CN106661217B - Polycarbonate glycol - Google Patents

Abstract

The polycarbonate glycol of the present invention includes the repetitive unit and terminal hydroxyl indicated by following formula (A), and deuterochloroform is being measured as solvent, by tetramethylsilane as primary standard substance¹In H NMR, when the integrated value of the signal of 3.90~4.45ppm is set as 1000, the integrated value of 3.33~3.43ppm is 0.1~10.0.(in formula (A), R indicates that the bivalent aliphatic or clicyclic hydrocarbon of carbon number 3~15 can select one kind or two or more in total repetitive unit).

Description

Polycarbonate glycol

Technical field

The present invention relates to polycarbonate glycol.

Background technology

Known polycarbonate glycol is such as soft chain segment polyurethane, thermoplastic elastomer (TPE), as hydrolytic resistance, fast light The excellent raw material such as property, resistance to oxidation deterioration, heat resistance.However, when polycarbonate glycol is used for coating composition, need Viscosity height and a large amount of solvent.In turn, the intermolecular interaction of polycarbonate glycol is strong, therefore there are the additives such as pigment Dispersion stabilization difference problem.

In order to solve such unfavorable condition, various liquid polycarbonate glycol are disclosed.For example, it is excellent to disclose compatibility It is different, viscosity is low, in poor solvent soluble coating with polycarbonate glycol (for example, referring to patent document 1).In addition, open Makrolon/polyether block copolymer of lowering viscousity (for example, referring to patent document 2).On the other hand, it discloses high hard Degree and erasibility is excellent and tone and thermal stability, hydrophily it is excellent, for the useful makrolon of coating, coating agent Glycol (for example, referring to patent document 3).

Existing technical literature

Patent document

Patent document 1:Japanese Unexamined Patent Publication 2002-179787 bulletins

Patent document 2:Japanese Unexamined Patent Publication 2006-124485 bulletins

Patent document 3:Japanese Unexamined Patent Publication 2013-10949 bulletins

Invention content

Problems to be solved by the invention

However, the technology described in for patent document 1 and 2, has polyether structure in polycarbonate glycol molecule, Therefore there is a situation where that heat resistance, chemical reagent resistance are insufficient.

In addition, for technology described in Patent Document 3, as the dihydroxy compounds of raw material, including intramolecular has ether The compound of property oxygen atom, therefore there is a situation where that chemical reagent resistance is insufficient.

In this way, in previous technology, do not disclose can obtain pigment dispersion stabilization it is excellent and with heat resistance, The polycarbonate glycol of the film of chemical reagent resistance.

Therefore, the purpose of the present invention is to provide for example suitable for the constituent material as coating, bonding agent, and then as poly- The polycarbonate glycol of the raw material of urethane, thermoplastic elastomer (TPE) etc..More specifically, the purpose of the present invention is to provide as painting In the case of the constituent material of material, can obtain pigment dispersion stabilization it is excellent and with heat resistance, chemical reagent resistance Film polycarbonate glycol.

The solution to the problem

Further investigation is repeated in the present inventor to solve the above-mentioned problems, as a result, it has been found that with by following formula (A) table The polycarbonate glycol of the repetitive unit and terminal hydroxyl that show has specific structure, so as to reached purpose, completes this Invention.

That is, the composition of the present invention is as described below.

[1] a kind of polycarbonate glycol, it includes the repetitive unit and terminal hydroxyl that are indicated by following formula (A),

Deuterochloroform is being measured as solvent, by tetramethylsilane as primary standard substance¹In H-NMR, by 3.90 When the integrated value of the signal of~4.45ppm is set as 1000, the integrated value of 3.33~3.43ppm is 0.1~10.0.

(in formula (A), R indicates that the bivalent aliphatic or clicyclic hydrocarbon of carbon number 3~15 can select in total repetitive unit It is one kind or two or more.)

[2] polycarbonate glycol according to above-mentioned [1], wherein the 90 of the repetitive unit indicated by formula (A)~ 100% is at least one unit in the group being made of the repetitive unit indicated by following formula (B)~(D).

[3] polycarbonate glycol according to above-mentioned [1] or [2], wherein end OH base ratios be 95.0~ 99.9%.

[4] the polycarbonate glycol composition according to any one of [1]~[3], wherein when being measured by ICP The content of at least one kind of metallic element is 0.0001~0.05 weight % in the group being made of titanium, yttrium, tin and zirconium.

[5] polycarbonate glycol according to any one of above-mentioned [1]~[4], wherein titanium when being measured by ICP, The total content of ytterbium, tin and zirconium is 0.0001~0.05 weight %.

[6] polycarbonate glycol according to any one of [1]~[5], wherein the content of P when being measured by ICP For 0.0001~0.05 weight %.

[7] polycarbonate glycol according to any one of above-mentioned [1]~[6], wherein amount of moisture be 10~ 500ppm。

[8] a kind of coating composition, it includes polycarbonate glycol described in any one of above-mentioned [1]~[7] and organic Polyisocyanates.

[9] a kind of coating composition, it includes described in any one of above-mentioned [1]~[7] polycarbonate glycol with it is organic Carbamate prepolymer obtained from polyisocyanates reaction, the carbamate prepolymer have terminal isocyanate group.

[10] a kind of coating composition it includes the polycarbonate glycol made described in any one of above-mentioned [1]~[7], has Polyurethane resin obtained from machine polyisocyanates and chain extender reaction.

[11] a kind of water system coating composition, it includes the makrolon two made described in any one of above-mentioned [1]~[7] Polyurethane resin obtained from alcohol, organic multiple isocyanate and chain extender reaction.

[12] a kind of thermoplastic polyurethane uses the polycarbonate glycol described in any one of above-mentioned [1]~[7] and has Machine polyisocyanates and obtain.

The effect of invention

In the case that the polycarbonate glycol of the present invention is used as the constituent material of coating, the dispersion stabilization for obtaining pigment is excellent Different and film with heat resistance, chemical reagent resistance.With these characteristics, therefore the polycarbonate glycol of the present invention can be with Suitably it is used as the constituent material of coating.

Description of the drawings

Fig. 1 is the polycarbonate glycol obtained by embodiment 4¹H-NMR analysis charts.

Specific implementation mode

Hereinafter, for mode for carrying out the present invention (hereinafter, brief note makees " present embodiment ".) carry out in detail It is bright.It should be noted that the present invention is not limited to the following embodiments and the accompanying drawings, various changes can be implemented within the scope of its subject matter Shape.

<Polycarbonate glycol>

The polycarbonate glycol of present embodiment includes the repetitive unit and terminal hydroxyl indicated by following formula (A).

In formula (A), R indicates that the bivalent aliphatic or clicyclic hydrocarbon of carbon number 3~15 can select 1 in total repetitive unit Kind or two or more.In formula (A), in the case that R is the bivalent aliphatic hydrocarbon without side chain, the chemical reagent resistance of polyurethane, Mechanical strength is got higher, therefore preferably, more preferable in the case of bivalent aliphatic hydrocarbon of the R for carbon number 4~9.

In addition, for the polycarbonate glycol of present embodiment, the repetitive unit indicated by above-mentioned formula (A) 90~ In the case that 100% is at least one unit in the group being made of the repetitive unit indicated by following formula (B)~(D), obtain To the good film of balance of chemical reagent resistance and mechanical strength, therefore preferably.In turn, the makrolon two of present embodiment The 90~100% of the repetitive unit of alcohol indicated by above-mentioned formula (A) are the repetitive unit indicated by following formula (C) and by following In the case of the repetitive unit that formula (D) indicates, even if it is also liquid in a low temperature of -5 DEG C, therefore more preferably.

It should be noted that in the polycarbonate glycol of present embodiment, by the ratio for the repetitive unit that formula (A) indicates From the viewpoint of heat resistance, hydrolytic resistance, preferably 95 moles of % or more and 100 mole of % are hereinafter, more preferably 97 rub % or more and 100 mole of % of that is hereinafter, be still more preferably 99 moles of % or more and 100 mole of % or less.

It is liquid under the preferred room temperature of polycarbonate glycol of present embodiment.The polycarbonate glycol of present embodiment is used as In the case of the constituent of coating, even if being used for transparent coating, it is also few that there is a situation where gonorrhoeas, therefore purposes is less subject to Limitation.It should be noted that in present embodiment, liquid refer to would be heated to 80 DEG C of polycarbonate glycol put into it is transparent Sample bottle, although seldom there are still flowings with being visually observed when the state being cooled to room temperature is transparent and inclination sample bottle The state of property.

