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and usually 70 mol% or less, based on the total amount of the compound containing the functional group that reacts with isocyanate such as chain extender Preferably, it is 50 mol% or less. Depending on this ratio, the molecular weight of the resulting urethane (meth) acrylate oligomer can be controlled. When the proportion of hydroxyalkyl (meth) acrylate is high, the molecular weight of the urethane (meth) acrylate oligomer tends to be small, and when the proportion is low, the molecular weight tends to be large.

  The amount of polycarbonate diol used is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more based on the total amount of polycarbonate diol and polyol used. If the amount of the polycarbonate diol used is larger than the above lower limit, the hardness and the stain resistance of the resulting cured product tend to be good, which is preferable.

  The amount of polycarbonate diol used is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total amount of polycarbonatediol and polyol used. Is 70% by mass or more. If the amount of polycarbonate diol used is larger than the above lower limit, the viscosity of the composition obtained is lowered to improve the workability, and the mechanical strength and the hardness and the abrasion resistance of the obtained cured product tend to be improved. preferable.

Furthermore, the amount of the polycarbonate diol used is preferably 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more based on the total amount of the polycarbonate diol and the polyol used. If the amount of the polycarbonate diol used is larger than the above lower limit, the elongation and weather resistance of the resulting cured product tend to be improved, which is preferable.

  Furthermore, in the case of using a chain extender, the amount of the polyol used is preferably 70 mol% or more, more preferably 80, based on the total amount of polycarbonate diol and the compound of the polyol and the chain extender combined. It is more preferably at least 90% by mole, particularly preferably at least 95% by mole. When the amount of polyol is larger than the above lower limit value, the liquid stability tends to be improved, which is preferable.

  At the time of production of the urethane (meth) acrylate oligomer, a solvent can be used for the purpose of adjusting the viscosity. The solvents may be used alone or in combination of two or more. As the solvent, any of known solvents can be used. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can be used usually at less than 300 parts by mass with respect to 100 parts by mass of solid content in the reaction system.

  In the production of the urethane (meth) acrylate oligomer, the total content of the urethane (meth) acrylate oligomer and the raw material compound produced is preferably 20% by mass or more based on the total amount of the reaction system, and 40 mass More preferably, it is at least%. The upper limit of the total content is 100% by mass. It is preferable that the total content of the urethane (meth) acrylate oligomer and the raw material compound thereof is 20% by mass or more, because the reaction rate tends to be high and the production efficiency tends to be improved.

  An addition reaction catalyst can be used in the production of the urethane (meth) acrylate oligomer. Examples of this addition reaction catalyst include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. 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 viewpoints of environmental adaptability, catalytic activity, and storage stability.

The addition reaction catalyst has an upper limit of usually 1,000 ppm or less, preferably 500 ppm or less, and a lower limit of usually 10 ppm or more, preferably 30 ppm or more, based on the total content of the urethane (meth) acrylate type oligomer to be produced and the raw material compound thereof. Used.
In addition, when a urethane (meth) acrylate oligomer is produced, if a reaction system contains a (meth) acryloyl group, a polymerization inhibitor can be used in combination. Examples of such polymerization inhibitors include phenols such as hydroquinone, methyl hydroquinone, hydroquinone monoethyl ether and dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, and manganese such as manganese acetate And salts, nitro compounds, nitroso compounds and the like. The polymerization inhibitors may be used alone or in combination of two or more. Among these, phenols are preferable as the polymerization inhibitor.

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 lower than the total content of the urethane (meth) acrylate type oligomer to be produced and the starting compound It is used at 50 ppm or more, preferably 100 ppm or more.
At the time of production of the urethane (meth) acrylate oligomer, the reaction temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. When the reaction temperature is 20 ° C. or higher, the reaction rate is increased, and the production efficiency tends to be improved, which is preferable. The reaction temperature is usually 120 ° C. or less, preferably 100 ° C. or less. It is preferable that the reaction temperature is 120 ° C. or less because side reactions such as allophanate reaction hardly occur. When the reaction system contains a solvent, the reaction temperature is preferably equal to or lower than the boiling point of the solvent, and when it contains (meth) acrylate, it is 70 ° C. from the viewpoint of preventing the reaction of (meth) acryloyl group. It is preferable that it is the following. 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 1000 or more, preferably 10000 or less, particularly preferably 5000 or less, particularly preferably 3000 or less. When the number average molecular weight of the urethane (meth) acrylate oligomer is equal to or more than the above lower limit, the three-dimensional processability of the resulting cured film becomes good, and the balance between the three-dimensional processability and the stain resistance tends to be excellent. When the number average molecular weight of the urethane (meth) acrylate oligomer is less than the above upper limit, the stain resistance of the cured film obtained from the composition becomes good, and the balance between the three-dimensional processability and the stain resistance tends to be excellent. Because it is preferable. This is because the three-dimensional processability and the contamination resistance depend on the distance between the crosslink points in the network structure, and when this distance is long, the structure becomes flexible and easy to stretch, and the three-dimensional processability is excellent. It is presumed that the structure is a strong structure and the contamination resistance is excellent.

<2-25. Polyester-based elastomer>
Furthermore, the polycarbonate diol of the present invention can be used as a polyester elastomer. The polyester elastomer is a copolymer composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of aliphatic polyether, aliphatic polyester or aliphatic polycarbonate. When the polycarbonate diol of the present invention is used as a component of the soft segment, physical properties such as heat resistance and water resistance are excellent as compared with the case where aliphatic polyether and aliphatic polyester are used. In addition, even when compared to known polycarbonate diols, polycarbonate ester elastomers having melt fluidity, that is, melt flow rates suitable for blow molding and extrusion molding, and excellent balance with mechanical strength and other physical properties It can be suitably used for various molding materials including fibers, films, and sheets, for example, molding materials such as elastic yarns and boots, gears, tubes, and packings. Specifically, it can be effectively applied to applications such as joint boots for automobiles, home electric appliance parts and the like which are required to have heat resistance and durability, and wire covering materials.

<2-26. Active energy ray curable polymer composition>
Below, the active energy ray curable polymer composition of this invention containing the above-mentioned urethane (meth) acrylate type oligomer is demonstrated.
The active energy ray-curable polymer composition of the present invention preferably has a calculated network cross-linking point molecular weight of the composition of 500 to 10,000.

  In the present specification, the calculated network inter-crosslinking point molecular weight of the composition is the average molecular weight between active energy ray reactive groups (hereinafter sometimes referred to as "crosslinking point") forming a network structure in the entire composition. Represents a value. The molecular weight between the calculated network crosslink points is correlated with the network area at the time of formation of the network structure, and the crosslink density decreases as the molecular weight between the calculated network crosslink points increases. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter sometimes referred to as "monofunctional compound") is reacted, it becomes a linear polymer, while the active energy A network structure is formed when a compound having two or more line reactive groups (hereinafter sometimes referred to as "polyfunctional compound") is reacted.

