JPWO2014069563A1 - Polyester polycarbonate polyol - Google Patents

Abstract

Provided is a polyester polycarbonate polyol that can provide a coating film with excellent adhesion by using raw materials such as polyurethane resin and urethane acrylate. A polyester polycarbonate polyol containing a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a hydroxyl group at the molecular end, wherein the repeating unit represented by formula (1) is These are polyester polycarbonate polyols containing two or more repeating units represented by formula (3), and polyurethane resins and urethane acrylates obtained using the same.

Description

  The present invention relates to a polyester polycarbonate polyol, and a polyurethane resin and a urethane acrylate obtained using the polyester polycarbonate polyol.

  Polycarbonate diol is useful as a raw material for polyurethane resins, urethane acrylates, thermoplastic elastomers, etc., and is obtained by copolymerizing 1,6-hexanediol with 1,4-butanediol or 1,5-pentanediol. It is known that a polyurethane resin having a good balance of hydrolysis resistance, light resistance, oxidation deterioration resistance, elastic recovery property and the like can be obtained using polycarbonate diol as a raw material (Patent Document 1).

  In recent years, techniques for controlling the primary terminal OH ratio of polycarbonate diol have been proposed in order to improve the polymerization reactivity in the reaction for producing a polyurethane resin or the like (Patent Documents 2 to 4).

JP-A-2-289616 Japanese Patent No. 3874664 WO2009 / 063767 WO2009 / 063768

  However, the coating agent composition using the polycarbonate diol of the prior art has a problem that the obtained coating film does not adhere to the coating object and is easily peeled off. In particular, the problem of adhesion was remarkable for a synthetic rubber such as ethylene-propylene-diene rubber (EPDM). An object of this invention is to provide the raw material which can solve this problem and can provide the coating film excellent in adhesiveness.

（式（２）中、Ｒ^２は、炭素数２〜２０の２価の炭化水素基を表す）
で表される繰り返し単位を、特定量で、ポリカーボネートポリオールに導入して、ポリエステルポリカーボネートポリオールとすることにより、上記の課題が解決されうることを見出し、本発明を完成するに至った。The inventor has the formula (2):

(In formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms)
It was found that the above-mentioned problems can be solved by introducing a repeating unit represented by the formula (1) into a polycarbonate polyol in a specific amount to obtain a polyester polycarbonate polyol, and the present invention has been completed.

（式（１）中、Ｒ^１は、炭素数２〜２０の２価の炭化水素基を表す。）

（式（２）中、Ｒ^２は、炭素数２〜２０の２価の炭化水素基を表す。）

（式（３）中、ｎは、２〜２０の整数を表す。）
本発明２は、式（２）で表される繰り返し単位の量が、式（１）及び式（２）で表される繰り返し単位の合計中、１〜６０モル％である、本発明１のポリエステルポリカーボネートポリオールに関する。
本発明３は、式（３）で表される繰り返し単位の量が、式（１）で表される繰り返し単位中、６０〜１００モル％である、本発明１又は２のポリエステルポリカーボネートポリオールに関する。
本発明４は、式（３）で表される繰り返し単位が、式（４）〜（７）で表される繰り返し単位からなる群から選ばれる２種以上である、本発明１〜３のいずれかのポリエステルポリカーボネートポリオールに関する。

本発明５は、式（３）で表される繰り返し単位が、式（５）及び式（７）で表される繰り返し単位である、本発明４のポリエステルポリカーボネートポリオールに関する。
本発明６は、式（５）で表される繰り返し単位の量が、式（５）及び式（７）で表される繰り返し単位中、３０〜９５モル％である、本発明５のポリエステルポリカーボネートポリオールに関する。
本発明７は、式（３）で表される繰り返し単位が、式（６）及び式（７）で表される繰り返し単位である、本発明４のポリエステルポリカーボネートポリオールに関する。
本発明８は、式（６）で表される繰り返し単位の量が、式（６）及び式（７）で表される繰り返し単位中、２０〜８０モル％である、本発明７のポリエステルポリカーボネートポリオールに関する。
本発明９は、式（２）で表される繰り返し単位が、式（４’）〜（７’）で表される繰り返し単位からなる群から選ばれる１種以上である、本発明１〜８のいずれかのポリエステルポリカーボネートポリオールに関する。

本発明１０は、式（２）で表される繰り返し単位が、式（６’）で表される繰り返し単位である、本発明９のポリエステルポリカーボネートポリオールに関する。
本発明１１は、数平均分子量が、５００〜５０００である、本発明１〜１０のいずれかのポリエステルポリカーボネートポリオールに関する。
本発明１２は、本発明１〜１１のいずれかのポリエステルポリカーボネートポリオールとポリイソシアネートを共重合して得られる、ポリウレタン樹脂に関する。
本発明１３は、本発明１〜１１のいずれかのポリエステルポリカーボネートポリオール、ポリイソシアネート及び水酸基含有（メタ）アクリレートを反応させて得られる、ウレタンアクリレートに関する。The present invention 1 is a polyester polycarbonate polyol containing a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a hydroxyl group at the molecular end.
The repeating unit represented by the following formula (1) relates to a polyester polycarbonate polyol containing two or more repeating units represented by the following formula (3).