For the polycarbonate glycol of present embodiment, make using deuterochloroform as solvent, by tetramethylsilane (TMS) On the basis of substance and measure¹In H-NMR spectrum, when the integrated value of the signal of 3.90~4.45ppm is set as 1000,3.33~ The integrated value (hereinafter referred to as " integrated value ratio ") of the signal of 3.43ppm is 0.1~10.0.Aforementioned¹In H-NMR spectrum, push away The signal for surveying 3.90~4.45ppm is the signal for the methylene for being bonded to carbonic ester, and the signal of 3.33~3.43ppm is to be bonded to The signal of the methylene of the oxygen of ether.Therefore, in the polycarbonate glycol of present embodiment, which, which becomes, indicates certain Repetitive unit contained in can be estimated as specific ether structure amount index.The polycarbonate glycol of present embodiment If the integrated value ratio is 0.1 or more, in the case of the constituent as coating, the dispersion for improving the additives such as pigment is steady It is qualitative, the integrated value than if 10.0 hereinafter, can then obtain having heat resistance, chemical reagent resistance film.In turn, for The polycarbonate glycol of present embodiment, the integrated value is than preferably 0.3~8.0, more preferably 0.5~5.0.For this implementation The polycarbonate glycol of mode, when which is in aforementioned range, in the case of the constituent for being used as coating, more into one Step improves the dispersion stabilization of pigment, can obtain the film with high-fire resistance, chemical reagent resistance, flatness.Another party Face, such as ethylene carbonate is used as carbonate source, in the item for being present in excess ethylene carbonate relative to diol starting materials When being reacted with 200 DEG C or more of high temperature under part, the poly- carbon in the molecule with the ether structure from ethylene carbonate is obtained Acid esters glycol.The polycarbonate glycol¹In H-NMR spectrum, the signal from ether structure can be estimated as in 3.45~3.48ppm Place occurs.It is different from the peak used in the present embodiment for calculating integral value ratio.In addition, usually using the poly- carbonic acid In the case that esterdiol is polymerized to polyurethane, heat resistance, weatherability reduce.

The end OH base ratios of the polycarbonate glycol of present embodiment are preferably 95.0~99.9%.End OH bases ratio Example if 99.9% hereinafter, will not then generate fine high molecular weight gel etc. and the flatness of film coated surface is made to reduce, the end It holds OH bases ratio if 95.0% or more, then will not promote the solidification of film and remain slippery feeling in film coated surface, therefore is excellent Choosing.End OH base ratios are more preferably 97.0~99.9%, are still more preferably 98.0~99.9%.

It should be noted that in the present embodiment, end OH bases ratio defines as described below.By 70g~100g Polycarbonate glycol under 0.4kPa pressure below, the temperature that is heated to 160 DEG C~200 DEG C be stirred, obtain quite In the fraction i.e. initial stage fraction of about 1g (0.7~2g) of about 1~2 weight % of the polycarbonate glycol.Make obtained fraction It is dissolved in the ethyl alcohol of about 100g (95~105g) and solution is made to recycle.Refer to that gas-chromatography point is carried out to the solution of recycling It analyses (hereinafter also referred to " GC analyses "), is calculated by following formula (1) according to the value of the peak area of obtained chromatography End OH base ratios.It should be noted that GC analysis use be equipped with DB-WAX (U.S.'s J＆W corporations) 30m as column, The gas-chromatography 6890 (U.S.'s Hewlett-Packard Company systems) that 0.25 μm of film thickness uses hydrogen flame for detector Ionization detector (FID) carries out.For the heating process of column, it is set as being warming up to after 250 DEG C from 60 DEG C with 10 DEG C/min 15 minutes processes are kept with the temperature.The identification at each peak in GC analyses is carried out using following GC-MS devices.GC devices make Use 6890 (U.S.'s Hewlett-Packard Company systems) being equipped with as the DB-WAX (U.S.'s J＆W corporations) of column. In GC devices, 220 DEG C are warming up to for 10 DEG C/min from 40 DEG C of initial stage temperature with heating rate.MS devices use Auto-massSUN (Japanese JEOL systems).In MS devices, with ionizing voltage 70eV, scanning range m/z=10~500, gain of photomultiplier (photomultiplier gain) 450V is measured.

End OH bases ratio (%)=A × 100 B ÷ (1)

A：Include the summation of the peak area of the alcohols (not including ethyl alcohol) of glycol

B：The summation of the peak area of glycol

End OH base ratios correspond to the ratio of total terminal groups of OH fiduciary point polycarbonate glycol.That is, it is as noted above, it will Polycarbonate glycol is under 0.4kPa pressure below, when being heated to 160 DEG C~200 DEG C of temperature, the end of polycarbonate glycol End part is distillated in a manner of alcohols (with reference to following formula (a)).It is not particularly limited as the alcohols distillated, for example, can arrange Enumerate the carbon that impurity, methanol etc. contained in the raw materials such as the glycol used in raw material, cyclohexanediol, 1,5- hexylene glycols are originated from raw material The monohydric alcohol of ester compound, the monohydric alcohol with unsaturated hydrocarbons generated by the side reaction in polymerizeing.

(in formula (a), X is-R²- OH or-R², R¹And R²Indicate hydrocarbon.)

The ratio of the glycol in total aldehydes in the fraction is end OH base ratios.

For the manufacturing method of the polycarbonate glycol of present embodiment, remove above-mentioned integrated value than controlling in specific model It is not particularly limited other than method in enclosing.

For example, Schnell works, Polymer Review's volumes 9 can be enumerated, described in p9~20 (1994) Various methods.It should be noted that being described below above-mentioned integrated value than controlling method in a specific range.

The number-average molecular weight of the polycarbonate glycol of present embodiment is preferably 300~5000.The number of polycarbonate glycol Average molecular weight is if 300 or more, then the low-temperature characteristics of obtained polyurethane is good.If the number-average molecular weight of polycarbonate glycol For 5000 hereinafter, when being then used as the constituent material of coating, coating solid constituent concentration etc. is unrestricted, in addition obtained poly- ammonia The molding processibility of ester does not also reduce, therefore preferably.The number-average molecular weight of polycarbonate glycol still more preferably be 450~ 3000。

It should be noted that in the present embodiment, the number-average molecular weight of polycarbonate glycol can pass through aftermentioned reality The method described in example is applied to measure.

In the case that the polycarbonate glycol of present embodiment manufactures glycol and carbonate products as raw material, such as It is upper described, it is, for example, possible to use Schnell works, Polymer Review's volumes 9, each described in p9~20 (1994) Kind of method manufactures.

The glycol used as raw material is not particularly limited, for example, can enumerate 1,3-PD, 1,4-butanediol, 1,5- pentanediols, 1,6-HD, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- dodecanediols, 1, 11- undecanes, 1,12- dodecanediols, 1,13- tridecyls glycol, 1,14- myristyls glycol, 1,15- 15 Alkyl diol etc. does not have the glycol of side chain；2- methyl-1s, 8- ethohexadiols, 2- ethyls -1,6-HD, 2- methyl-1s, 3- third Glycol, 3- methyl-1s, 5- pentanediols, 2,4- dimethyl -1,5- pentanediols, 2,4- diethyl -1,5- pentanediols, 2- butyl -2- Ethyl -1,3- propylene glycol, 2,2- dimethyl -1,3- propylene glycol etc. have the glycol of side chain；1,4 cyclohexane dimethanol, 2- are bis- The cyclic diols such as (4- hydroxy-cyclohexyls)-propane, 1,4- cyclohexanediols.The one kind or two or more of the glycol may be used as poly- carbonic acid The raw material of esterdiol.Never have in the glycol of side chain and is used as the raw material of polycarbonate glycol with one kind or two or more glycol In the case of, the chemical reagent resistance of film, mechanical strength are got higher, therefore preferably, from 1,4-butanediol, 1,5-PD, 1,6- The one kind or two or more original as polycarbonate glycol is used in hexylene glycol, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols The case where material is preferred.2 kinds of glycol selected from 1,4- butanediols, 1,5- pentanediols, 1,6-HD are used as poly- carbonic acid The case where raw material of esterdiol is still more preferably.1,5- pentanediols, 1,6-HD are particularly preferably used as poly- carbonic acid The case where raw material of esterdiol.

In the manufacture of the polycarbonate glycol of present embodiment using glycol of more than two kinds as raw material in the case of, The ratio of these raw materials is not particularly limited, but preferably sets the ratio of raw material used so that obtained polycarbonate glycol is normal Lower temperature is liquid.In the case that 2 kinds of glycol are used as raw material, input is preferably set between 20/80~80/20 with molar ratio computing Amount.If in the range, obtained polycarbonate glycol is liquid.It is still more preferably if being set as 30/70~70/30 , if being set as 40/60~60/40, even if also it is liquid at 0 DEG C or less, therefore more preferably.

In turn, in the range of not damaging the performance of polycarbonate glycol of present embodiment, there are 3 in 1 molecule The compound of the above hydroxyl, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythrite etc. can be used as poly- The raw material of carbonate diol.Compound with 3 or more hydroxyls in 1 molecule is excessive as the raw material of polycarbonate glycol Ground is in use, generating crosslinking in the polymerisation of makrolon and causing gelation.Therefore, even if will have 3 in 1 molecule In the case that the compound of a above hydroxyl is used as the raw material of polycarbonate glycol, the compound is relative to as makrolon two The molal quantity of the glycol of the raw material of alcohol is preferably set to 0.1~5 mole of %.The ratio is more preferably 0.1~1 mole of %.

The example of the carbonic ester of raw material as the polycarbonate glycol as present embodiment is not particularly limited, example Such as, the dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate can be enumerated；Carbonic acid two The diaryl carbonates such as phenyl ester；Ethylene carbonate, trimethylene carbonate, 1,2- propylene carbonates, 1,2- butylidene carbonic acid Alkylene carbonates such as ester, 1,3- carbonates, 1,2- pentylidene carbonic esters etc..It can be by a kind or 2 kinds among them Above carbonic ester is used as the raw material of polycarbonate glycol.From be easy to get, the condition of polymerisation set difficulty sight It selects and sets out, it is preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, ethylene carbonate.