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

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

  When a monofunctional compound is contained in the composition, it is calculated that the molecule formed by equimolar combination of the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound with the monofunctional compound at the crosslinking point. Assuming that the reaction is performed so as to locate at the center of the chain, the molecular chain extension by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound as the total active energy ray reaction of the polyfunctional compound in the composition. It becomes half of the value divided by the radix. Here, since it is considered that the molecular weight between the calculated network crosslink points is twice the average molecular weight per one crosslink point, the portion extended by the monofunctional compound with respect to the calculated molecular weight between the network crosslink points calculated in the multifunctional compound is The value is obtained by dividing the total molecular weight of the monofunctional compound by the total number of active energy ray reactive groups of the polyfunctional compound in the composition.

  For example, in a composition comprising a mixture of 40 moles of a monofunctional compound having a molecular weight of 100 and 4 moles of a bifunctional compound having a molecular weight of 1,000, the number of active energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The elongation by the monofunctional compound in the calculated molecular weight between network crosslinking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslink points of the composition is 1000 + 500 = 1500.

  From the above, in the mixture of the monofunctional compound MA mole of molecular weight WA, the fB functional compound MB mole of molecular weight WB and the fC functional compound MC mole of molecular weight WC, the calculated network crosslink point molecular weight of the composition Can be expressed by the following equation.

The molecular weight between calculated network crosslink points of the active energy ray-curable polymer composition of the present invention calculated as described above is preferably 500 or more, more preferably 800 or more, and 1,000 or more. Is more preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, still more preferably 4,000 or less And particularly preferably 3,000 or less.

  When the molecular weight between calculated network crosslink points is 10,000 or less, the contamination resistance of the cured film obtained from the composition becomes good, and the balance between the three-dimensional processability and the contamination resistance tends to be excellent, which is preferable. In addition, when the molecular weight between calculated network crosslink points is 500 or more, the three-dimensional processability of the obtained cured film becomes good, and the balance between the three-dimensional processability and the stain resistance tends to be excellent, which is preferable. This is because the three-dimensional processability and the contamination resistance depend on the distance between the crosslink points in the network structure, and when this distance is long, the structure becomes flexible and easy to stretch, and the three-dimensional processability is excellent. It is presumed that the structure is a strong structure and the contamination resistance is excellent.

The active energy ray-curable polymer composition of the present invention may further contain other 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 oligomer is 40% by mass or more based on the total amount of the active energy ray reactive component including the urethane (meth) acrylate oligomer It is preferable that it is 60 mass% or more. In addition, the upper limit of this content is 100 mass%. When the content of the urethane (meth) acrylate oligomer is 40% by mass or more, the curability is good, and the mechanical strength at the time of forming the cured product is not too high, and the three-dimensional processability tends to be improved. It is preferable because it exists.

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

  Further, in the active energy ray-curable polymer composition of the present invention, the content of the total amount of the active energy ray-reactive component containing a urethane (meth) acrylate oligomer is the curing speed and surface curability as a composition. It is preferable that the content is 60% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more based on the total amount of the composition from the viewpoint of excellentness and no tackiness. And still more preferably 95% by mass or more. In addition, the upper limit of this content is 100 mass%.

  As the active energy ray reactive monomer, any known active energy ray reactive monomer can be used. These active energy ray reactive monomers are used for the purpose of adjusting the hydrophilicity and hydrophobicity of urethane (meth) acrylate oligomers, and the physical properties such as hardness and elongation of cured products when the resulting composition is a cured product. Be done. The active energy ray-reactive monomer may be used alone or in combination of two or more.

Such active energy ray reactive monomers include, for example, vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specifically, for example, styrene, α-methylstyrene, α-chlorostyrene , Vinyl toluene, vinyl vinyl monomers such as divinyl benzene; vinyl acetate, vinyl butyrate, N-vinyl formamide,
Vinyl ester monomers such as N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, divinyl adipate and the like; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; diallyl phthalate, trimethylolpropane diallyl ether, allyl glycidyl ether Allyl compounds such as: (meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethyl methacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) (Meth) acrylamides such as acrylamide, N-t-butyl (meth) acrylamide, (meth) acryloyl morpholine, methylene bis (meth) acrylamide; (meth) acrylic acid, ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate ( Meta) hexyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholinyl (meth) acrylate, (meth) acrylic Acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid glycidyl, (meth) acrylic acid dimethylaminoethyl, (meth) acrylic acid Diethylaminoethyl, benzyl (meth) acrylate, cyclohexene (meth) acrylate Phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ( Monofunctional (meth) acrylates such as allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and phenyl (meth) acrylate; and ethylene glycol di (meth) acrylate Di (meth) acrylic acid diethylene glycol, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetra ethylene glycol, di (meth) acrylic acid polyethylene glycol (n = 5 to 14), di (meth) acrylic acid Propylene glycol, di (meth) acrylic acid dip Polyethylene glycol di (meth) acrylate tripropylene glycol di (meth) acrylate tetrapropylene glycol di (meth) acrylate polypropylene glycol di (meth) acrylate (n = 5 to 14) di-(meth) acrylic acid 1-3 Butylene glycol, di (meth) acrylic acid-1,4-butanediol, poly (butylene 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) acrylic acid ester, di (meth) acrylic acid dicyclopentane diol, di (meth) Acrylic acid tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, Trimethylolpropane polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate 2.) Multifunctional (meth) acrylates such as acrylates, propylene oxide-added bisphenol F di (meth) acrylates, tricyclodecane dimethanol di (meth) acrylates, bisphenol A epoxy di (meth) acrylates, bisphenol F epoxy di (meth) acrylates; It can be mentioned.

  Among these, in particular, in applications requiring coating properties, (meth) acryloyl morpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Tricyclic cyclohexyl, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylamide, etc., having a ring structure in the molecule 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, di (meth) acrylic acid-1,9-nonanediol, di (meta) Acrylic acid neopentyl glycol, di (meth) acrylic acid tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

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

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

  The said polymerization initiator is mainly used for the purpose of improving the start efficiency of the polymerization reaction which advances with irradiation of active energy rays, such as an ultraviolet-ray and an electron beam. As the polymerization initiator, a light / BR> FuW polymerization initiator which is a compound having a property of generating a radical by light is generally used, and any known light radical polymerization initiator can be used. The polymerization initiators may be used alone or in combination of two or more. Furthermore, a photo radical polymerization initiator and a photosensitizer may be used in combination.

As a radical photopolymerization initiator, for example, benzophenone, 2,4,6-trimethyl benzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenyl benzophenone, methyl ortho benzoyl benzoate, thioxanthone, diethyl thioxanthone, isopropyl thioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl benzoyl formate, 2-methyl-1- [4- ( [Cylthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4, 4-trimethylpentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6 in that the curing rate 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-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ] -2-Methyl-propan-1-one is more preferred.

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, a photocationic agent together with the above-mentioned radical photopolymerization initiator as a polymerization initiator A polymerization initiator may be included. Any of known photo cationic polymerization initiators 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 100 parts by mass in total of the active energy ray-reactive components. More preferably, it is 5 parts by mass or less. It is preferable that the content of the photopolymerization initiator is 10 parts by mass or less, since a decrease in mechanical strength due to the initiator decomposition product hardly occurs.