(In formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In formula (3), n represents an integer of 2 to 20)
Invention 2 provides the amount of the repeating unit represented by the formula (2) in the total amount of the repeating units represented by the formula (1) and the formula (2) of 1 to 60 mol%. It relates to a polyester polycarbonate polyol.
This invention 3 relates to the polyester polycarbonate polyol of this invention 1 or 2 whose quantity of the repeating unit represented by Formula (3) is 60-100 mol% in the repeating unit represented by Formula (1).
Invention 4 is any one of Inventions 1 to 3, wherein the repeating unit represented by formula (3) is at least two selected from the group consisting of repeating units represented by formulas (4) to (7). It relates to the polyester polycarbonate polyol.

This invention 5 relates to the polyester polycarbonate polyol of this invention 4 whose repeating unit represented by Formula (3) is a repeating unit represented by Formula (5) and Formula (7).
This invention 6 is the polyester polycarbonate of this invention 5 whose quantity of the repeating unit represented by Formula (5) is 30-95 mol% in the repeating unit represented by Formula (5) and Formula (7). Relates to polyols.
This invention 7 relates to the polyester polycarbonate polyol of this invention 4 whose repeating unit represented by Formula (3) is a repeating unit represented by Formula (6) and Formula (7).
This invention 8 is polyester polycarbonate of this invention 7 whose quantity of the repeating unit represented by Formula (6) is 20-80 mol% in the repeating unit represented by Formula (6) and Formula (7). Relates to polyols.
This invention 9 is this invention 1-8 whose repeating unit represented by Formula (2) is 1 or more types chosen from the group which consists of a repeating unit represented by Formula (4 ')-(7'). To a polyester polycarbonate polyol.

This invention 10 relates to the polyester polycarbonate polyol of this invention 9 whose repeating unit represented by Formula (2) is a repeating unit represented by Formula (6 ').
This invention 11 relates to the polyester polycarbonate polyol in any one of this invention 1-10 whose number average molecular weight is 500-5000.
This invention 12 relates to the polyurethane resin obtained by copolymerizing the polyester polycarbonate polyol and polyisocyanate in any one of this invention 1-11.
This invention 13 relates to the urethane acrylate obtained by making the polyester polycarbonate polyol of any of this invention 1-11, polyisocyanate, and a hydroxyl-containing (meth) acrylate react.

  By using the polyester polycarbonate polyol of the present invention as a raw material such as polyurethane resin or urethane acrylate, a coating film having excellent adhesion can be provided. According to the polyester polycarbonate polyol of the present invention, excellent adhesion of the coating film can be obtained especially for a synthetic rubber such as ethylene-propylene-diene rubber (EPDM).

  The polyester polycarbonate polyol of this invention contains the repeating unit represented by Formula (1), the repeating unit represented by Formula (2), and the hydroxyl group of a molecule terminal.

（式（１）中、Ｒ^１は、炭素数２〜２０の２価の炭化水素基を表す。）In the present invention, the repeating unit represented by the formula (1) is as follows.

(In formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

  In this invention, the repeating unit represented by Formula (1) contains 2 or more types of repeating units represented by Formula (3). The repeating unit represented by the formula (3) may be 2 to 5 types, and is preferably 2 or 3 types from the viewpoint that the physical properties of the polyester polycarbonate polyol can be easily controlled.

（式（３）中、ｎは、２〜２０の整数を表す。）In the present invention, the repeating unit represented by the formula (3) is as follows.

(In formula (3), n represents an integer of 2 to 20)

  The amount of the repeating unit represented by the formula (3) is preferably 60 mol% or more in the repeating unit represented by the formula (1) in order to reduce the viscosity and facilitate handling. This amount is preferably 90 mol% or more, more preferably 100 mol%, and all the repeating units represented by the formula (1) are repeating units represented by the formula (3). May be.

As a repeating unit represented by Formula (3), the repeating unit represented by Formula (4)-(7) is mentioned, Among these, it can be 2 or more types.

  For example, as the repeating unit represented by Formula (3), the repeating units represented by Formula (5) and Formula (7) can be combined. This combination is preferable when it is used as a raw material for a synthetic resin such as a polyurethane resin, because solvent resistance can be easily provided to the synthetic resin.

In this combination, the amount of the repeating unit represented by the formula (5) can be 30 to 95 mol% in the repeating units represented by the formula (5) and the formula (7). Within this range, the polyester polycarbonate polyol can be expected to have fluidity (for example, a viscosity of 500 to 7000 cP) at room temperature (25 ° C.) or under heating (for example, under heating up to 55 ° C.). This amount is preferably 51 to 95 mol%, more preferably 60 to 95 mol%. Here, the viscosity is a value measured at a predetermined temperature using an E-type viscometer (“BROOLFIELD viscometer LV DV-II + Pro” manufactured by BROOKFIELD) as follows.
When the viscosity is 300 to 1900 cP: Using “Spindle CPE-42” as a cone, the value measured at a rotation speed of 0.3 rpm was taken as the viscosity.
When the viscosity is 1901 to 4000 cP: “Spindle CPE-52” was used as the cone, and the value measured at a rotation speed of 0.6 rpm was taken as the viscosity.
When the viscosity is 4001 to 20000 cP: “Spindle CPE-52” was used as the cone, and the value measured at a rotation speed of 0.3 rpm was taken as the viscosity.
When the viscosity is 20001 to 60000 cP: Using “Spindle CPE-52” as a cone, the value measured at a rotational speed of 0.1 rpm was taken as the viscosity.
When the viscosity is 60001 to 100,000 cP: The value measured at a rotation speed of 0.05 rpm using “Spindle CPE-52” as a cone was taken as the viscosity.