Catalyst is preferably added in the manufacture of the polycarbonate glycol of present embodiment.It is not limited especially as the catalyst It is fixed, for example, the alkali metal such as lithium, sodium, potassium can be enumerated；The alkoxide of the alkaline-earth metal such as magnesium, calcium, strontium, barium, hydride, oxide, The alkaline alkali metal salt and alkali salt of amide, carbonate, hydroxide, nitrogenous borate and then organic acid.In addition, Be not particularly limited as aforementioned catalytic agent, for example, can enumerate aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, Germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, the metal of ytterbium, salt, alkoxide, Organic compound.It can select using one or more catalyst among them.Using sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead, In the case of one or more catalyst among the metal of ytterbium, salt, alkoxide, organic compound, polycarbonate glycol is carried out well Polymerization, for using the influence of the urethane reaction of obtained polycarbonate glycol also few, therefore it is preferred that.As aforementioned Catalyst, still more preferably use titanium, ytterbium, tin, zirconium the case where.

It can also include above-mentioned catalyst in the polycarbonate glycol of present embodiment.In the makrolon of present embodiment In glycol, the content of the catalyst is preferably 0.0001~0.05 weight to use the gauge of metallic element that ICP is measured Measure %.The content of the catalyst then carries out the polymerization of polycarbonate glycol well if aforementioned range, for obtained by using Polycarbonate glycol urethane reaction influence it is also few.Gold of the content of the catalyst to use ICP to be measured The gauge for belonging to element is more preferably 0.0005~0.02 weight %.

It is when being measured by ICP, selected from by titanium, ytterbium, tin and zirconium group for the polycarbonate glycol of present embodiment At group at least one kind of metallic element content be preferably 0.0001~0.05 weight %, more preferably 0.0005~0.02 Weight %.In addition, for the polycarbonate glycol of present embodiment, when being measured by ICP, titanium, ytterbium, tin and zirconium Total content is preferably 0.0001~0.05 weight %, more preferably 0.0005~0.02 weight %.

It should be noted that in the present embodiment, the content of the metallic element in polycarbonate glycol can be by rear The method of embodiment record is stated to measure.

For the polycarbonate glycol of present embodiment, for example, in the case of the raw material as polyurethane, phosphatization is preferably used Object is closed to handle the catalyst used in the manufacture of polycarbonate glycol.It is not particularly limited as phosphorus compound, for example, It can enumerate：Trimethyl phosphate, triethyl phosphate, tributyl phosphate, di(2-ethylhexyl)phosphate (2- ethylhexyls) ester, triphenyl phosphate, The phosphotriesters such as tricresyl phosphate, cresyl diphenyl phosphate；Acid phosphate methyl esters, acid phosphate ester, acid phosphate Propyl ester, acidic isopropyl phosphate, acid butyl phosphate, acid phosphate lauryl, acid phosphate stearyl ester, acid phosphate 2- ethyls Own ester, acid phosphate isodecyl base ester, acid phosphate butoxyethyl, acid phosphate grease, acid phosphate lignocerane base ester, acid Formula phosphoric acid glycol ester, 2-hydroxyethyl methacrylate base phosphate ester acid, dibutylphosphoric acid ester, phosphoric acid mono-n-butylester, mono phosphoric acid ester The acid phosphoric acid esters such as bis- (2- ethylhexyls) esters of isodecyl base ester, phosphoric acid；Triphenyl phosphite, trisnonyl phenyl phosphite, phosphorous Sour front three phenyl ester, triethyl phosphite, phosphorous acid three (2- ethylhexyls) ester, three decyl ester of phosphorous acid (ト リ デ シ Le ホ ス Off ァ イ ト), trilauryl, phosphorous acid three (tridecyl) ester, trioleyl phosphite, phosphorous acid diphenyl list (2- second Base hexyl) ester, phosphorous acid diphenyl list decyl ester, phosphorous acid diphenyl (single decyl) ester, trilauryl phosphite, phosphorous acid two Bis- (2- ethylhexyls) esters of ethyl ester, phosphorous acid, phosphorous acid dilauryl, phosphorous acid two (octadecylene base) ester, diphenyl phosphite, Tetraphenyl dipropyleneglycol, bis- (decyl) pentaerythritol diphosphites, phosphorous acid three (octadecyl) ester, two Asias The phosphorous acid esters such as phosphoric acid pentaerythrite two (octadecyl) ester, phosphorous acid three (2,4- di-tert-butyls) ester；And then phosphoric acid, Asia Phosphoric acid, hypophosphorous acid etc..

It can also include phosphorus compound in the polycarbonate glycol of present embodiment.In the makrolon two of present embodiment In alcohol, the content of phosphorus compound is preferably 0.0001~0.05 weight to use the content meter of P elements (P) that ICP is measured Measure %.For the polycarbonate glycol of present embodiment, the content of phosphorus compound is if aforementioned range, for example, being used as polyurethane Raw material in the case of, in the manufacture reaction of the polyurethane, the catalysis that uses in polycarbonate glycol manufacture can not be influenced Agent, in turn, influence of the phosphorus compound to the manufacture reaction of polyurethane, the physical property generation of reaction product are also few.Present embodiment In polycarbonate glycol, the content of the P elements (P) when being measured by ICP is more preferably 0.0005~0.02 weight %.

In the polycarbonate glycol of present embodiment, amount of moisture is preferably 10~500ppm.For the poly- of present embodiment Carbonate diol, amount of moisture is if 500ppm hereinafter, gonorrhoea then will not be generated with reacting for isocyanates by water, be preferred. In addition, the amount of moisture of the polycarbonate glycol of present embodiment if 10ppm or more, then can obtain the high film of the transparency, Therefore it is preferred that.Presumption is this is because can be estimated as the part of specific ether structure and hydrone forms certain knot specified in the application Zoarium, to be improved with the compatibility of solvent, polycarbonate glycol equably exists in a solvent.The amount of moisture if 10~ 250ppm, then the effect become significantly, then still more preferably if 15~150ppm.

It should be noted that in the present embodiment, the amount of moisture of polycarbonate glycol can be by aftermentioned embodiment The method of record is found out.

In the specific example of the manufacturing method of the polycarbonate glycol of present embodiment described below.Present embodiment is gathered Being made without for carbonate diol is particularly limited to, for example, can be divided into for 2 stages to carry out.With molar ratio (glycol：Carbonic ester) example Such as 20：1~1：10 ratio mixes glycol and carbonic ester, and it is anti-to carry out the first stage at 100~250 DEG C under normal or reduced pressure It answers.It, can be by the methanol of generation with the mixture with dimethyl carbonate in the case of using dimethyl carbonate as carbonic ester Form removal obtains low-molecular polycarbonate glycol.It, can be by life in the case of using diethyl carbonate as carbonic ester At ethyl alcohol removed in the form of the mixture with diethyl carbonate and obtain low-molecular polycarbonate glycol.In addition, conduct In the case that carbonic ester uses ethylene carbonate, the ethylene glycol of generation can be gone in the form of the mixture with ethylene carbonate It removes and obtains low-molecular polycarbonate glycol.Then, second stage reaction is following reaction：By the reaction of aforementioned first stage Product is heated with 160~250 DEG C under reduced pressure, removes unreacted glycol and carbonic ester, and make low-molecular polycarbonate Glycol is condensed, and obtains the reaction of the polycarbonate glycol of regulation molecular weight.

In the present embodiment, as by integrated value than controlling method in aforementioned range, for example, it is preferable to aforementioned the In one elementary reaction, increases the molar ratio of glycol and improve reaction temperature.Molar ratio (the glycol of glycol and carbonic ester：Carbonic acid Ester) it is more preferably 81：19~68：32, still more preferably it is 78：22~73：27.Reaction temperature is preferably 150~250 DEG C, More preferably 180~250 DEG C.It is preferred that 80% or more of aforementioned reaction time first stage is carried out under above-mentioned reaction temperature, If carrying out 90% or more at above-mentioned temperature more preferably.

And then the ether diol compound indicated by following formula (E) can also be added as raw material glycol.In formula (E), n and Integer that m is 3~12 can be n=m or n ≠ m.In the case of the integer that n and m is 4~12, obtain having resistance to Hot, chemical reagent resistance film, therefore it is preferred that, the dispersion stabilization of pigment is excellent in the case of the integer that n and m are 4~6 It is different, therefore still more preferably.

HO-(Ch₂)_n-O-(CH₂)_m-OH (E)

The ether diol compound can also be put into together with glycol and carbonic ester to manufacture polycarbonate glycol or can also It adds the ether diol compound in polycarbonate glycol, ether structure is imported with ester exchange reaction in polycarbonate glycol. In the case of adding the ether diol compound in polycarbonate glycol, with 100~250 DEG C of temperature into one preferably after addition Step heat treatment.

In addition, the end OH bases ratio of the polycarbonate glycol used in present embodiment can be according to miscellaneous in raw material The manufacturing conditions such as matter, temperature and time and then use dialkyl carbonate and/or diaryl carbonates in the carbonic ester as raw material 1 method is selected according to conditions such as the input ratios of glycol and carbonic ester in raw material or make its proper combination in the case of ester To adjust.As the carbonic ester of raw material, in the case of using dialkyl carbonate and/or diaryl carbonate, and as target Polycarbonate glycol molecular weight accordingly using stoichiometric amount or ratio proximate to it input as raw material glycol and Carbonic ester and when making its reaction is many case where the end remaining of polycarbonate glycol is originated from the alkyl of carbonic ester, aryl.Cause This, 1.01~10 times of stoichiometric amount are for example set as by the amount of the glycol relative to carbonic ester in raw material, to poly- carbonic acid Esterdiol can reduce end alkyl, terminal aryl group and increase terminal hydroxyl.And then due to side reaction, the end of polycarbonate glycol End becomes vinyl, or for example in the case where using dimethyl carbonate as carbonic ester, becomes methyl ester, methyl ether.Usually For, reaction temperature is higher, the reaction time is longer, and side reaction more easy tos produce.