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

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 100 parts by mass in total of the active energy ray-reactive components. And 5 parts by mass or less are more preferable. It is preferable that the content of the photosensitizer is 10 parts by mass or less, since a reduction in the crosslink density is unlikely to cause a decrease in mechanical strength.
The additive is optional, and various materials added to the composition used for the same application can be used as the additive. An additive may be used individually by 1 type, and may mix and use 2 or more types. As such additives, for example, glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder Fillers, etc .; Carbon materials such as carbon fibers, carbon black, graphite, carbon nanotubes, fullerenes such as C60 (fillers, carbon materials may be collectively referred to as "inorganic component"); Agents, heat stabilizers, UV absorbers, HALS (hindered amine light stabilizers), anti-fingerprint agents, surface hydrophilizing agents, antistatic agents, slipperiness imparting agents, plasticizers, mold release agents, antifoaming agents, leveling agents, Modifiers such as anti-settling agent, surfactant, thixotropy-imparting agent, lubricant, flame retardant, flame retardant aid, polymerization inhibitor, filler, silane coupling agent, etc .; pigment, dye, hue adjustment Colorants and the like; and, monomer and / or oligomer thereof, or a curing agent required for the synthesis of inorganic components, catalysts, curing accelerators like; and the like.

In the active energy ray-curable polymer composition of the present invention, the content of the additive is preferably 10 parts by mass or less, based on 100 parts by mass of the total of the active energy ray-reactive components. More preferably, it is at most parts by mass. It is preferable that the content of the additive is 10 parts by mass or less, since a decrease in the crosslink density is unlikely to cause a decrease in mechanical strength.
The said solvent is for the purpose of adjustment of the viscosity of the active energy ray curable polymer composition of this invention according to the coating system for forming the coating film of the active energy ray curable polymer composition of this invention, for example. It can be used. The solvents may be used alone or in combination of two or more. 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, and methyl isobutyl ketone. The solvent can be generally used at 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 is no limitation in particular as a method of making the active energy ray curable polymer composition of this invention contain arbitrary components, such as the above-mentioned additive etc., A conventionally well-known mixing, the dispersion | distribution method, etc. are mentioned. In order to disperse the optional component more reliably, it is preferable to carry out the dispersing process using a disperser. Specifically, for example, two-roll, three-roll, bead mill, ball mill, sand mill, pebble mill, trom mill, sand grinder, segment barrier triter, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill , A kneader, a homogenizer, an ultrasonic dispersion machine and the like.

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

  As a coating method of the active energy ray curable polymer composition of the present invention, a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll coater method Although known methods such as 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, among them, a bar coater method and a gravure coater method are preferable.

<2-27. 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 active energy rays.
As the active energy ray to be used for curing the composition, infrared rays, visible rays, ultraviolet rays, X rays, electron rays, α rays, β rays, γ rays and the like can be used. It is preferable to use an electron beam or ultraviolet light from the viewpoint of apparatus cost and productivity, and as a light source, an electron beam irradiation apparatus, an ultra high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He-Cd lasers, solid 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. Moreover, in the case of ultraviolet irradiation, it is preferable that it is 50-1,000 mJ / cm < ² >. The atmosphere at the time of curing may be air, an inert gas such as nitrogen or argon. In addition, irradiation may be performed in a closed space between a film or glass and a metal mold.

  The film thickness of the cured film is appropriately determined depending on the intended application, 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, expression of designability and functionality after three-dimensional processing is good, and when it is 200 μm or less, internal curability and three-dimensional processability are good, which is preferable. In 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 comprising the above-mentioned cured film on a substrate.
The laminate is not particularly limited as long as it has a layer formed of a cured film, and may have a layer other than the substrate and the cured film between the substrate and the cured film, You may Further, the laminate may have a plurality of layers of a base material and a cured film.
As a method of obtaining a laminate having a plurality of cured films, a method in which all the layers are laminated in an uncured state and then cured by active energy rays, or after the lower layer is cured or semi-cured by active energy rays A known method such as a method of applying the upper layer and curing again with active energy rays, a method of applying the respective layers to a release film or a base film, and then bonding the layers in an uncured or semicured state is applied. Although possible, it is preferable to use a method of curing with active energy rays after laminating in an uncured state from the viewpoint of enhancing the adhesion between layers. As a method of laminating in an uncured state, a known method such as sequential application in which the upper layer is applied after laminating the lower layer or simultaneous multilayer application in which two or more layers are simultaneously applied from the multiple slits is applied Although it is possible, it is not this limitation.

As the base material, for example, various shapes such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate and (meth) acrylic resin, or plates made of metal The article of
The cured film can be a film excellent in contamination resistance and hardness against general household contaminants such as ink and ethanol, and a laminate using the cured film as a film on various substrates has designability and surface It can be excellent in protection.

In addition, the active energy ray-curable polymer composition of the present invention has flexibility, elongation at break, mechanical strength, and contamination resistance that can follow deformation during three-dimensional processing, considering the molecular weight between calculated network crosslinking points. It is possible to provide a cured film that simultaneously has the same properties and hardness.
In addition, it is expected that the active energy ray-curable polymer composition of the present invention can easily produce a thin film resin sheet by single-layer coating.

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

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

EXAMPLES Hereinafter, the present invention will be more specifically described by way of 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: polycarbonate diol]
<Quantification of phenoxy group content, dihydroxy compound content and phenol content>
A polycarbonate diol is dissolved in CDCl ₃ and 400 MHz ¹ H-NMR (AL-400 manufactured by Nippon Denshi Co., Ltd.) is measured, phenoxy group, dihydroxy compound, and phenol are identified from the signal position of each component, and each is integrated The content of was calculated. The detection limit at that time is 100 ppm as the weight of phenol based on the weight of the whole sample, and the compound represented by the formula (A) and the dihydroxy compound such as the compound represented by the formula (B) are 0.1 wt% is there. The proportion of phenoxy group is determined from the ratio of the integral value of one proton of phenoxy group to the integral value of one proton of all terminals, and the detection limit of phenoxy group is 0.05% with respect to all terminals. .

<Hydroxyl number>
The hydroxyl value of the polycarbonate diol was measured by a method using an acetylation reagent in accordance with JIS K155-1 (2007).
<Measurement of APHA value>
In accordance with JIS K0071-1 (1998), the APHA value was measured in comparison with a standard solution containing polycarbonate diol in a colorimetric tube. The reagent used the color standard solution 1000 degree | times (1 mgPt / mL) (Kishida Chemical).

<Measurement of melt viscosity>
The polycarbonate diol was heated to 80 ° C. and melted, and then the melt viscosity was measured at 80 ° C. using an E-type viscometer (DV-II + Pro manufactured by BROOKFIELD, cone: CPE-52).
<Measurement of glass transition temperature (Tg), melting peak temperature, heat of fusion>
About 10 mg of polycarbonate diol is enclosed in an aluminum pan, and EXSTAR
Using a DSC 6200 (Seiko Instruments Co., Ltd.), under a nitrogen atmosphere, at a speed of 20 ° C per minute from 30 ° C to 150 ° C, at a speed of 40 ° C per minute at a speed of 150 ° C to -120 ° C, at a speed of 20 ° C per minute The temperature was raised and lowered from -120 ° C to 120 ° C, and the inflection point at the second temperature rise was determined as the glass transition temperature (Tg), and the melting peak temperature and the heat of fusion from the melting peak.