  Further, for example, as the repeating unit represented by the formula (3), the repeating units represented by the formula (6) and the formula (7) can be combined. This combination is preferable when used as a raw material for a synthetic resin such as a polyurethane resin because it can easily provide high flexibility to the synthetic resin.

  In this combination, the amount of the repeating unit represented by the formula (6) can be 20 to 80 mol% in the repeating units represented by the formula (6) and the formula (7). Within this range, the polyester polycarbonate polyol can be expected to have fluidity (for example, a viscosity of 500 to 7000 cP) at room temperature (25 ° C.) or under heating (for example, under heating up to 55 ° C.). This amount is more preferably 30 to 70 mol%, particularly preferably more than 50 mol% and 70 mol% or less.

  Further, for example, as a repeating unit represented by formula (3), a combination of repeating units represented by formula (4), formula (5) and formula (7), or formula (4) and formula (6) Combinations of repeating units represented by formula (7) can also be used.

As the repeating unit represented by the formula (1) other than the formula (3), R ¹ is a branched alkylene group having 2 to 20 carbon atoms, such as a propylene group, an isobutylene group, or a 2-methyltetramethylene group. A 2-methylpentamethylene group, a 3-methylpentamethylene group, an isononamethylene group, a 2-methylnonamethylene group, etc .; a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, such as a cyclopentylene group, Cyclohexylene group, 1,2-dimethylenecyclopentane group, 1,3-dimethylenecyclopentane group, 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group 4,4′-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group, etc .; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms For example, phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group, 1,4-dimethylenebenzene group, naphthylene group, 4,4′-methylenediphenylene group, 2, A repeating unit such as 2-diphenylenepropane group can be mentioned.

（式（２）中、Ｒ^２は、炭素数２〜２０の２価の炭化水素基を表す。）In the present invention, the repeating unit represented by the formula (2) is as follows.

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

R ² is a linear or branched alkylene group having 2 to 20 carbon atoms, such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene. Group, propylene group, isobutylene group, 2-methyltetramethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, isononamethylene group, 2-methylnonamethylene group, etc .; Unsubstituted cycloalkylene group, for example, cyclopentylene group, cyclohexylene group, 1,2-dimethylenecyclopentane group, 1,3-dimethylenecyclopentane group, 1,2-dimethylenecyclohexane group, 1,3 -Dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedi Chloroxylene group, 2,2-dicyclohexylenepropane group, etc .; substituted or unsubstituted arylene group having 6 to 20 carbon atoms, such as phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group 1, 4-dimethylenebenzene group, naphthylene group, 4,4′-methylenediphenylene group, 2,2-diphenylenepropane group and the like.

R ² is preferably a linear alkylene group having 2 to 20 carbon atoms, and examples thereof include repeating units represented by formulas (4 ′) to (7 ′), and one or more of these may be used. it can.

  Among these, the formula (6 ′) is preferable because the raw material is easily available.

  The amount of the repeating unit represented by the formula (2) can be 1 to 60 mol% in the total of the repeating units represented by the formula (1) and the formula (2). If it is this range, fluidity | liquidity (for example, viscosity 500-7000 cP) will be easy at room temperature (25 degreeC) or under heating (for example, under heating to 55 degreeC), maintaining hydrolysis resistance. Can be obtained. This amount is preferably 2 to 50 mol%, more preferably 3 to 30 mol%.

  In the present invention, the manner in which the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) exist is not particularly limited, and may be random or block. The manner of existence of the repeating unit represented by formula (3) contained in the repeating unit represented by formula (1) is not particularly limited, and may be random or block.

  In the polyester polycarbonate polyol of the present invention, the number average molecular weight Mn can be 500 to 5,000. If it is this range, fluidity | liquidity (for example, viscosity 500-7000 cP) can be easily obtained at room temperature (25 degreeC) or under heating (for example, 55 degreeC), and it is excellent in handleability. The number average molecular weight Mn is preferably 500 to 3500, and more preferably 500 to 3000. In this specification, the number average molecular weight Mn is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577. Specifically, the hydroxyl value is measured and calculated by (56.1 × 1000 × valence) / hydroxyl value by end group quantification method (in this formula, the unit of hydroxyl value is [mgKOH / g]. Is). In the above formula, the valence is the number of hydroxyl groups in one molecule.

  In the polyester polycarbonate polyol of the present invention, the weight average molecular weight Mw can be 500 to 15000. The weight average molecular weight Mw is preferably 1000 to 13000. In this specification, the weight average molecular weight Mw is a value measured by GPC.

  In the polyester polycarbonate polyol of the present invention, the degree of dispersion Mw / Mn can be 1.0 to 3.0. The dispersity Mw / Mn is preferably 2.0 to 2.3.