<Purposes>

The polycarbonate glycol of present embodiment can be used as poly- in addition as coating, the constituent material of bonding agent The raw material of urethane, thermoplastic elastomer (TPE) may further be used for the purposes such as the modifying agent of polyester, polyimides.Especially this reality In the case of constituent material of the polycarbonate glycol as coating for applying mode, the stably dispersing of the additives such as pigment can be obtained Property good, the heat resistance and excellent coating of chemical reagent resistance.

The thermoplastic polyurethane of present embodiment can be obtained using above-mentioned polycarbonate glycol and polyisocyanates.

The coating composition of present embodiment includes above-mentioned polycarbonate glycol and organic multiple isocyanate.

In addition, the coating composition of present embodiment, which preferably comprises, makes above-mentioned polycarbonate glycol and organic polyisocyanic acid Carbamate prepolymer obtained from ester reaction, the carbamate prepolymer have terminal isocyanate group.

In turn, the coating composition of present embodiment more preferably includes to make above-mentioned polycarbonate glycol, organic polyisocyanate cyanogen Polyurethane resin obtained from acid esters and chain extender reaction still more preferably includes to make above-mentioned polycarbonate glycol, have Polyurethane resin obtained from machine polyisocyanates and chain extender reaction, water system coating composition.

It as used organic multiple isocyanate, is not particularly limited, for example, 2,4- toluene diisocyanates can be enumerated Acid esters, 2,6- toluene di-isocyanate(TDI)s and its mixture (TDI), crude TDI, diphenyl methane -4,4 '-diisocyanate (MDI), crude MDI, naphthalene -1,5- diisocyanate (NDI), 3,3 '-dimethyl -4,4 '-diphenylene diisocyanate, poly- Asia Aromatic series two is different well known to methyl polphenyl isocyanate, xylylene diisocyanate (XDI), phenylene vulcabond etc. Cyanate, 4,4 '-methylene-bis-cyclohexyl diisocyanates (hydrogenation MDI), hexamethylene diisocyanate (HMDI), different Fo Er Aliphatic diisocyanate well known to ketone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenation XDI) etc. and these The modified product of isocyanuric acid esterification, the carbodiimidization of isocyanates are modified product, biuretized modified product etc..These organic polyisocyanates Cyanate, which can be used alone, can also be applied in combination two or more.In addition, these organic multiple isocyanates can with end-capping reagent and Isocyanate group is covered to use.

It, can be according to it is expected used as copolymerization in addition, in the reacting of polycarbonate glycol and organic multiple isocyanate The chain extender of synthesis point.It is not particularly limited as chain extender, it is, for example, possible to use the common chain extender in polyurethane field, That is water, low molecular polylol, polyamines etc..As the example of chain extender, be not particularly limited, for example, can enumerate ethylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, neopentyl glycol, 1,10- decanediols, 1,1- hexamethylenes two The low molecules such as methanol, 1,4 cyclohexane dimethanol, benzene dimethanol, bis- (to hydroxyl) hexichol, bis- (p-hydroxybenzene) propane are polynary Alcohol；Ethylenediamine, hexamethylene diamine, isophorone diamine, xylylene diamine, diphenyl diamine, diaminodiphenyl-methane Equal polyamines.These chain extenders, which can be used alone, can also be applied in combination two or more.

The method of coating composition (coating) as manufacture present embodiment can use well known manufacturer in field Method.For example, the coating host agent and include that mixing is obtained by above-mentioned polycarbonate glycol before it will apply can be manufactured The double-formulation solvent system coating composition of the curing agent of machine polyisocyanates；Including make above-mentioned polycarbonate glycol with it is organic more The one-pack type solvent system coating group of carbamate prepolymer with isocyanates terminal groups obtained from isocyanates reaction Close object；Including making polyurethane resin obtained from above-mentioned polycarbonate glycol, organic multiple isocyanate and chain extender reaction One-pack type solvent system coating composition；Or one-pack type water system coating composition.

In the coating composition (coating) of present embodiment, for example, curing accelerator can be added according to various uses (catalyst), filler, dispersant, fire retardant, dyestuff, organic or inorganic pigment, releasing agent, fluidity regulator, plasticizer, Antioxidant, ultra-violet absorber, light stabilizer, antifoaming agent, levelling agent, colorant, solvent etc..

It is not particularly limited as pigment, for example, titanium dioxide, zinc oxide, iron oxide, calcium carbonate, sulphur can be enumerated The inorganic pigments such as sour barium, chrome yellow, clay, talcum, carbon black, azo system, diazonium system, condensation azo system, thioindigo system, indanthrone (indanthrone) system, anthraquinone system, benzimidazole system, phthalocyanine system, isoindolinone system, be, quinacridone, dioxanes The organic pigments such as system, diketopyrrolopyrrolecocrystals system.

It is not particularly limited as curing accelerator, for example, dibutyltin diacetate, two sad dibutyl can be enumerated Tin, dibutyl tin laurate, triethylamine, diethanol amine, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene sulfonic acid etc..

It is not particularly limited as ultra-violet absorber, for example, benzophenone series, enumerate BTA system, cyanogen can be enumerated Base acrylic ester, salicylate system, oxanilide system.As ultra-violet stabilizer, the amine compound that is obstructed can be enumerated.

Solvent as coating is not particularly limited, for example, can enumerate dimethylformamide, diethylformamide, Dimethylacetylamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dioxanes, cyclohexanone, benzene, first Benzene, dimethylbenzene, ethyl cellosolve, ethyl acetate, butyl acetate, ethyl alcohol, isopropanol, n-butanol, water etc..These solvents can make With a kind or it is used in mixed way a variety of.

The method of thermoplastic polyurethane as manufacture present embodiment is not particularly limited, and can use and be led in polyurethane The technology of well known polyurethane-reinforcement reaction in domain.For example, by above-mentioned polycarbonate glycol and organic multiple isocyanate in air Pressure makes its reaction at room temperature~200 DEG C, so as to manufacture thermoplastic polyurethane.It, can be in the case of using chain extender From reaction initially addition, can also on the way be added from reaction.For the manufacturing method of the thermoplastic polyurethane of present embodiment, example Such as, it is referred to U.S. Patent No. 5070173.

In polyurethane-reinforcement reaction, well known polymerization catalyst, solvent can be used.Used polymerization catalyst does not have It is particularly limited to, for example, dibutyl tin laurate can be enumerated.

It is steady that heat stabilizer (such as antioxidant), light stabilizer etc. are preferably added in the thermoplastic polyurethane of present embodiment Determine agent.In addition it is also possible to add plasticizer, inorganic filler, lubricant, colorant, silicone oil, foaming agent, fire retardant etc..

Embodiment

Then the present invention is illustrated by embodiment and comparative example.

Embodiment below is not carried out to the scope of the present invention any to exemplify the embodiment of the present invention and record It limits.

In embodiment below and comparative example, the physics value shown is measured with following methods.

1. the integrated value of polycarbonate glycol than decision (¹H-NMR)

The integrated value ratio in polycarbonate glycol is determined as described below.

First, sample is dissolved into deuterochloroform (Aldrich Corporation systems), obtains 3 weight/vol%'s Solution.Tetramethylsilane (TMS) is added in terms of chemical shift reference in the solution, Bruker is used for obtained solution The Bio Spin Avance600 of corporation are measured¹H-NMR.In the measurement, it is set as resonant frequency：600.13MHz, pulse it is wide Degree：30 °, stand-by period：3 seconds, cumulative frequency：128 times, tms signal is set as 0ppm, is obtained¹H-NMR spectrum.For poly- carbon Integrated value ratio in acid esters glycol, using in aforementioned measurement¹The product of obtained in H-NMR, 3.90~4.45ppm signal The integrated value of the signal of score value and 3.33~3.43ppm is found out with following formula (2).

Integrated value ratio=E/D × 1000 (2)

D：The integrated value of the signal of 3.90~4.45ppm

E：The integrated value of the signal of 3.33~3.43ppm

2. the analysis (ICP) containing ingredient in polycarbonate glycol

Each ingredient contained in analysis polycarbonate glycol as described below.First, sample is weighed into Teflon (registrations Trade mark) system decomposition container in, be added high-purity nitric acid (Northeast chemistry system), use microwave decomposition device (Milestone General, Inc. system, ETHOS TC) it is decomposed.Sample is completely broken down, and obtained decomposed solution is water white transparency. Pure water is added in decomposed solution, detection liquid is made.For obtained detection liquid, inductively coupled plasma analytical equipment is used (Thermo Fisher Scientific K.K. systems, iCAP6300Duo), the titer based on each element is quantified.