<Mole ratio and average carbon number of dihydroxy compounds after hydrolysis>
Approximately 0.5 g of polycarbonate diol was precisely weighed, placed in a 100 mL Erlenmeyer flask, and dissolved by adding 5 mL of tetrahydrofuran. Next, 45 mL of methanol and 5 mL of a 25 wt% aqueous sodium hydroxide solution were added. The condenser was set in a 100 mL Erlenmeyer flask, and hydrolysis was performed by heating in a 75-80 ° C. water bath for 30 minutes. After leaving it to be cooled at room temperature, 5 mL of 6 N hydrochloric acid was added to neutralize sodium hydroxide, and the pH was adjusted to 2 to 4. The whole was transferred to a 100 mL volumetric flask, the inside of the Erlenmeyer was washed twice with an appropriate amount of methanol, and the washing was also transferred to the 100 mL volumetric flask. After adding an appropriate amount of methanol to make 100 mL, the solutions were mixed in a measuring flask. The supernatant was collected, filtered through a filter, and analyzed by GC. The concentration of each dihydroxy compound was prepared beforehand from each dihydroxy compound known as a standard substance, and the weight percentage was calculated from the area ratio obtained by GC. The molar ratio of each dihydroxy compound was calculated from the weight% obtained by GC and the molecular weight of each dihydroxy compound. The average carbon number was calculated from the carbon number and molar ratio of each dihydroxy compound.

(Analysis conditions)
Device: Agilent 6850 (manufactured by Agilent Technologies)
Column: Agilent J & W GC Column DB-WAX
Inner diameter 0.25 mm, Length 60 m, Film thickness 0.25 μm
Detector: Hydrogen flame ionization detector (FID)
Temperature rising program: 150 ° C (2 minutes), 150 ° C → 245 ° C (5 ° C / min, 19 minutes), 245 ° C (2 minutes)

<Proportion of ether group to carbonate group>
The polycarbonate diol was hydrolyzed in the same manner as the molar ratio of the dihydroxy compound after hydrolysis and analyzed by GC. The compound was identified by GC-MS about a structure unknown thing. The concentration of the dihydroxy compound containing an ether group after hydrolysis was prepared in advance using diethylene glycol as a calibration curve, and the weight percentage was calculated from the area ratio obtained by GC. The molar ratio of each dihydroxy compound was calculated from the weight% obtained by GC and the molecular weight of the dihydroxy compound. From the molar ratio of each dihydroxy compound, the molar ratio of the dihydroxy compound containing an ether group, and the molecular weight of the polycarbonate diol calculated from the above hydroxyl value, the ether group content ratio to the carbonate group was calculated and calculated.

(Analysis conditions)
Instrument: Agilent 7890B (manufactured by Agilent Technologies)
Column: Agilent J & W GC Column DB-WAXETR
Inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm
Detector: Hydrogen flame ionization detector (FID)
Temperature rising program: 100 ° C → 250 ° C (5 ° C / min) <THF remaining amount>
A solution prepared by adding 250 mg of monochlorobenzene to 500 mL of N-methylpyrrolidone was used as an internal standard solution. 0.50 g of polycarbonate diol was precisely weighed and dissolved in 5 mL of the above-mentioned internal standard solution weighed with a whole pipet. The resulting solution was analyzed by gas chromatography (GC). For the concentration of THF, a calibration curve was prepared in advance from THF known as a standard substance, and the weight% was calculated from the area ratio obtained by gas chromatography (GC).

(Analysis conditions)
Device: Agilent 6850 (manufactured by Agilent Technologies)
Column: Agilent J & W GC Column DB-WAX
Inner diameter 0.25 mm, Length 60 m, Film thickness 0.25 mm
Detector: Hydrogen flame ionization detector (FID)
Temperature rising program: 150 ° C → 190 ° C (5 minutes) 190 → 245 ° C (40 minutes)
Injection volume: 1 μL
Inlet temperature: 200 ° C
Detector temperature: 245 ° C (FID detector)

[Evaluation method: polyurethane]
<Isocyanate group concentration measurement>
Dilute 20 mL of a mixed solution of di-n-butylamine / toluene (weight ratio: 2/25) with 90 mL of acetone and titrate with 0.5 N aqueous hydrochloric acid to measure the amount of aqueous hydrochloric acid required for neutralization, blank value And Thereafter, 1 to 2 g of the reaction solution is extracted, 20 mL of a mixed solution of di-n-butylamine / toluene is added, and the mixture is stirred at room temperature for 30 minutes. The amount of hydrochloric acid aqueous solution required for neutralization was measured by titration, and the amount of the remaining amine was quantified. From the volume of the hydrochloric acid aqueous solution required for neutralization, the concentration of isocyanate group was determined by the following equation.
Isocyanate group concentration (% by weight) = A * 42.02.D
A: Isocyanate group (mol) contained in the sample used for this measurement
A = (B-C) x 0.5 / 1000 x f
B: Amount (mL) of 0.5 N aqueous hydrochloric acid solution required for blank measurement
C: Amount (mL) of 0.5 N aqueous hydrochloric acid solution required for this measurement
D: Sample used for this measurement (g)
f: titer of hydrochloric acid solution

<Solution viscosity measurement>
A viscometer TV-22 (made by Toki Sangyo Co., Ltd.) was placed in a solution (concentration: 30% by weight) in which polyurethane was dissolved in dimethylformamide, and a rotor of 3 ° × R14 was set, and the solution viscosity of the polyurethane solution was measured at 25 ° C. .

<Molecular weight measurement>
Dimethylacetamide solution is prepared so that the molecular weight of polyurethane becomes 0.14% by weight of polyurethane, and GPC apparatus (made by Tosoh Corporation, product name “HLC-8220” (column: Tskgel GMH-XL 2)) The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of standard polystyrene were measured using

<Ole acid resistance evaluation method>
The polyurethane solution is applied on a fluoroplastic sheet (fluorinated tape Nitofron 900, thickness 0.1 mm, Nitto Denko Corporation) with a 9.5 mil applicator, followed by 1 hour at 60 ° C., followed by 0.5 at 100 ° C. Let dry for hours. After drying at 80 ° C. for 15 hours in a vacuum state at 100 ° C. for 15 hours, the film is allowed to stand for 12 hours or more under constant temperature and humidity of 23 ° C. and 55% RH. The pieces were cut out, placed in a 250 ml glass bottle containing 50 ml of a test solvent, and allowed to stand for 1 week or 16 hours in a thermostatic bath under a nitrogen atmosphere at 80 ° C. After the test, the front and back of the test piece were lightly wiped with a paper wiper, and then the weight was measured to calculate the weight increase ratio from before the test. The closer to 0% weight change, the better the oleic acid resistance.

<Polyurethane ethanol resistance evaluation method>
After producing a urethane film by the same method as shown in the above-mentioned <Oleic acid resistance evaluation method>, a test piece of the urethane film cut into 3 cm × 3 cm was cut out. The weight of the test piece was measured by a precision balance, and then put into a glass petri dish with an inner diameter of 10 cmφ containing 50 ml of a test solvent, and immersed for 1 hour at a room temperature of about 23 ° C. After the test, the test piece was taken out and lightly wiped with a paper wiper, and then the weight was measured to calculate the weight increase ratio from before the test.