  In the polyester polycarbonate polyol of the present invention, the acid value can be 0 to 1 mg KOH / g. Within this range, a polyurethane resin having particularly good physical properties can be obtained using this as a raw material. The acid value is preferably 0 to 0.1 mgKOH / g, and more preferably 0 to 0.05 mgKOH / g. In this specification, the acid value is a value measured according to the indicator titration method of JIS K1557.

  The present invention has a hydroxyl group at the molecular end. The present invention is preferably a polyester polycarbonate diol having hydroxyl groups at both molecular ends.

  The present invention can include a repeating unit other than the repeating units represented by formulas (1) and (2) (other repeating units). The other repeating units are preferably 10 mol% or less, more preferably 5 mol% or less in the repeating unit of the present invention.

  Examples of other repeating units include repeating units derived from polybutadiene polyol.

  In the present invention, the ratio of the number of moles of the repeating unit represented by the formula (1) or (2) or the repeating unit represented by the formula (3) in the repeating unit is consumed in the polyester polycarbonate polyol of the present invention. It can be converted from the raw material. Specifically, it can be determined from the ratio of the number of moles of raw materials charged in the production of the polyester polycarbonate polyol. However, when the raw material diol is distilled in the production process, the raw material diol distilled is subtracted.

  Although the manufacturing method in particular of the polyester polycarbonate polyol of this invention is not restrict | limited, The method of making the diol corresponding to Formula (1), the lactone corresponding to Formula (2), and carbonate ester react is mentioned. In this method, the temperature during the reaction can be 50 to 250 ° C., preferably 70 to 220 ° C. The pressure during the reaction can be 0 to 1000 mmHg, preferably 0.1 to 760 mmHg. The reaction time can be 5 to 48 hours.

  The reaction is preferably performed while removing by-produced alcohol out of the system. At that time, if the carbonate ester escapes from the system by azeotroping with the by-produced alcohol, an excessive amount of carbonate ester may be added.

  The reaction may be performed with or without a catalyst. In the case of using a catalyst, examples include catalysts used in known transesterification reactions, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, A metal such as germanium, tin, lead, antimony, arsenic, or cerium, or a salt, alkoxide, or organic compound thereof can be used. Particularly preferred are compounds such as sodium, titanium, zirconium, tin, such as sodium hydride, titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin. Examples include dimethoxide and dibutyltin oxide. The amount of the catalyst used is preferably 1 to 20000 ppm by weight, more preferably 10 to 5000 ppm by weight, particularly 20 to 4000 ppm by weight, based on the total charge in the production of the polyester polycarbonate polyol. preferable.

  After completion of the reaction, the polyester polycarbonate polyol of the present invention can be obtained by distilling off unreacted diols and lactones as necessary.

  Diols for deriving the repeating unit represented by the formula (1) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7 carbon atoms having no side chain such as 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. ˜20 alkane diols. These diols can induce the repeating unit represented by the formula (3) and are used in two or more kinds.

  Furthermore, as diols, 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1, Alkane diols having 2 to 20 carbon atoms having side chains such as 3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis C 6-2 such as (hydroxyethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, 2,7-norbornanediol Diols having the following alicyclic structure: Fragrance having 6 to 20 carbon atoms such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 2,7-naphthalenediethanol Examples thereof include diols having a group cyclic structure.

  In addition, polyhydric alcohols such as trimethylolpropane, pentaerythritol, and sorbitol can be used.

  Lactones that derive the repeating unit represented by formula (2) include ω-lactone, β-propiolactone, β-butyrolactone, β-valerolactone, δ-valerolactone, and β-methyl-δ-valerolactone. Lactones having 3 to 21 carbon atoms such as δ-caprolactone, ε-caprolactone, α-methyl-ε-caprolactone, ω-enanthlactone, ω-caprolactone, and ω-laurolactone, preferably ε- Caprolactone.

  Examples of the carbonic acid ester include aliphatic carbonic acid esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonic acid esters such as diphenyl carbonate, cyclic carbonic acid esters such as ethylene carbonate, and the like, from which it is easy to remove unnecessary by-products. An aliphatic carbonate or a cyclic carbonate is preferable, and dimethyl carbonate or ethylene carbonate is particularly preferable.

  The polyester polycarbonate polyol of the present invention can be used as raw materials such as polyurethane and urethane acrylate, coating agents, paints and ink additives, and the like.

  A polyurethane resin can be obtained by reacting the polyester polycarbonate polyol and polyisocyanate of the present invention.

  Examples of the polyisocyanate that can be used in the production of the polyurethane resin of the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), diphenylmethane-4,4′-. Aromatic diisocyanates such as diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, crude TDI, polymethylene polyphenyl isocyanate, crude MDI; Known aromatic aliphatic diisocyanates such as isocyanate (XDI) and phenylene diisocyanate; 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate Known aliphatic diisocyanates such as socyanate (IPDI), cyclohexane-1,2-diylbis (methylene) diisocyanate (hydrogenated XDI), and isocyanurate-modified products, carbodiimidization-modified products, biuret-modified products of these isocyanates Etc.

  In the production of the polyurethane resin of the present invention, a chain extender can be used as a copolymerization component. As the chain extender, a known chain extender can be used, and examples thereof include water, a low molecular polyol, and a polyamine. For the chain extender, for example, "Latest polyurethane application technology" (CMC Co., Ltd., issued in 1985) can be referred to.