3. the decision of the OH terminal groups ratios of polycarbonate glycol

The end OH base ratios in polycarbonate glycol are determined as described below.First, it is measured in the eggplant type flask of 300ml Take the polycarbonate glycol of 70g~100g.Using be connected with fraction recycling collection ball rotary evaporator, 0.4kPa with Under pressure under, with about 180 DEG C of heating bath the polycarbonate glycol in aforementioned eggplant type flask heated, stirred, receiving The fraction for about 1~2 weight % for being equivalent to the polycarbonate glycol, the initial stage fraction of i.e. about 1g (0.7~2g) are obtained in collection ball. So that obtained fraction is dissolved in the ethyl alcohol of about 100g (95~105g), solution is made to recycle.To the solution of recycling into Promoting the circulation of qi analysis of hplc (hereinafter referred to as " GC analyses "), according to the value of the peak area of obtained chromatography, by following formula (1) the end OH base ratios in polycarbonate glycol are calculated.It should be noted that GC analyses use the DB- being equipped with as column (the U.S. Hewlett-Packard Company of gas-chromatography 6890 of WAX (U.S.'s J＆W corporations) 30m, 0.25 μm of film thickness System), detector is carried out using flame ionization ditector (FID).The heating process of column be set as with 10 DEG C/min from 60 DEG C are warming up to after 250 DEG C, and 15 minutes processes are kept with the temperature.The identification at each peak in GC analyses uses following GC- MS devices carry out.GC devices use the 6890 (U.S. Hewlett- for being equipped with the DB-WAX (U.S.'s J＆W corporations) as column Packard Company systems).In GC devices, 220 DEG C are warming up to from initial stage temperature for 40 DEG C with 10 DEG C/min of heating rate.MS Device uses Auto-massSUN (Japanese JEOL systems).In MS devices, with ionizing voltage 70eV, scanning range m/z=10 ~500, gain of photomultiplier 450V is measured.

End OH bases ratio (%)=A × 100 B ÷ (1)

A：Include the summation of the peak area of the alcohols (not including ethyl alcohol) of glycol

B：The summation of the peak area of glycol

4. the decision of the composition of polycarbonate glycol

The composition of polycarbonate glycol determines as described below.First, 1g samples are measured in the eggplant type flask of 100ml Product are added ethyl alcohol 30g, potassium hydroxide 4g, obtain mixture.Obtained mixture is carried out 1 hour in 100 DEG C of oil bath Heating.After aforementioned mixture is cooled to room temperature, 1~2 drop is added to as the phenolphthalein of indicator in aforementioned mixture, is used Hydrochloric acid is neutralized.Later, aforementioned mixture is subjected to cooling in 3 hours with refrigerator, after filtering removes the salt of precipitation, to filtrate Gas-chromatography (GC) is carried out to analyze.It should be noted that GC analyses use DB-WAX (the J＆W companies of the U.S. being equipped with as column System) 30m, 0.25 μm of film thickness gas-chromatography GC14B (Shimadzu Seisakusho Ltd.'s system), by diethylene glycol diethylester be used as internal standard, inspection Device is surveyed to carry out using flame ionization ditector (FID).The heating process of column be set as keeping at 60 DEG C 5 minutes after with 10 DEG C/min of processes for being warming up to 250 DEG C.Based on the area value of glycol obtained from being analyzed as GC, makrolon two is determined The composition of alcohol.

5. the decision of the number-average molecular weight of polycarbonate glycol

For the number-average molecular weight of polycarbonate glycol, using acetic anhydride and pyridine, based on molten with the ethyl alcohol of potassium hydroxide " neutralization titration (the JIS K0070-1992) " that liquid is titrated determines hydroxyl value (OH values), is calculated using following formula (3).

Number-average molecular weight=2/ (value × 10 OH^-3/56.1) (3)

6. the confirmation of the character of polycarbonate glycol

It would be heated to 80 DEG C of polycarbonate glycol to put into transparent sample bottle, visually observe the shape being cooled to room temperature State.Although will be transparent and when tilting sample bottle less but there are still the case where mobility to be expressed as liquid, by opaque or Even if tilting sample bottle, state, also indeclinable either case and the case where the two, are expressed as solid.

7. dispersion stabilization

Using the coating fluid and dispersions of polyurethanes obtained by polycarbonate glycol, evaluated according to JIS K5600-2-5 Dispersion stabilization.3 hours are placed at 25 DEG C it should be noted that for coating fluid, after preparation to evaluate.

8. the alcohol resistance of film

Using the film obtained by polycarbonate glycol, it is made to adhere to 50% ethyl alcohol (EtOH) aqueous solution, is transferred at 20 DEG C It sets 4 hours, with the appearance of visual valuation film.The degree and amount of defect are indicated with grade 0~5 based on JISK5600-8-1, Alcohol resistance as film.

9. the acid resistance of film

For the film obtained by polycarbonate glycol, with visual valuation 0.1mol/L H₂SO₄It is small 24 in aqueous solution When at room temperature impregnate after appearance of film.Based on JIS K5600-8-1, the degree and amount of defect are indicated with grade 0~5, are made For the acid resistance of film.

10. the flatness of film

For using polyurethane film obtained from polycarbonate glycol, laser microscope (Olympus is used Corporation systems, OLS4100) find out the amplitude (μm) of surface relief.

11. the mechanical properties of polyurethane

Will use polycarbonate glycol obtained from polyurethane film cut the long strip type for 10mm × 80mm, 23 DEG C, 3 days obtained substances are cured under the thermostatic chamber of 50%RH as test body.For the test body, Tensilon tension tests are used It is (single to measure fracture strength with distance 50mm, tensile speed 100mm/ minutes between chuck for device (ORIENTEC systems, RTC-1250A) Position：) and elongation at break (unit MPa：%).

12. the heat resistance of polyurethane

Polyurethane film cuts the long strip type for 10mm × 80mm obtained from polycarbonate glycol being used, at 120 DEG C Warm-air dryer in place 5 days made of substance as test body.Later, for the test body, with above-mentioned polyurethane machine Method shown in tool physical property measures fracture strength (unit：MPa).Strength retention is found out by following formula (4), as polyurethane Heat resistance index.

Strength retention (%)=E/D × 100 (4)

E：Fracture strength (MPa) after heat-resistance test

D：Fracture strength (MPa) before heat-resistance test

13. the oil resistivity of polyurethane film

Make the oleic acid of 0.1g be attached to polyurethane film obtained from polycarbonate glycol will be used to cut for 10mm × In the test body of the long strip type of 80mm, placed 4 hours at 20 DEG C, with the appearance of visual valuation test body.Based on JISK5600- 8-1 indicates the degree and amount of defect with grade 0~5, as oil resistivity.

14. the measurement of the amount of moisture in polycarbonate glycol

Using moisture content determining device (KF-100 types, Mitsubishi Chemical Analytech Co., Ltd.s system), The amount of moisture in polycarbonate glycol is measured with volumetric analysis based on JIS K0068.

15. the transparency of film

The film obtained by polycarbonate glycol is impregnated 1 week in 90 DEG C of distilled water.Later, water is wiped from film Point, film is cured 3 days in 23 DEG C, the thermostatic chamber of 50%RH.Based on JIS K 7105, the total of the front and back film of dipping is found out Light transmittance is found out the transparency of film by following formula (5).

The transparency=F/G × 100 (5)

G：The total light transmittance (%) of film before dipping

F：The total light transmittance (%) of film after dipping

[embodiment 1]

In the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler, 275g is put into (3.1mol) dimethyl carbonate, 500g (4.8mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.2g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.It will reaction temperature Degree is set as 190 DEG C, when the methanol that distillation removal generates is with the mixture of dimethyl carbonate react within 12 hours.Later, will Pressure in aforementioned flask is to 12kPa, side distillation removal glycol and dimethyl carbonate, while further carrying out 5 at 195 DEG C Hour reaction.Later, 0.22g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, to aforementioned flask Interior mixture carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Obtained poly- carbon is shown in table 1 The analysis result of acid esters glycol.The polycarbonate glycol is referred to as PC-1.Obtained polycarbonate glycol has by formula (A) The repetitive unit and terminal hydroxyl of expression, the R and ratio of each repetitive unit are as shown in table 1.In addition, measuring the water in PC-1 Component, result 82ppm.

[embodiment 2]

In the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler, 310g is put into (3.4mol) dimethyl carbonate, 500g (4.8mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.2g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone Except the methanol of generation and the mixture of dimethyl carbonate, carried out 2 hours after reacting while reaction temperature is set as 160 DEG C, it will be anti- It answers temperature to be increased to 190 DEG C further to carry out reacting for 12 hours.Later, by the pressure in aforementioned flask to 12kPa, Bian Zheng It evaporates and removes glycol and dimethyl carbonate, while further carrying out reacting for 5 hours at 195 DEG C.Later, phosphorus is used as in aforementioned flask Compound adds 0.22g acid phosphate 2- ethylhexyls, at 120 DEG C heat within 5 hours to the mixture in aforementioned flask, To obtain polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.By the makrolon two Alcohol is referred to as PC-2.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl indicated by formula (A), respectively repeats list The R and ratio of member are as shown in table 1.

[embodiment 3]

In the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler, 350g is put into (3.9mol) dimethyl carbonate, 500g (4.8mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.2g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone Except the methanol of generation and the mixture of dimethyl carbonate, carried out 3 hours after reacting while reaction temperature is set as 150 DEG C, it will be anti- It answers temperature to be increased to 190 DEG C further to carry out reacting for 12 hours.Later, by the pressure in aforementioned flask to 12kPa, Bian Zheng It evaporates and removes glycol and dimethyl carbonate, while further carrying out reacting for 5 hours at 195 DEG C.Later, phosphorus is used as in aforementioned flask Compound adds 0.22g acid phosphate 2- ethylhexyls, at 120 DEG C heat within 5 hours to the mixture in aforementioned flask, To obtain polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.By the makrolon two Alcohol is referred to as PC-3.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl indicated by formula (A), respectively repeats list The R and ratio of member are as shown in table 1.