<Method of measuring glass transition temperature (Tg)>
About 5 mg of a polyurethane film piece prepared in the same manner as for the evaluation of oleic acid resistance is enclosed in an aluminum pan, and EXSTAR DSC 6200 (manufactured by Seiko Instruments Inc.) is used under a nitrogen atmosphere at a rate of 10 ° C./min. Temperature raising and lowering operations were performed at 250 ° C., 250 ° C. to −100 ° C., and −100 ° C. to 250 ° C., and the inflection point at the second temperature rise was made the glass transition temperature (Tg).

<Room temperature tensile test method>
According to JIS K6301 (2010), a polyurethane test piece in the form of a strip having a width of 10 mm, a length of 100 mm and a thickness of about 50 μm was measured using a tensile tester [Orientech Co., Ltd., product name “Tensilon UTM-III-100”]. A tensile test was conducted at a temperature of 23 ° C. (relative humidity 55%) at a chuck distance of 50 mm, at a tensile speed of 500 mm / min, and the stress at 100% elongation of the test piece was measured. Further, Young's modulus was taken as the slope of the stress value at the initial elongation, and specifically, it was taken as the value of stress at an elongation of 1%.

<Low temperature tensile test method>
According to JIS K6301 (2010), a polyurethane test piece in the form of a strip having a width of 10 mm, a length of 100 mm, and a thickness of about 50 μm was measured using a tensile tester [Shimadzu Corporation, product name “
Using autograph AG-X 5 kN ′ ′], a film was set at a distance between chucks of 50 mm in a thermostatic bath [product name “THERMOSTATIC CHAMBER TCR 2 W-200 T” manufactured by Shimadzu Corporation, product name, set at −10 ° C.]. Then, after leaving still at -10 degreeC for 3 minutes, the tension test was implemented at 500 mm / min in tensile velocity, and the stress at the time of 100% elongation of the test piece was measured. Further, Young's modulus was taken as the slope of the stress value at the initial elongation, and specifically, it was taken as the value of stress at an elongation of 1%.

<Polyurethane low temperature cycle test method>
A tensile tester [Product name “Autograph AG-X 5kN” manufactured by Shimadzu Corporation, a strip-shaped polyurethane test piece having a width of 10 mm, a length of 100 mm and a thickness of about 90 μm according to JIS K6301 (2010)] Using a load cell 100N], a film was set at a distance between chucks of 50 mm in a thermostatic chamber [product name "THERMOSTATIC CHAMBER TCR 2 W-200T" manufactured by Shimadzu Corporation, product name, set at -10 ° C. Subsequently, it was allowed to stand at -10 ° C for 3 minutes, and then it was stretched to 300% at a tensile rate of 500 mm / min, subsequently contracted to the original length at the same rate, and this was repeated twice. The ratio of the stress at 250% elongation at the first contraction to the stress at 250% elongation at the first elongation (hereinafter sometimes referred to as "ratio 1") was determined. The stress at 250% elongation at the second elongation (hereinafter sometimes referred to as “ratio 2”) was determined relative to the stress at 250% elongation at the first elongation.

<Heat resistance evaluation>
The polyurethane film prepared in the same manner as the oleic acid resistance evaluation is made into a strip of width 100 mm, length 100 mm and thickness about 50 μm, and heated in a gear oven at a temperature of 120 ° C. for 400 hours. Weight average molecular weight of sample after heating (Mw) was measured by the method described in <Molecular weight measurement>.

[Evaluation of synthetic leather]
<KES test>
The synthetic leather sample was cut into 8 cm × 20 cm and attached to a KES surface tester (Kato Tech KES-FB4) equipped with a silicone rubber sensor (5 mm square) under an environment of temperature 20 ° C. and humidity 50%. . The sensor was placed on the sample and moved at a speed of 1 mm / sec with a load of 50 gf to detect the dynamic coefficient of friction (MID) and the standard deviation of dynamic coefficient of friction (MMD). Also, the value of MID / MMD was calculated by dividing the value of MID by the value of MMD. When the MID is large and the value of MID / MMD is large, it indicates that the wet feeling and the sliming feeling are good.

<Touch test>
The feel when sliding on the synthetic leather with a finger was evaluated as follows.
4 points: heavy feel like wet 3 points: feel like slightly wet 2 points: feel slightly dry 1 point: feel dry and slippery

<Ole acid resistance test>
A test piece obtained by cutting a synthetic leather sample into 2 cm × 2 cm was placed in a 250 ml glass bottle containing 50 ml of oleic acid and allowed to stand at 80 ° C. for 72 hours while covered. Remove the test piece from the glass bottle, lightly absorb oleic acid adhering to the surface of the test piece with a paper towel (manufactured by Oji Nepia Co., Ltd., Napier Super Absorbent Kitchen Towel) and suck it out, and observe the surface of the test piece at that time, The surface of the coated film was raised to one point.
About what did not have a visual change in the coating film surface, it rubbed by fixed power with the said paper-made towel, and it evaluated by the following score by the frequency | count that float and peeling arose on the coating film surface.
(Number of frictions where peeling was observed on the coating surface)
5 points: 50 times or more (without peeling)
4 points: 40 or more and less than 50 times 3 points: 30 or more and less than 40 times 2 points: less than 30 times 1 point: 0 times

<Warability>
Two 3 cm × 12 cm test pieces were cut in each of the longitudinal direction and the lateral direction of the synthetic leather in accordance with JIS L 1096-1972. Fix the obtained test piece between the two grips opened in advance by 20 mm of a Scott-type testing machine (Scot-type friction-wear tester, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in a state where the synthetic leather surfaces are joined together, Reciprocal friction was performed 1000 times with a load of 9.81 N at a distance of 40 mm. The appearance change of the surface of the test piece obtained as a result was evaluated as follows.
5 points: no change 4 points: slight skin floating on the surface of the leather is confirmed 3 points: skin floating is clearly observed on the surface of the leather 2 points: skin floating and cracks from the leather surface 1 point: The skin is broken from the surface of the leather and peeling has occurred

Raw materials used
The raw materials used for producing the polycarbonate diol of this example are as follows.
1,4-butanediol (hereinafter sometimes abbreviated as 1,4 BD): 1,3-propanediol manufactured by Mitsubishi Chemical Corporation (hereinafter sometimes abbreviated as 1,3 PDO): Wako Pure Chemical Industries, Ltd. Manufactured by DuPont Co., Ltd. 1,6-hexanediol (hereinafter sometimes abbreviated as 1,6HD): BASF 1,10-decanediol (hereinafter sometimes abbreviated as 1, 10DD): Toyokuni Oil 1,12-dodecanediol (hereinafter sometimes abbreviated as 1,12 DDD): Wako Pure Chemical Industries, Ltd. 3-methyl-1,5-pentanediol (hereinafter abbreviated as 3M1, 5PD) A): Wako Pure Chemical Industries, Ltd. Diphenyl carbonate (hereinafter sometimes abbreviated as DPC): Mitsubishi Chemical Co., Ltd. ethylene carbonate (hereinafter E) May be abbreviated as C): manufactured by Mitsubishi Chemical Co., Ltd. magnesium acetate tetrahydrate: manufactured by Wako Pure Chemical Industries, Ltd. tetrabutyl orthotitanate: manufactured by Tokyo Chemical Industry Co., Ltd.