  As the low molecular polyol, a diol having a molecular weight of 300 or less can be used. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Aliphatic diols such as neopentyl glycol and 1,10-decanediol; alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol; xylylene glycol and bis (P-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2 -Hydroxyethoxy) phenyl] cyclohexane and the like. Preferably, ethylene glycol and 1,4-butanediol are used.

  Depending on the use of the polyurethane resin, a known polymer polyol may be used as a chain extender as long as the effects of the present invention are not impaired. Examples of the polymer polyol include polyester polyol, polyether carbonate having a polyoxyalkylene chain (polyether carbonate polyol), and the like. As for the polymer polyol, for example, “Polyurethane foam” (Polymer Publication, 1987) can be referred to.

  As a method for producing the polyurethane resin of the present invention, a known polyurethane reaction technique can be used. For example, the polyester polycarbonate diol of the present invention and an organic polyisocyanate are used at room temperature (25 ° C.) to 200 at atmospheric pressure. A polyurethane resin can be produced by reacting at ° C. When a chain extender is used, it may be added from the beginning of the reaction or may be added from the middle of the reaction. Regarding the method for producing the polyurethane resin, for example, U.S. Pat. No. 5,070,173 can be referred to.

  In the polyurethane reaction, a known polymerization catalyst can be used, and examples thereof include organic metal salts such as tertiary amine, tin, and titanium. As for the polymerization catalyst, pages 23 to 32 of Keiji Yoshida “Polyurethane resin” (published by Nihon Kogyo Shimbun, 1969) can be referred to.

  The polyurethane reaction can be performed in the presence of a solvent. Examples of the solvent include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve and the like.

  In the polyurethane reaction, an end stopper can be used. Examples of the terminal terminator include compounds containing only one active hydrogen that reacts with an isocyanato group, such as monohydric alcohols such as ethyl alcohol and propyl alcohol, and secondary amines such as diethylamine and di-n-propylamine. It is done.

  You may mix | blend stabilizers, such as a heat stabilizer (for example, antioxidant) and a light stabilizer, with the polyurethane resin of this invention. Examples of the antioxidant include aliphatic, aromatic, or alkyl group-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, and dialkyl. Phosphorus compounds such as pentaerythritol diphosphite and dialkyl bisphenol A diphosphite; phenol derivatives (especially hindered phenol compounds); thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, thiodipropionic acid esters, etc. Sulfur compounds; tin compounds such as tin malate and dibutyltin monoxide are listed.

  Antioxidants can be classified into primary, secondary, and tertiary anti-aging agents. As hindered phenol compounds as primary anti-aging agents, Irganox 1010 (trade name; manufactured by BASF), Irganox 1520 (trade name; manufactured by BASF) Etc.) are preferred. As the phosphorus-based compound as the secondary anti-aging agent, PEP-36, PEP-24G, HP-10 (all trade names: manufactured by Asahi Denka Co., Ltd.) and Irgafos 168 (trade names: manufactured by BASF) are preferable. Furthermore, thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP) are preferable as the sulfur compound as the tertiary antiaging agent.

Examples of the light stabilizer include an ultraviolet absorption type light stabilizer and a radical scavenging type light stabilizer,
Examples of the ultraviolet light absorbing light stabilizer include benzotriazole-based compounds and benzophenone-based compounds. Examples of the radical scavenging light stabilizer include hindered amine compounds. These stabilizers may be used alone or in combination of two or more. The added amount of these stabilizers is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and still more preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of the polyurethane resin.

  You may mix | blend a plasticizer with the polyurethane resin of this invention. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate; tricresyl phosphate, triethyl phosphate , Tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, tris-dichloropropyl phosphate, etc .; trimellitic acid such as trimellitic acid octyl ester, trimellitic acid isodecyl ester Esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl Fatty acid esters such as azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methylacetylricinoleate; pyromellitic esters such as pyromellitic octyl ester; epoxidized soybean oil, epoxidized linseed oil, Epoxy plasticizers such as epoxidized fatty acid alkyl esters; polyether plasticizers such as adipic acid ether esters and polyethers; liquid rubbers such as liquid NBR, liquid acrylic rubber and liquid polybutadiene; non-aromatic paraffin oils and the like It is done. These plasticizers may be used alone or in combination of two or more. The addition amount of the plasticizer is appropriately selected according to the required hardness and physical properties, but is preferably 0.1 to 50 parts by weight per 100 parts by weight of the polyurethane resin.

  Furthermore, you may mix | blend an inorganic filler, a lubricant, a coloring agent, a silicone oil, a foaming agent, a flame retardant etc. with the polyurethane resin of this invention. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, and carbon black. These various additives can be used in amounts generally used for conventional polyurethane resins.

  The Shore D hardness of the polyurethane resin of the present invention is preferably in the range of 20 to 70, more preferably 25 to 50. If the Shore D hardness is 20 or more, the heat resistance and scratch resistance are sufficiently high, and if the Shore D hardness is 70 or less, the obtained low temperature performance and soft feeling will not be insufficient. Regarding the molecular weight of the polyurethane resin of the present invention, the polystyrene-equivalent number average molecular weight (Mn) measured by GPC analysis and the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC analysis are in the range of 10,000 to 200,000, respectively. It is preferable that

  The polyester polycarbonate polyol of the present invention can be used as a raw material for urethane acrylate.