[comparative example 1]

In the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler, 420g is put into (4.7mol) dimethyl carbonate, 500g (4.8mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.2g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone Except the methanol of generation and the mixture of dimethyl carbonate, carried out 10 hours after reacting while reaction temperature is set as 140 DEG C, it will be anti- It answers temperature to be increased to 190 DEG C further to carry out reacting for 10 hours.Later, by the pressure in aforementioned flask to 12kPa, Bian Zheng It evaporates and removes glycol and dimethyl carbonate, while further carrying out reacting for 5 hours at 195 DEG C.Later, phosphorus is used as in aforementioned flask Compound adds 0.22g acid phosphate 2- ethylhexyls, at 120 DEG C heat within 5 hours to the mixture in aforementioned flask, To obtain polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.By the makrolon two Alcohol is referred to as PC-21.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl indicated by formula (A), each to repeat The R and ratio of unit are as shown in table 1.

[embodiment 4]

245g is added in the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler (2.8mol) ethylene carbonate, 450g (4.3mol) 1,5- pentanediols, 520g (4.4mol) 1,6-HD.In aforementioned flask 0.35g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone After carrying out reaction in 3 hours at 165 DEG C except the ethylene glycol of generation and the mixture side of ethylene carbonate, reaction temperature is improved It further carries out reacting for 12 hours to 185 DEG C.Later, by the pressure in aforementioned flask to 11kPa, side distillation removal glycol It further carries out reacting for 7 hours at 190 DEG C with ethylene carbonate side.Later, it is added as phosphorus compound in aforementioned flask 0.39g acid phosphate 2- ethylhexyls at 120 DEG C heat within 5 hours, to be gathered to the mixture in aforementioned flask Carbonate diol.The analysis result of obtained polycarbonate glycol is shown in table 1.In addition, being shown in FIG. 1 obtained Polycarbonate glycol¹H-NMR analysis charts.The polycarbonate glycol is referred to as PC-4.Obtained polycarbonate glycol tool There are the repetitive unit and terminal hydroxyl indicated by formula (A), the R and ratio of each repetitive unit as shown in table 1.In addition, measuring The result of amount of moisture in PC-4 is 117ppm.

[embodiment 5]

215g is added in the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler (2.4mol) ethylene carbonate, 450g (4.3mol) 1,5- pentanediols, 520g (4.4mol) 1,6-HD.In aforementioned flask 0.35g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone After carrying out reaction in 1 hour at 165 DEG C except the ethylene glycol of generation and the mixture side of ethylene carbonate, reaction temperature is improved It further carries out reacting for 14 hours to 185 DEG C.Later, by the pressure in aforementioned flask to 11kPa, side distillation removal glycol It further carries out reacting for 7 hours at 190 DEG C with ethylene carbonate side.Later, it is added as phosphorus compound in aforementioned flask 0.39g acid phosphate 2- ethylhexyls at 120 DEG C heat within 5 hours, to be gathered to the mixture in aforementioned flask Carbonate diol.The analysis result of obtained polycarbonate glycol is shown in table 1.The polycarbonate glycol is referred to as PC-5.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl that are indicated by formula (A), the R of each repetitive unit with And ratio is as shown in table 1.

[embodiment 6]

190g is added in the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler (2.2mol) ethylene carbonate, 450g (4.3mol) 1,5- pentanediols, 520g (4.4mol) 1,6-HD.In aforementioned flask 0.35g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone Except the ethylene glycol of generation and the mixture side of ethylene carbonate carry out reacting for 12 hours at 190 DEG C.It later, will be in aforementioned flask Pressure to 11kPa, further carry out reacting for 7 hours at 190 DEG C in distillation removal glycol and ethylene carbonate.It Afterwards, 0.39g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, existed to the mixture in aforementioned flask It carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Point of obtained polycarbonate glycol is shown in table 1 Analyse result.The polycarbonate glycol is referred to as PC-6.Obtained polycarbonate glycol has the repetition list indicated by formula (A) Member and terminal hydroxyl, the R and ratio of each repetitive unit are as shown in table 1.

[comparative example 2]

180g is added in the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler (2.1mol) ethylene carbonate, 450g (4.3mol) 1,5- pentanediols, 520g (4.4mol) 1,6-HD.In aforementioned flask 0.35g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.Side distillation is gone Except the ethylene glycol of generation and the mixture side of ethylene carbonate carry out reacting for 12 hours at 195 DEG C.It later, will be in aforementioned flask Pressure to 11kPa, further carry out reacting for 7 hours at 190 DEG C in distillation removal glycol and ethylene carbonate.It Afterwards, 0.39g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, existed to the mixture in aforementioned flask It carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Point of obtained polycarbonate glycol is shown in table 1 Analyse result.The polycarbonate glycol is referred to as PC-22.Obtained polycarbonate glycol has the repetition indicated by formula (A) Unit and terminal hydroxyl, the R and ratio of each repetitive unit are as shown in table 1.

[embodiment 7]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 375g is put into (3.2mol) diethyl carbonate, 460g (4.4mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.15g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.At 190 DEG C In the mixture of ethyl alcohol and dimethyl carbonate that distillation removal generates react within 12 hours.It later, will be in aforementioned flask Pressure further carries out 5 hours in the mixture of distillation removal glycol and diethyl carbonate at 200 DEG C to 14kPa Reaction.Later, 0.17g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, in aforementioned flask Mixture carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.The obtained poly- carbon of analysis is shown in table 1 The result of acid esters glycol.The polycarbonate glycol is referred to as PC-7.Obtained polycarbonate glycol has to be indicated by formula (A) Repetitive unit and terminal hydroxyl, the R and ratio of each repetitive unit be as shown in table 1.

[embodiment 8]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 375g is put into (3.2mol) diethyl carbonate, 460g (4.4mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.In aforementioned flask 0.15g butyl titanates are added as catalyst, stir and heat under normal pressure the mixture in aforementioned flask.At 190 DEG C In the mixture of ethyl alcohol and dimethyl carbonate that distillation removal generates react within 12 hours.It later, will be in aforementioned flask Pressure further carries out 4 hours in the mixture of distillation removal glycol and diethyl carbonate at 210 DEG C to 14kPa Reaction.Later, 0.17g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, in aforementioned flask Mixture carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.The obtained poly- carbon of analysis is shown in table 1 The result of acid esters glycol.The polycarbonate glycol is referred to as PC-8.Obtained polycarbonate glycol has to be indicated by formula (A) Repetitive unit and terminal hydroxyl, the R and ratio of each repetitive unit be as shown in table 1.

[embodiment 9]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 220g is put into (2.5mol) ethylene carbonate, 300g (3.3 moles) 1,4- butanediols, 500g (4.8mol) 1,5- pentanediols.In aforementioned flask It is middle that catalyst is used as to add 0.2g butyl titanates, stir and heat under normal pressure the mixture in aforementioned flask.It distills on side The mixture side for removing the ethylene glycol and ethylene carbonate that generate is carried out 3 hours at 165 DEG C after reacting, and reaction temperature is carried Height further carries out reacting for 12 hours to 185 DEG C.Later, by the pressure in aforementioned flask to 11kPa, side distillation removal two Alcohol and ethylene carbonate side further carry out reacting for 7 hours at 190 DEG C.Later, add as phosphorus compound in aforementioned flask Add 0.22g acid phosphate 2- ethylhexyls, the mixture in aforementioned flask at 120 DEG C heat within 5 hours, to obtain Polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.The polycarbonate glycol is referred to as PC-9.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl that are indicated by formula (A), the R of each repetitive unit with And ratio is as shown in table 1.

[embodiment 10]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 245g is put into (2.8mol) ethylene carbonate, 620g (6.9 moles) 1,4- butanediols, 240g (2.0mol) 1,6-HD.In aforementioned flask It is middle that catalyst is used as to add 0.2g butyl titanates, stir and heat under normal pressure the mixture in aforementioned flask.It distills on side The mixture side for removing the ethylene glycol and ethylene carbonate that generate is carried out 3 hours at 165 DEG C after reacting, and reaction temperature is carried Height further carries out reacting for 12 hours to 185 DEG C.Later, by the pressure in aforementioned flask to 11kPa, side distillation removal two Alcohol and ethylene carbonate side further carry out reacting for 7 hours at 190 DEG C.Later, add as phosphorus compound in aforementioned flask Add 0.22g acid phosphate 2- ethylhexyls, the mixture in aforementioned flask at 120 DEG C heat within 5 hours, to obtain Polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.The polycarbonate glycol is referred to as PC-10.Obtained polycarbonate glycol has the repetitive unit and terminal hydroxyl that are indicated by formula (A), the R of each repetitive unit with And ratio is as shown in table 1.

[embodiment 11]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 250g is put into (2.8mol) ethylene carbonate, 1100g (9.3mol) 1,6-HD.In aforementioned flask 0.3g metatitanic acids are added as catalyst Four butyl esters stir and heat under normal pressure the mixture in aforementioned flask.The ethylene glycol and carbonic acid that side distillation removal generates are sub- After the mixture side of ethyl ester carries out reaction in 3 hours at 165 DEG C, it is small that reaction temperature is increased to 185 DEG C of further progress 12 Shi Fanying.Later, by the pressure in aforementioned flask to 11kPa, in distillation removal glycol and ethylene carbonate at 190 DEG C It is lower further to carry out reacting for 7 hours.Later, 0.33g acid phosphate 2- ethyl hexyls are added as phosphorus compound in aforementioned flask Ester at 120 DEG C heat within 5 hours, to obtain polycarbonate glycol to the mixture in aforementioned flask.Show in table 1 Go out the analysis result of obtained polycarbonate glycol.The polycarbonate glycol is referred to as PC-11.Obtained makrolon Glycol has the repetitive unit and terminal hydroxyl indicated by formula (A), the R and ratio of each repetitive unit as shown in table 1.