Example 1
<Manufacture and evaluation of polycarbonate diol>
1,4-butanediol (1,4 BD): 879.5 g, 1,10-decanediol (1,1) as a raw material in a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator. 10DD): 597.6 g, diphenyl carbonate: 2622.8 g, magnesium acetate tetrahydrate aqueous solution: 6.7 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 55 mg) was charged, and nitrogen gas was substituted . Under stirring, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol from the system. Next, the pressure is lowered to 9.3 kPa for 90 minutes, and further lowered to 0.7 kPa for 30 minutes to continue the reaction, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compound out of the system. The mixture was reacted for 60 minutes to obtain a polycarbonate diol-containing composition.

The obtained polycarbonate diol containing composition was sent to a thin film distillation apparatus at a flow rate of 20 g / min, and thin film distillation (temperature: 180 to 190 ° C., pressure: 40 to 67 Pa) was performed. As a thin film distillation apparatus, an internal condenser with a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m ² , a jacketed Kamata Scientific Co., Ltd. molecular distillation apparatus MS-300 special type was used. The same applies to the following examples and comparative examples.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 1.

<Production and evaluation of polyurethane>
Using the polycarbonate diol obtained by the above method, a specific polyurethane was produced by the following operation.

(Prepolymer (PP) formation reaction)
91.00 g of the above polycarbonate diol previously heated to 80 ° C. is placed in a separable flask provided with a thermocouple and a cooling tube, and the flask is immersed in an oil bath at 60 ° C. to obtain 4,4'-dicyclohexylmethane Add 21.90 g of diisocyanate (hereinafter H12MDI, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.335 g of triisooctyl phosphite (hereinafter TiOP, manufactured by Tokyo Chemical Industry Co., Ltd.) as a reaction inhibitor, and keep the inside of the flask under a nitrogen atmosphere The temperature was raised to 80 ° C. in about 1 hour while stirring at 60 rpm. After raising the temperature to 80 ° C., 7.2 mg (81.9 wt ppm based on the total weight of polycarbonate diol and isocyanate) of Neostan U-830 (hereinafter U-830, manufactured by Nitto Kasei Co., Ltd.) as a urethanization catalyst is added to generate heat. The oil bath was heated to 100 ° C. and stirred for about 2 hours. The concentration of the isocyanate group was analyzed to confirm that the theoretical amount of the isocyanate group was consumed.

(Chain extension reaction)
109.00 g of the obtained prepolymer (PP) was diluted with 11.46 g of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.). Subsequently, 237.90 g of dehydrated N, N-dimethylformamide (hereinafter, DMF, manufactured by Wako Pure Chemical Industries, Ltd.) was added, the flask was immersed in an oil bath at 55 ° C., and the prepolymer was dissolved while stirring at about 200 rpm. After analyzing the concentration of isocyanate group of the prepolymer solution, immerse the flask in an oil bath set at 35 ° C, and while stirring at 150 rpm, necessary amount of isophorone diamine (following IPDA, manufactured by Tokyo Kasei Co., Ltd.) 5 calculated from residual isocyanate .74g was added in portions. After stirring for about 1 hour, 0.550 g of morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end terminator is added, and stirring is further performed for 1 hour to obtain a polyurethane solution having a viscosity of 125 Pa · s and a weight average molecular weight of 151,000. The The evaluation results of the properties and physical properties of this polyurethane are shown in Table 3.

[Examples 2 to 10]
<Manufacture and evaluation of polycarbonate diol>
In the production of the polycarbonate diol of Example 1, the reaction was carried out under the same conditions and method as in Example 1 except that the type and amount of PCD polymerization raw material were changed to the type and amount of raw material listed in Table 1. A diol-containing composition was obtained.
The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Example 1. The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 1.

<Production and evaluation of polyurethane>
Polycarbonate Diol (PCD) Used in the Preparation of the Polyurethane of Example 1
The reaction was carried out under the same conditions and methods as in Example 1 except that the type of PCD and the amount of each raw material charged were changed to PCD and the amount described in Table 3, respectively, to obtain a polyurethane solution. The properties and physical properties of this polyurethane are shown in Table 3.

<Manufacture and evaluation of synthetic leather>
The synthetic leather was manufactured by the following operation using the polyurethane solution obtained by the above-mentioned method about Example 2, 3, 6.
After adding 20 parts by weight of methyl ethyl ketone to 100 parts by weight of the polyurethane solution obtained by the above method to make a uniform solution, a release paper (manufactured by Dainippon Printing Co., Ltd., DNTP. APT. DE-) is used using a 6 mil applicator. 3) applied on top. After drying this in a dryer at 100 ° C. for 2 minutes, using a 6-mil applicator on a dried coating, a urethane resin solution for an adhesive <100 parts by weight of a urethane resin for an adhesive described below, black pigment (DIC (stock A mixed solution of 20 parts by weight of carbon black) 30 parts by weight of methyl ethyl ketone (MEK) and 10 parts by weight of DMF was applied and dried in a dryer at 100 ° C. for 1 minute. Place the wet-based urethane layer side shown below on the adhesive so that air does not enter, press-bond with a stretch bar, dry for 2 minutes with a dryer at 100 ° C, and then for 15 hours with a dryer at 80 ° C. It was dry. Thereafter, the resultant was left to cool at room temperature to peel off the release paper, to obtain synthetic leather. The evaluation results of the obtained synthetic leather are shown in Table 6.
In addition, the raw materials used for synthetic leather preparation are as follows.

(Urethane resin for adhesives)
Urethane solution with solid content of 30% by weight Solvent composition: MEK / DMF = 40/60 weight ratio Urethane composition:
PC-2000 / 1, 4 BDG / MDI = 0.9 / 1.1 / 2.0 mol ratio PC-2000: polycarbonate diol molecular weight 2000
14BG: 1,4-butanediol MDI: 4,4'-diphenylmethane diisocyanate

(Wet basis)
A polyurethane resin consisting of polycarbonate diol, polytetramethylene glycol and MDI prepared by wet coagulation on a woven fabric

Production Examples 1 and 2
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, the 1, 4 BD, 1, 10 DD, DPC, an aqueous solution of magnesium acetate tetrahydrate (concentration: 8.4 g / L), The amounts listed in Table 4 below were introduced as raw materials and replaced with nitrogen gas. Under stirring, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Thereafter, the pressure was lowered to 24 kPa over 2 minutes, and then reacted for 90 minutes while removing phenol from the system. Next, the pressure is lowered to 9.3 kPa for 90 minutes, and further lowered to 0.7 kPa for 30 minutes to continue the reaction, and then the temperature is raised to 170 ° C. to remove phenol and unreacted dihydroxy compound out of the system. The mixture was reacted for 90 minutes to obtain a polycarbonate diol-containing composition (Production Example 1 and Production Example 2 in Table 4).

The obtained polycarbonate diol containing composition was sent to a thin film distillation apparatus at a flow rate of 20 g / min, and thin film distillation (temperature: 180 to 190 ° C., pressure: 40 to 67 Pa) was performed. As a thin film distillation apparatus, an internal condenser having a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m 2, a jacketed Kamata Scientific Co., Ltd. molecular distillation apparatus MS-300 special type was used.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 4 (Production Example 1 and Production Example 2).