  The urethane acrylate can be obtained by reacting the polyester polycarbonate polyol of the present invention, polyisocyanate, and (meth) acrylate having a reactive group with an isocyanato group. Specifically, urethane acrylate can be prepared by a method according to the methods described in JP-A Nos. 6-145636 and 2003-183345.

  As the polyisocyanate, for example, a polyisocyanate that can be used for the production of a polyurethane resin can be used. Among them, isophorone diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate are easy to handle. One or more selected from the group consisting of (hydrogenated MDI), 4,4′-diphenylenemethane diisocyanate (MDI), methylcyclohexylene diisocyanate (hydrogenated TDI), and 2,4-tolylene diisocyanate (TDI) are preferable. .

  Examples of the group reactive with the isocyanato group in the (meth) acrylate having a group reactive with the isocyanato group include a hydroxyl group, an amino group, and a thiol group. Specifically, a hydroxyl group-containing (meth) acrylate can be used, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy -3-butoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl acrylate, 2-hydroxy-3-phenyloxy (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, glycerin Mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, tetramethylolmethane tri (meth) acrylate, triethylene glycol mono (meth) acrylate, polypropylene glycol Rumono (meth) acrylate, polycaprolactone glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate. Among them, it is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate because it is easy to handle. One or more are preferred.

  A coating agent can be prepared by blending the urethane acrylate of the present invention with a photoinitiator and optionally (meth) acrylate. As the photoinitiator, known ones can be used, such as benzophenone, substituted benzophenone, acetophenone, substituted acetophenone, benzoin, benzoin alkyl ester, xanthone, substituted xanthone, phosphine oxide, diethoxyacetophenone, benzoin methyl ether, benzoin ethyl. Ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thioxanthone, N-methyldiethanol-amine-benzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-benzyl-2- (dimethylamino) ) -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like. Of these, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is preferable from the viewpoint of reactivity and easy handling.

  The (meth) acrylate is not particularly limited, and compounds exemplified by the above hydroxyl group-containing (meth) acrylate can also be used. Among these, in terms of reactivity, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri ( One or more selected from the group consisting of (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol tetra (meth) acrylate are preferred.

  The coating agent can contain a solvent, for example, ketone (acetone, methyl ethyl ketone, etc.), ester (methyl acetate, ethyl acetate, etc.), ether (diethyl ether, tetrahydrofuran, etc.), hydrocarbon (n- Hexane, benzene, etc.).

  The polyester polycarbonate polyol of the present invention is useful for raw materials such as polyurethane and urethane acrylate, coating agents, paint and ink additives, and the like.

  Next, an Example and a comparative example are given and this invention is demonstrated further in detail.

The number average molecular weight was measured as follows.
The hydroxyl value was measured in accordance with JIS K 1577, Method B. The number average molecular weight Mn was calculated from the measured hydroxyl value according to the following formula.
Number average molecular weight Mn = (56.1 × 1000 × 2) / hydroxyl value

  The acid value was measured according to the indicator titration method of JIS K 1557.

The viscosity is a value measured at a predetermined temperature using an E-type viscometer (“BROOLFIELD viscometer LV DV-II + Pro” manufactured by BROOKFIELD) as follows.
When the viscosity is 300 to 1900 cP: Using “Spindle CPE-42” as a cone, the value measured at a rotation speed of 0.3 rpm was taken as the viscosity.
When the viscosity is 1901 to 4000 cP: “Spindle CPE-52” was used as the cone, and the value measured at a rotation speed of 0.6 rpm was taken as the viscosity.
When the viscosity is 4001 to 20000 cP: “Spindle CPE-52” was used as the cone, and the value measured at a rotation speed of 0.3 rpm was taken as the viscosity.
When the viscosity is 20001 to 60000 cP: Using “Spindle CPE-52” as a cone, the value measured at a rotational speed of 0.1 rpm was taken as the viscosity.
When the viscosity is 60001 to 100,000 cP: The value measured at a rotation speed of 0.05 rpm using “Spindle CPE-52” as a cone was taken as the viscosity.
The weight average molecular weight (Mw) is a value in terms of polystyrene measured using GPC.
Moreover, Mw and Mn used for calculation of the degree of dispersion (Mw / Mn) are also polystyrene-converted values measured using GPC. For this reason, Mn used for calculation of the degree of dispersion is different from Mn calculated from the hydroxyl value.

  The ratio of the number of moles of each repeating unit in the obtained polyester polycarbonate diol was calculated from the amount of raw materials charged.

Example 1
The raw materials were charged so that 1,6-hexanediol: 1,5-pentanediol = 48: 52 (molar ratio). Further, the raw materials were charged so that the total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 9: 1 (molar ratio).
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer and a nitrogen introduction tube, 350.2 g (3.89 mol) of dimethyl carbonate, 186.8 g (1.58 mol) of 1,6-hexanediol, First, 178.4 g (1.71 mol) of 1,5-pentanediol, 41.8 g (0.37 mol) of ε-caprolactone, and 0.05 g of titanium tetrabutoxide were charged with methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring. The ester exchange reaction was carried out for 10 hours while distilling off the mixture. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of the distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 466.43 g of a polyester polycarbonate diol.
The number average molecular weight (based on JIS K 1577 method B) of the obtained polyester polycarbonate diol is 992, the acid value is 0.02 mg KOH / g, the weight average molecular weight is 2800, and the degree of dispersion is 2.1. Met. The viscosity is shown in Table 1.