[embodiment 12]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 235g is put into (2.6mol) dimethyl carbonate, 400g (3.9mol) 1,5- pentanediols, 450g (3.8mol) 3- methyl-1s, 5- pentanediols.Preceding It states in flask and adds 0.05g butyl titanates as catalyst, stir and heat under normal pressure the mixture in aforementioned flask. Reaction temperature is set as 190 DEG C, when the methanol that distillation removal generates is with the mixture of dimethyl carbonate react within 12 hours. Later, by the pressure in aforementioned flask to 12kPa, side distillation removal glycol and dimethyl carbonate, while into one at 195 DEG C Step react within 5 hours.Later, 0.06g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, to preceding It states the mixture in flask to carry out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Obtained by being shown in table 1 Polycarbonate glycol analysis result.The polycarbonate glycol is referred to as PC-12.Obtained polycarbonate glycol has The repetitive unit and terminal hydroxyl indicated by formula (A), the R and ratio of each repetitive unit are as shown in table 1.

[embodiment 13]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 190g is put into (2.1mol) dimethyl carbonate, 1000g (6.2mol) 1,9- nonanediols.In aforementioned flask 0.3g metatitanic acids are added as catalyst Four butyl esters stir and heat under normal pressure the mixture in aforementioned flask.Reaction temperature is set as 190 DEG C, side distillation removal The methanol of generation with the mixture side of dimethyl carbonate react within 12 hours.Later, extremely by the pressure in aforementioned flask 12kPa, side distillation removal glycol and dimethyl carbonate, while further carrying out reacting for 5 hours at 195 DEG C.Later, in aforementioned burning 0.33g acid phosphate 2- ethylhexyls are added as phosphorus compound in bottle, the mixture in aforementioned flask is carried out at 120 DEG C It heats within 5 hours, to obtain polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.It should Polycarbonate glycol is referred to as PC-13.Obtained polycarbonate glycol is with the repetitive unit and end hydroxyl indicated by formula (A) Base, the R and ratio of each repetitive unit are as shown in table 1.

[synthesis 1 of ether diol compound]

In the glass system four-hole boiling flask for the 500ml for having blender, separatory funnel, thermometer and cooling tube, input Potassium hydroxide (reagent superfine, purity 85%, Wako Pure Chemical Industries, Ltd.'s system) 26.4g (0.4mol) and 1,6-HD (Aldrich Corporation systems) 118.0g (1.0mol), carries out stirring for 30 minutes in 120 DEG C of oil bath.With in flask Temperature be after 100 DEG C of mode sets oil bath, the bromo- 1- hexanols of 72.4g (0.4mol) 6- to be put into separatory funnel, with every It is secondary to be marginally added dropwise with 10 minutes.It is added dropwise after terminating, the temperature of oil bath is increased to 140 DEG C, further carry out 2 hours instead It answers.After being cooled to room temperature, 200ml ethyl alcohol (reagent superfine, Wako Pure Chemical Industries, Ltd.'s system) is added in flask, is carried out It stirs within 5 minutes.After the content of filter flask, filtrate is moved in the eggplant type flask of 500ml, ethyl alcohol is removed with evaporator Later, the rectifying column of regular filler is filled in installation, is carried out distillation and is refined, to obtain 18.2g 6 (6- hydroxyls hexyloxy)- 1- hexanols (in above-mentioned formula (E), m=n=6, purity 92%).The ether diol compound is referred to as EC-1.

[synthesis 2 of ether diol compound]

In the synthesis 1 of ether diol compound, 1,6- hexylene glycols are replaced with into 1,5-PD (Aldrich Corporation systems) 104.0g (1.0mol), is reacted with identical method, obtains 15.7g6 (5- hydroxyls penta in addition to this Oxygroup) -1- hexanols (in above-mentioned formula (E), m=6, n=5, purity 90%).The ether diol compound is referred to as EC-2.

[synthesis 3 of ether diol compound]

In the synthesis 1 of ether diol compound, 1,6- hexylene glycols are replaced with into 1,5-PD (Aldrich Corporation systems) 104.0g (1.0mol), the bromo- 1- hexanols of 6- are replaced with into the bromo- 1- amylalcohols 66.8g (0.4mol) of 5-, remove this Reacted in the identical method of external application, obtain 12.6g 5 (5- hydroxyls amoxy) -1- amylalcohols (in above-mentioned formula (E), m=n =5, purity 94%).The ether diol compound is referred to as EC-3.

[embodiment 14]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 770g is put into (8.8mol) ethylene carbonate, 450g (4.3mol) 1,5- pentanediols, 520g (4.4mol) 1,6-HD, 1.61g (0.007mol)EC-1、1.38g(0.007mol)EC-3。

0.8g butyl titanates are added as catalyst in aforementioned flask, stir and heat under normal pressure aforementioned flask Interior mixture.In the mixture of ethylene glycol and ethylene carbonate that distillation removal generates 15 hours are carried out at 170 DEG C instead It answers.Later, by the pressure in aforementioned flask to 11kPa, in distillation removal glycol and ethylene carbonate at 190 DEG C into One step react within 7 hours.Later, 0.89g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, it is right Mixture in aforementioned flask carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Gained is shown in table 1 The analysis result of the polycarbonate glycol arrived.The polycarbonate glycol is referred to as PC-14.Obtained polycarbonate glycol tool There are the repetitive unit and terminal hydroxyl indicated by formula (A), the R and ratio of each repetitive unit as shown in table 1.

[embodiment 15]

In the 2L glass system flasks for having the rectifying column and agitating device of filling regular filler, 830g is put into (9.4mol) ethylene carbonate, 450g (5.0mol) 1,4- butanediols, 520g (4.4mol) 1,6-HD, 1.72g (0.008mol)EC-1。

0.8g butyl titanates are added as catalyst in aforementioned flask, stir and heat under normal pressure aforementioned flask Interior mixture.In the mixture of ethylene glycol and ethylene carbonate that distillation removal generates 15 hours are carried out at 170 DEG C instead It answers.Later, by the pressure in aforementioned flask to 11kPa, in distillation removal glycol and ethylene carbonate at 190 DEG C into One step react within 7 hours.Later, 0.89g acid phosphate 2- ethylhexyls are added as phosphorus compound in aforementioned flask, it is right Mixture in aforementioned flask carries out heating for 5 hours at 120 DEG C, to obtain polycarbonate glycol.Gained is shown in table 1 The analysis result of the polycarbonate glycol arrived.The polycarbonate glycol is referred to as PC-15.Obtained polycarbonate glycol tool There are the repetitive unit and terminal hydroxyl indicated by formula (A), the R and ratio of each repetitive unit as shown in table 1.

[embodiment 16]

In the glass system flask for the 2L for having the rectifying column and agitating device of filling regular filler, 780g is put into (8.7mol) dimethyl carbonate, 500g (4.8mol) 1,5- pentanediols, 490g (4.2mol) 1,6-HD.

0.5g butyl titanates are added as catalyst in aforementioned flask, stir and heat under normal pressure aforementioned flask Interior mixture.The mixture for the methanol and dimethyl carbonate that side distillation removal generates, while reaction temperature is set as 140 DEG C of progress After reaction in 10 hours, reaction temperature is increased to 190 DEG C and further carries out reacting for 10 hours.It later, will be in aforementioned flask Pressure is to 12kPa, side distillation removal glycol and dimethyl carbonate, while further carrying out reacting for 5 hours at 195 DEG C.It will After temperature is set as 80 DEG C, 2.52g (0.012mol) EC-2 is added, carries out stirring for 10 hours at 180 DEG C.Later, in aforementioned burning 0.55g acid phosphate 2- ethylhexyls are added as phosphorus compound in bottle, the mixture in aforementioned flask is carried out at 120 DEG C It heats within 5 hours, to obtain polycarbonate glycol.The analysis result of obtained polycarbonate glycol is shown in table 1.It should Polycarbonate glycol is referred to as PC-16.Obtained polycarbonate glycol is with the repetitive unit and end hydroxyl indicated by formula (A) Base, the R and ratio of each repetitive unit are as shown in table 1.

[table 1]

In ※ tables 1, C5, C6, C9 indicate (CH successively₂)₅、(CH₂)₆、(CH₂)₉, MPD expressions (CH₂)₂CH(CH₃)(CH₂)₂。

[application examples 1]

Using 40g polycarbonate glycol PC-1,0.75g as BYK-331 (BYK Chemical systems), the 5g of levelling agent as CR-50 (stone originates in 0.25 μm of industry system, average grain diameter), the 1.25g of pigment are in diluent (dimethylbenzene/butyl acetate=70/30 (weight ratio)) in for 2 weight % mode dissolved the solution of dibutyl tin laurate and 40g diluents mixed, Stirring, obtains coating host agent.In obtained coating host agent, organic multiple isocyanates of the 7.5g as curing agent is added (duranate TPA-100, Asahi Chemical Corp's system, isocyanates (NCO) content：23.1%) coating fluid, is modulated. By on the coating solution to acrylonitrile-butadiene-styrene (ABS) (ABS) resin plate, at room temperature diluent wave within 2 hours After dissipating, so that it is heating and curing at 80 DEG C 2 hours, obtain film.Dispersion stabilization is evaluated with coating fluid, resistance toization is evaluated with film It learns agents, the results are shown in table 2.