[Example 11]
<Manufacture and evaluation of polycarbonate diol>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 360 g of the polycarbonate diol obtained in Production Example 1 and 640 g of the polycarbonate diol obtained in Production Example 2 are charged, and nitrogen gas substitution is performed. did. The internal temperature was raised to 120 ° C., and the mixture was stirred for 30 minutes under nitrogen flow to mix polycarbonate diol. The evaluation results of the properties and physical properties of the obtained polycarbonate diol are shown in Table 4.

<Production and evaluation of polyurethane>
Using the polycarbonate diol obtained by the above method, a specific polyurethane was produced by the following operation.

(Prepolymer (PP) formation reaction)
In a separable flask provided with a thermocouple and a condenser, 90.94 g of polycarbonate diol described in Example 11 (hereinafter sometimes abbreviated as "PCD") preheated to 80 ° C. is placed, and oil at 60 ° C. After immersing the flask in a bath, 18.59 g of 4,4'-dicyclohexylmethane diisocyanate (hereinafter sometimes abbreviated as "H12 MDI"; manufactured by Tokyo Chemical Industry Co., Ltd.) and triisooctyl phosphite as a reaction inhibitor 0.324 g (hereinafter sometimes abbreviated as "TiOP", manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the temperature in the flask was raised to 80 ° C. in about 1 hour while being stirred at 60 rpm in a nitrogen atmosphere. After the temperature was raised to 80 ° C., Neostan U-830 (hereinafter referred to as “U-830” as a urethanization catalyst) (produced by Nitto Kasei Co., Ltd.) 5.1 mg (based on the total weight of polycarbonate geo and isocyanate) ppm) was added, and after the exotherm had subsided, the oil bath was heated to 100.degree. C. and stirred for about 2 hours. The concentration of the isocyanate group was analyzed to confirm that the theoretical amount of the isocyanate group was consumed.

(Chain extension reaction)
102.61 g of the obtained prepolymer (hereinafter sometimes abbreviated as "PP") was diluted with 10.72 g of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.). Subsequently, 221.1 g of dehydrated N, N-dimethylformamide (hereinafter sometimes abbreviated as "DMF", manufactured by Wako Pure Chemical Industries, Ltd.) is added, and the flask is immersed in an oil bath at 55 ° C and stirred at about 200 rpm The prepolymer was dissolved while. After analyzing the concentration of isocyanate group of the prepolymer solution, immerse the flask in an oil bath set at 35 ° C, and while stirring at 150 rpm, necessary amount of isophorone diamine (hereinafter abbreviated as "IPDA") calculated from the remaining isocyanate Separately, 4.82 g of Tokyo Chemical Industry Co., Ltd. was added. After stirring for about 1 hour, 0.398 g of morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a chain stopper is added, and stirring is further performed for 1 hour to obtain a polyurethane solution having a viscosity of 167 Pa · s and a weight average molecular weight of 164,000. The The evaluation results of the properties and physical properties of this polyurethane are shown in Table 5.

[Comparative Example 1, Comparative Example 5]
<Manufacture and evaluation of polycarbonate diol>
In the production of the polycarbonate diol of Example 1, the reaction was carried out under the same conditions and method as in Example 1 except that the type and amount of PCD polymerization raw materials were changed to the amounts of raw materials and raw materials listed in Table 2. A diol-containing composition was obtained.

The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Example 1.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 2.

<Production and evaluation of polyurethane>
In the production of the polyurethane of Example 1, the reaction was carried out under the same conditions and method as in Example 1 except that the polycarbonate diol (PCD) to be used and the preparation amounts of the respective raw materials were changed to the preparation amounts described in Table 3. A solution was obtained. The evaluation results of the properties and physical properties of this polyurethane are shown in Table 3.

[Comparative Examples 2 to 4, Comparative Example 6]
<Evaluation of polycarbonate diol>
The polycarbonate diols shown below were used respectively. The evaluation results of the properties and physical properties of each polycarbonate diol are shown in Table 2.
Comparative Example 2: Polycarbonate diol manufactured using 1, 6 HD as a raw material (Asahi Kasei Chemicals Corporation "Duranol (registered trademark)" grade: T-6002)
Comparative example 3: Polycarbonate diol manufactured using 1, 4 BD, 1, 6 HD as a raw material (Asahi Kasei Chemicals Co., Ltd. "Duranol (registered trademark)" grade: T-4672)
Comparative Example 4: Polycarbonate diol manufactured using 1, 5 PD, 1, 6 HD as a raw material (Asahi Kasei Chemicals Co., Ltd. "Duranol (registered trademark)" grade: T-5652)
Comparative Example 6: Polycarbonate diol using 1, 9 ND, 2 M 1, 8 OD as a raw material (made by Kuraray Co., Ltd. trade name: Kuraray polyol C-2065 N)

<Production and evaluation of polyurethane>
Polyurethane was produced using the above polycarbonate diol as PCD which is a raw material for producing polyurethane.

  In the production of the polyurethane of Example 1, the reaction was carried out under the same conditions and method as in the preparation of the polyurethane diol used as the raw material, except that the preparation amounts of the raw materials were changed to the types of the raw materials listed in Table 3 and the preparation amounts. To obtain a polyurethane solution. The evaluation results of the properties and physical properties of this polyurethane are shown in Table 3.

<Manufacture and evaluation of synthetic leather>
With regard to Comparative Examples 2 to 4, synthetic leather was manufactured under the same conditions and methods as in Example 2 except that the polyurethane used was changed to the polyurethane manufactured in each Comparative Example. The evaluation results of this synthetic leather are shown in Table 6.

Comparative Example 7
<Polycarbonate diol production and evaluation>
In the production of the polycarbonate diol of Example 1, the same procedure was followed except that the amounts of raw materials and raw materials charged were changed to the amounts of raw materials (1, 6 HD and 3 M 1, 5 PD) and raw materials listed in Table 2. The reaction was carried out to obtain a polycarbonate diol-containing composition.

The obtained polycarbonate diol-containing composition was subjected to thin film distillation in the same manner as in Example 1.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 2.

<Production and evaluation of polyurethane>
For the production of polyurethane by mixing the polycarbonate diol obtained by the above method and the polycarbonate diol used in Comparative Example 6 (manufactured by Kuraray Co., Ltd., trade name: Kuraray polyol C-2065N) in a weight ratio of 75:25 It was used as a raw material (PCD).

  In the preparation of the polyurethane of Example 1, the reaction was carried out under the same conditions and method as in Example 1 except that the raw material (PCD) obtained by this mixing was used and the preparation amount of the raw materials was changed to the preparation amount shown in Table 3. Conducted to obtain a polyurethane solution. The evaluation results of the properties and physical properties of this polyurethane are shown in Table 3.