Example 2
The raw materials were charged so that 1,6-hexanediol: 1,5-pentanediol = 48: 52 (molar ratio). In addition, the raw materials were charged so that the total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 7: 3 (molar ratio).
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introducing tube, dimethyl carbonate 292.8 g (3.25 mol), 1,6-hexanediol 162.9 g (1.38 mol), A mixture of 155.5 g (1.49 mol) of 1,5-pentanediol, 140.5 g (1.23 mol) of ε-caprolactone and 0.05 g of titanium tetrabutoxide was prepared. Methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring The ester exchange reaction was carried out for 10 hours while distilling off the mixture. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 501.03 g of a polyester polycarbonate diol.
The obtained polyester polycarbonate diol has a number average molecular weight (according to JIS K 1577, method B) of 985, an acid value of 0.03 mg KOH / g, a weight average molecular weight of 2800, and a dispersity of 2.1. Met. The viscosity is shown in Table 1.

Example 3
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer and a nitrogen introduction tube, 351.8 g (3.91 mol) of dimethyl carbonate, 169.5 g (1.43 mol) of 1,6-hexanediol, Charged 168.4 g (1.62 mol) of 1,5-pentanediol, 38.7 g (0.34 mol) of ε-caprolactone, and 0.05 g of titanium tetrabutoxide. Methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring The ester exchange reaction was carried out for 11 hours while distilling off the mixture. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of the distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 430.37 g of a polyester polycarbonate diol.
The number average molecular weight (based on JIS K 1577, Method B) of the obtained polyester polycarbonate diol is 1938, the acid value is 0.03 mg KOH / g, the weight average molecular weight is 5500, and the degree of dispersion is 2.2. Met. The viscosity is shown in Table 1.

Example 4
The raw materials were charged so that 1,6-hexanediol: 1,5-pentanediol = 48: 52 (molar ratio). In addition, the raw materials were charged so that the total of 1,6-hexanediol and 1,5-pentanediol: ε-caprolactone = 97: 3 (molar ratio).
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 377.2 g (4.19 mol) of dimethyl carbonate, 201.0 g (1.70 mol) of 1,6-hexanediol, Charged 192.0 g (1.84 mol) of 1,5-pentanediol, 11.3 g (0.1 mol) of ε-caprolactone and 0.05 g of titanium tetrabutoxide, and methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring. The ester exchange reaction was carried out for 10 hours while distilling off the mixture. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 458.21 g of polyester polycarbonate diol.
The number average molecular weight (based on JIS K 1577 method B) of the obtained polyester polycarbonate diol is 993, the acid value is 0.02 mg KOH / g, the weight average molecular weight is 2800, and the degree of dispersion is 2.1. Met. The viscosity is shown in Table 1.

Comparative Example 1
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 372.0 g (4.13 mol) of dimethyl carbonate, 195.6 g (1.66 mol) of 1,6-hexanediol, The ester exchange reaction was carried out while 186.8 g (1.79 mol) of 1,5-pentanediol and 0.05 g of titanium tetrabutoxide were charged while distilling off the mixture of methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring. It went for 10 hours. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 439.20 g of polycarbonate diol.
The obtained polycarbonate diol has a number average molecular weight (based on JIS K 1577, Method B) of 991, an acid value of 0.05 mg KOH / g, a weight average molecular weight of 2900, and a dispersity of 2.2. there were. The viscosity is shown in Table 1.

Comparative Example 2
In a 1000 ml glass round bottom flask equipped with a rectifying column, a stirrer, a thermometer, and a nitrogen introduction tube, 387.0 g (4.30 mol) of dimethyl carbonate, 185.2 g (1.57 mol) of 1,6-hexanediol, A transesterification reaction was conducted while charging 184.0 g (1.77 mol) of 1,5-pentanediol and 0.05 g of titanium tetrabutoxide while distilling off a mixture of methanol and dimethyl carbonate in a nitrogen stream under normal pressure and stirring. I went for 12 hours. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
Thereafter, the pressure was gradually reduced to 30 mmHg, and a transesterification reaction was further carried out at 180 ° C. for 10 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of the distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 422.01 g of polycarbonate diol.
The obtained polycarbonate diol has a number average molecular weight (based on JIS K 1577, Method B) of 1934, an acid value of 0.04 mg KOH / g, a weight average molecular weight of 5600, and a dispersity of 2.2. there were. The viscosity is shown in Table 1.

Application examples 1 to 4, comparative application examples 1 and 2
92.2 g of polyester polycarbonate diol of Example 1, 41.5 g of isophorone diisocyanate (IPDI), 23.1 g of 2-hydroxyethyl acrylate (HEA), 0.09 g of urethanization catalyst (ZrAcAc: zirconium acetylacetonate), paramethoxyphenol (Polymerization inhibitor) 0.16 g was charged and reacted to obtain urethane acrylate. The obtained urethane acrylate (UA) and 2-hydroxyethyl acrylate (HEA) were mixed at a weight ratio shown in Table 2 to obtain a composition of Application Example 1. Using the polyester polycarbonate diol of Examples 2 to 4 and the polycarbonate diol of Comparative Examples 1 and 2, compositions were similarly prepared. Table 2 shows the obtained urethane acrylate (UA) and the viscosity of the composition.