[application examples 2~16]

As polycarbonate glycol, using PC-2~16, coating fluid is modulated in the same manner as application examples 1 in addition to this.It uses The coating fluid gets similarly film with application examples 1 in addition to this.Dispersion stabilization is evaluated with coating fluid, is evaluated with film resistance to Chemical agents the results are shown in table 2.

[comparing application examples 1 and 2]

As polycarbonate glycol, using PC-21 and 22, coating fluid is modulated in the same manner as application examples 1 in addition to this.Make With the coating fluid, film is got similarly with application examples 1 in addition to this.Dispersion stabilization is evaluated with coating fluid, is evaluated with film Chemical reagent resistance the results are shown in table 2.

[table 2]

In ※ tables 2, dispersion stabilization is indicated using will compare the reading value of application examples 1 as its ratio when 1.

[application examples 17]

In the reaction vessel for having reflux condenser, thermometer, agitating device, 200g polycarbonate glycol PC- is put into 1,66.2g isophorone diisocyanate, dihydromethyl propionic acid 23.3g, 700g methyl ethyl ketone neutralized with triethylamine (MEK), it carries out reacting for 2 hours at 50 DEG C, obtains the carbamate prepolymer that end is isocyanates.It will be in reaction vessel Temperature be set as after 30 DEG C, 640g was added with 20g/ minutes speed in the carbamate prepolymer when being stirred Distilled water, obtain the lotion of carbamate prepolymer solution.In turn, in reaction vessel, by the second two as chain extender 20 weight % aqueous solutions 23.8g of amine spend 30 minutes and add while stirring.Later, by the temperature in reaction vessel be set as 40 DEG C into One step react within 30 minutes.After reflux condensing tube is replaced with simple distillation device, side spends 3 hours under reduced pressure will be anti- It answers the interior temperature of container to be warming up to MEK of 80 DEG C of side distillation removals as solvent, obtains the water-dispersed of about 30 weight % of solid constituent Polyurethane resin.Titanium dioxide (CR-50, stones of the 5g as pigment are added in obtained water dispersible polyurethane resin 100g The industry system of originating in, 0.25 μm of average grain diameter) and stir.Using obtained polyurethane resin (they is dissipated containing aqueous pigment Body), evaluate the dispersion stabilization of pigment.It is shown in table 3 evaluation result.In turn, by water dispersible polyurethane resin at 40 DEG C It after keeping 1 month, forms a film on a glass, with 120 DEG C be heat-treated within 30 minutes after placing 24 hours at room temperature, obtain To 100 μm of thickness, the sample film of width 10mm, length 60mm.Using the film, flatness is evaluated.It is shown in table 3 evaluation knot Fruit.

[application examples 18~32]

As polycarbonate glycol, using PC-2~16, it is carried out similarly, obtains water-dispersed with application examples 17 in addition to this Polyurethane resin and sample film carry out each evaluation.It is shown in table 3 the evaluation result.

[comparing application examples 3 and 4]

As polycarbonate glycol, using PC-21 and 22, it is carried out similarly in addition to this with application examples 17, obtains water Dispersed polyurethane resin and sample film carry out each evaluation.It is shown in table 3 the evaluation result.

[table 3]

In ※ tables 3, dispersion stabilization and flatness are indicated using will compare the value of application examples 3 as its ratio when 1.

[application examples 33]

In the reactor for being equipped with agitating device, thermometer, cooling tube, the PC- that 200g is obtained in embodiment 1 is put into 1, the dibutyl tin laurate of 34g hexamethylene diisocyanates, 0.02g as catalyst makes its reaction 5 small at 70 DEG C When, obtain the carbamate prepolymer with terminal isocyanate (NCO) base.600g is added in the prepolymer as solvent Dimethylformamide, obtain solution.Later, isophorone diamine of the 17g as chain extender is added in obtained solution, It carries out stirring for 1 hour at 35 DEG C, obtains polyurethane resin solution.Obtained polyurethane resin solution flows on a glass Prolong, places 30 minutes at room temperature, after so that solvent is vaporized, put into 100 DEG C of drying machine 2 hours, make it dry, obtain Polyurethane film.Using the polyurethane film, the evaluation of physical property is carried out, the evaluation result is shown in table 4.

[application examples 34~48]

As polycarbonate glycol, using PC-2~16, is operated in the same manner as application examples 33 in addition to this, obtain polyurethane Film.Using the polyurethane film, the evaluation of physical property is carried out, the evaluation result is shown in table 4.

[comparing application examples 5 and 6]

It is operated in the same manner as application examples 33 using PC-21 and 22 as polycarbonate glycol, obtains polyurethane film. Using the polyurethane film, the evaluation of physical property is carried out, the evaluation result is shown in table 4.

[table 4]

[embodiment 17]

The polycarbonate glycol obtained in 100g embodiments 1 is put into the mayonnaise bottle (ズ bottles of マ ヨ ネ ー) of 500g In, 5 days are placed without closeing the lid in 23 DEG C, the thermostatic chamber of relative humidity 50%.After the placement, to poly- in mayonnaise bottle Carbonate diol carries out after stirring well, measures the amount of moisture in polycarbonate glycol, result 630ppm.By the poly- carbon Acid esters glycol is referred to as PC-17.

[embodiment 18]

The polycarbonate glycol obtained in 100g embodiments 4 is put into the mayonnaise bottle of 500g, 23 DEG C, it is relatively wet 5 days are placed without closeing the lid in the thermostatic chamber of degree 50%.After the placement, good to the polycarbonate glycol in mayonnaise bottle The amount of moisture in polycarbonate glycol, result 980ppm are measured after ground stirring.The polycarbonate glycol is referred to as PC- 18。

[embodiment 19]

It will be polymerize and added phosphorus compound with the method described in embodiment 1, heat the poly- carbon obtained from Acid esters glycol is transplanted in the drying box covered tightly, is cooled to room temperature.It is sampled, is measured in polycarbonate glycol in drying box Amount of moisture result be 8ppm.The polycarbonate glycol is referred to as PC-19.

[application examples 49~51]

PC-17~19 are used as polycarbonate glycol, modulate coating fluid in the same manner as application examples 1 in addition to this.It uses The coating fluid gets similarly film with application examples 1 in addition to this.The transparency is evaluated with film, is shown in table 5 its result. It should be noted that for the film obtained by application examples 1 and application examples 4, also the evaluation transparency, the results are shown in table 5. It should be noted that in application examples 51, being modulated in drying box for coating host agent carries out.

[table 5]

The application is based on Japanese patent application (Patent 2014-164969) filed in August in 2014 13 days, by its content This is incorporated in as reference.

Industrial availability

For the present invention polycarbonate glycol, can obtain pigment dispersion stabilization it is excellent and with heat resistance, The film of chemical reagent resistance.Polycarbonate glycol with these characteristics, therefore the present invention can be particularly adapted to be used as applying The constituent of material.

Claims (12)

1. a kind of polycarbonate glycol, it includes the repetitive unit and terminal hydroxyl that are indicated by following formula (A),

Deuterochloroform is being measured as solvent, by tetramethylsilane as primary standard substance¹In H-NMR, by 3.90~ When the integrated value of the signal of 4.45ppm is set as 1000, the integrated value of 3.33~3.43ppm is 0.1~10.0,

In formula (A), R indicates the bivalent aliphatic or clicyclic hydrocarbon of carbon number 3~15, in total repetitive unit, optional a kind or 2 kinds More than.

2. polycarbonate glycol according to claim 1, wherein the 90~100 of the repetitive unit indicated by formula (A) Mole % is at least one unit in the group being made of the repetitive unit indicated by following formula (B)~(D),

3. polycarbonate glycol according to claim 1 or 2, wherein end OH base ratios are 95.0~99.9%,

The end OH base ratios refer to being calculated by end OH bases ratio (%)=A × 100 B ÷ (1) in gas chromatographic analysis The ratio gone out,

Wherein, A：Include the summation of the peak area of the alcohols of glycol, wherein not including ethyl alcohol；

B：The summation of the peak area of glycol.

4. polycarbonate glycol according to claim 1 or 2, wherein when being measured by ICP selected from by titanium, ytterbium, tin with And the content of at least one kind of metallic element in the group of zirconium composition is 0.0001~0.05 weight %.

5. polycarbonate glycol according to claim 1 or 2, wherein titanium, ytterbium, tin and zirconium when being measured by ICP Total content is 0.0001~0.05 weight %.

6. polycarbonate glycol according to claim 1 or 2, wherein the content of P when being measured by ICP is 0.0001 ~0.05 weight %.

7. polycarbonate glycol according to claim 1 or 2, wherein amount of moisture is 10~500ppm.

8. a kind of coating composition, it includes polycarbonate glycol according to any one of claims 1 to 7 and organic polyisocyanate cyanogen Acid esters.

9. a kind of coating composition, it includes make polycarbonate glycol according to any one of claims 1 to 7 and organic polyisocyanate Carbamate prepolymer obtained from polyisocyanate reactant, the carbamate prepolymer have terminal isocyanate group.

10. a kind of coating composition, it includes make polycarbonate glycol according to any one of claims 1 to 7, organic polyisocyanate Polyurethane resin obtained from cyanate and chain extender reaction.

11. a kind of water system coating composition, it includes make polycarbonate glycol according to any one of claims 1 to 7, organic Polyurethane resin obtained from polyisocyanates and chain extender reaction.

12. a kind of thermoplastic polyurethane, polycarbonate glycol described in any one of claim 1~7 and organic more is used Isocyanates and obtain.