[Production Example 3]
<Manufacture and evaluation of polycarbonate diol>
The amounts listed in Table 4 below for 1, 4 BD, 1, 10 DD, EC, tetrabutyl orthotitanate in a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator were used as raw materials And was purged with nitrogen gas. Under stirring, the internal temperature was raised to 130 ° C. to heat and dissolve the contents. Then, after pressure was reduced to 4.7 kPa over 2 minutes, it was made to react, pressure over 900 minutes over 3.3 kPa. Subsequently, 379.7 g of ethylene carbonate was added, and then the temperature was changed to 180 ° C., the pressure was changed to 16.7 kPa, and the reaction was performed for 480 minutes. The temperature was further changed to 190 ° C. and the pressure to 24.0 kPa, the pressure was lowered to 0.7 kPa over 240 minutes, and the reaction was further allowed to react at 0.7 kPa for 150 minutes to obtain a polycarbonate diol-containing composition.
Thin film distillation was performed in the same manner as in Production Example 1.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 4.

Production Example 4
<Manufacture and evaluation of polycarbonate diol>
The amounts listed in Table 4 below for 1, 4 BD, 1, 10 DD, EC, tetrabutyl orthotitanate in a 5 L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator were used as raw materials And was purged with nitrogen gas. Under stirring, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Thereafter, the pressure was lowered to 12.0 kPa over 2 minutes and then reacted for 760 minutes. Next, after adding 396.0 g of ethylene carbonate, the temperature was changed to 180 ° C. and the pressure was changed to 12.0 kPa, and then the pressure was decreased to 3.3 kPa over 380 minutes, and further reacted for 0.7 minutes at 270 kPa. And a polycarbonate diol-containing composition.
Thin film distillation was performed in the same manner as in Production Example 1.
The evaluation results of the properties and physical properties of the polycarbonate diol obtained by thin film distillation are shown in Table 4.

Comparative Example 8
<Manufacture and evaluation of polycarbonate diol>
In a 5 L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator, 127 g of polycarbonate diol obtained in Production Example 3 and 451 g of polycarbonate diol obtained in Production Example 4 are charged, and nitrogen gas substitution is performed. did. The internal temperature was raised to 120 ° C., and the mixture was stirred for 30 minutes under nitrogen flow to mix polycarbonate diol.
The evaluation results of the properties and physical properties of the obtained polycarbonate diol are shown in Table 4.

<Production and evaluation of polyurethane>
In the production of the polyurethane of Example 11, the same procedure was followed except that the polycarbonate diol (PCD) used was changed to the PCD produced in Comparative Example 8 and the preparation amounts of the respective raw materials were changed to the preparation amounts described in Table 2, respectively. The reaction was carried out under the following conditions and method to obtain a polyurethane. The properties and physical properties of this polyurethane are shown in Table 5.

In the “stress at −10 ° C. and 100% elongation” in Table 3, the value is smaller in the example than in the comparative example, and it is understood that the flexibility at low temperature is good. Moreover, since the values of “80 ° C. oleic acid resistance change rate” and “room temperature ethanol resistance change rate” are small, it can be seen that the chemical resistance is good. Furthermore, since the value of “the rate of change in weight average molecular weight in terms of polystyrene after heat resistance test” is small, it can be seen that the heat resistance is good, and the examples show that their physical properties are good. Therefore, it is understood that the polycarbonate diol of the present invention is a polycarbonate diol as a raw material of polyurethane excellent in the balance of the chemical resistance, the low temperature characteristics and the heat resistant physical properties as compared with the conventional polycarbonate diol.

  From Table 5, in “room temperature ethyl acetate resistant weight change rate [%]”, those having an ether group ratio of 5.0 mol% or less to the carbonate group of polycarbonate diol are more than 5.0 mol%. It can be seen that the chemical resistance of ethyl acetate is good.

  From the “KES test” in Table 6, it is understood that in the example, the value of MID is 2.02 or more and the MID / MMD is 67.8 or more in comparison with the comparative example, and the wet feeling and the sliming feeling are good. . Furthermore, it can be seen from the “oleic acid resistance” that the examples are clearly better in oleic acid resistance than the comparative examples. Therefore, it is possible to obtain synthetic leather excellent in the balance of the chemical resistance, the low temperature characteristic, the heat resistance, and the physical property of touch feeling compared with the conventional product by using the polycarbonate diol of the present invention. I know that there is.

Claims (14)

A polycarbonate diol comprising a structural unit derived from a compound represented by the following formula (A) and a structural unit derived from a compound represented by the following formula (B), wherein the following formula is contained in all the structural units of the polycarbonate diol: Compound represented by the following formula (A) in which the ratio of the total of structural units derived from the compound represented by (A) and structural units derived from the compound represented by the following formula (B) is 50 mol% or more The molar ratio of the structural unit derived from and the structural unit derived from the compound represented by the following formula (B) is 70:30 to 98: 2, and the ratio of the ether group to the carbonate group of the polycarbonate diol The polycarbonate diol whose hydroxyl value is 20 mg-KOH / g or more and 450 mg-KOH / g or less which is 5.0 mol% or less.
HO-R ¹ -OH (A)
HO-R ² -OH (B)
(In the above formula (A), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and in the above formula (B), R ² represents a substituted or unsubstituted carbon atom having 10)示 す represents a divalent alkylene group having a carbon number of 12. The carbon atom in the alkylene group of R ¹ and R ² is a primary carbon atom, a secondary carbon atom or a tertiary carbon atom.) The polycarbonate diol according to claim 1, wherein an average carbon number of a dihydroxy compound obtained by hydrolyzing the polycarbonate diol is 4 or more and 5.5 or less. The polycarbonate diol according to claim 1 or 2 , wherein the hydroxyl value is 20 mg-KOH / g or more and 60 mg-KOH / g or less. 4. The compound according to any one of claims 1 to 3 , wherein the compound represented by the formula (A) is at least one compound selected from the group consisting of 1,3-propanediol and 1,4-butanediol. Polycarbonate diol as described. The compound represented by the above formula (B) is at least one compound selected from the group consisting of 1,10-decanediol, 1,11-undecanediol and 1,12-dodecanediol. The polycarbonate diol according to any one of 4 . The polycarbonate diol according to any one of claims 1 to 5 , wherein at least one of the compound represented by the formula (A) and the compound represented by the formula (B) is derived from a plant. A polyurethane comprising the polycarbonate diol according to any one of claims 1 to 6 . The artificial leather or synthetic leather manufactured using the polyurethane of Claim 7 . A paint or a coating agent produced using the polyurethane according to claim 7 . The elastic fiber manufactured using the polyurethane of Claim 7 . The water-based polyurethane paint manufactured using the polyurethane of Claim 7 . A pressure-sensitive adhesive or an adhesive produced using the polyurethane according to claim 7 . The active energy ray curable polymer composition which uses the polycarbonate diol of any one of Claims 1-6 . A method for producing the polycarbonate diol according to any one of claims 1 to 6 , which comprises using a compound represented by the following formula (A), a compound represented by the following formula (B) and a carbonate compound A method for producing a polycarbonate diol, which comprises polycondensation by transesterification.
HO-R ¹ -OH (A)
HO-R ² -OH (B)
(In the above formula (A), R ¹ represents a substituted or unsubstituted divalent alkylene group having 3 to 4 carbon atoms, and in the above formula (B), R ² represents a substituted or unsubstituted carbon atom having 10)二 represents a divalent alkylene group having a carbon number of 12. The carbon atom in the alkylene group of R ¹ and R ² is a primary carbon atom, a secondary carbon atom or a tertiary carbon atom.)