Urethane acrylate and 2-hydroxyethyl acrylate in each application example and comparative application example were mixed at a weight ratio of 0.8: 0.2, and Irgacure 819 (manufactured by BASF) was used as an initiator for 80 parts by weight of the mixture. 1 part by weight and 19 parts by weight of ethyl acetate as a solvent were added to obtain a coating agent.
About the obtained coating agent, the following was measured. The results are shown in Table 3.
Adhesiveness: The coating agent was applied to each substrate so that the film thickness was 0.07 mm after drying, dried at 80 ° C. for 30 minutes, and then cured at a cumulative light intensity of 1000 mJ / cm ² using a high-pressure mercury lamp, After leaving at room temperature for one day, 4 cm ² was cut into 100 × 10 × 10 squares with a cutter, and a cross-cut peel test was performed using a cellophane tape. Specifically, the cellophane tape was affixed and peeled a predetermined number of times, the number of remaining cells was counted, and the measurement results were shown as follows.
100/10 Remaining 100 squares after 10 peel tests 48/1 Remaining 48 squares after 1 peel test
0/1 One peel test, 0 mass remaining

ＡＢＳ：アクリロニトリル−ブタジエン−スチレン、
ＰＥＴ：ポリエチレンテレフタレート
ＥＰＤＭ：エチレン−プロピレン−ジエンゴム、
ＰＣ：ポリカーボネート

ABS: acrylonitrile-butadiene-styrene,
PET: polyethylene terephthalate EPDM: ethylene-propylene-diene rubber,
PC: Polycarbonate

  From the results in Table 3, it can be seen that when the polyester polycarbonate polyol of the present invention is used, a coating agent having high adhesion to EPDM can be obtained.

Moreover, the following was measured about the obtained coating agent. The results are shown in Table 4.
Solvent resistance: The coating agent was applied to the substrate so that the film thickness was 0.07 mm after drying, dried at 80 ° C. for 30 minutes, and then cured with a high-pressure mercury lamp at an integrated light quantity of 1000 mJ / cm ² . After leaving at room temperature for 1 day, absorbent cotton soaked with each solvent was left for 24 hours, wiped with a waste cloth, and visually evaluated.
○ After wiping off, there is no change in the coating film ○-After wiping off, there are traces or cloudiness of absorbent cotton. △ After wiping off, there is a slight floating

  From the results in Table 4, it can be seen that the polyester polycarbonate polyol of the present invention can provide a coating agent having not only inorganic acid resistance and organic acid resistance but also high neutral detergent resistance.

  By using the polyester polycarbonate polyol of the present invention as a raw material such as polyurethane resin or urethane acrylate, a coating film having excellent adhesion can be provided, and industrial utility is high.

Claims (13)

A polyester polycarbonate polyol containing a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a hydroxyl group at the molecular end,
The polyester polycarbonate polyol in which the repeating unit represented by the following formula (1) contains two or more repeating units represented by the following formula (3).

(In formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In the formula (2), R ² represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(In formula (3), n represents an integer of 2 to 20)   The polyester polycarbonate polyol according to claim 1, wherein the amount of the repeating unit represented by the formula (2) is 1 to 60 mol% in the total of the repeating units represented by the formula (1) and the formula (2). .   The polyester polycarbonate polyol of Claim 1 or 2 whose quantity of the repeating unit represented by Formula (3) is 60-100 mol% in the repeating unit represented by Formula (1). The repeating unit represented by Formula (3) is 2 or more types chosen from the group which consists of a repeating unit represented by Formula (4)-(7), The any one of Claims 1-3. Polyester polycarbonate polyol.

  The polyester polycarbonate polyol of Claim 4 whose repeating unit represented by Formula (3) is a repeating unit represented by Formula (5) and Formula (7).   The polyester polycarbonate polyol of Claim 5 whose quantity of the repeating unit represented by Formula (5) is 30-95 mol% in the repeating unit represented by Formula (5) and Formula (7).   The polyester polycarbonate polyol of Claim 4 whose repeating unit represented by Formula (3) is a repeating unit represented by Formula (6) and Formula (7).   The polyester polycarbonate polyol of Claim 7 whose quantity of the repeating unit represented by Formula (6) is 20-80 mol% in the repeating unit represented by Formula (6) and Formula (7). The repeating unit represented by formula (2) is at least one selected from the group consisting of repeating units represented by formulas (4 ′) to (7 ′). The polyester polycarbonate polyol described in 1.

  The polyester polycarbonate polyol according to claim 9, wherein the repeating unit represented by the formula (2) is a repeating unit represented by the formula (6 ').   The polyester polycarbonate polyol according to any one of claims 1 to 10, wherein the number average molecular weight is 500 to 5,000.   A polyurethane resin obtained by copolymerizing the polyester polycarbonate polyol according to any one of claims 1 to 11 and a polyisocyanate.   The urethane acrylate obtained by making the polyester polycarbonate polyol of any one of Claims 1-11, polyisocyanate, and a hydroxyl-containing (meth) acrylate react.