WO2019069802A1

WO2019069802A1 - Polyurethane resin, molded article, and method for producing polyurethane resin

Info

Publication number: WO2019069802A1
Application number: PCT/JP2018/036241
Authority: WO
Inventors: 大輔長谷川; 浩明田子; 宏金山; 山崎　聡
Original assignee: 三井化学株式会社
Priority date: 2017-10-05
Filing date: 2018-09-28
Publication date: 2019-04-11
Also published as: TW201922834A; JP6946447B2; JPWO2019069802A1; KR102351760B1; TWI802596B; KR20200041348A; CN111065666A; CN111065666B

Abstract

In a reaction product of a polyisocyanate component including bis(isocyanatomethyl)cyclohexane and a polyol component including a low-molecular-weight polyol having a molecular weight of less than 400 and a carbonyl group-containing polyol having a number-average molecular weight of from 400 to 1200, the coagulation temperature measured by a differential scanning calorimeter is equal to or greater than the coagulation temperature T1 of the hard segment phase represented by the formula and equal to or less than the coagulation temperature T2 of the hard segment phase represented by the formula. Coagulation temperature T1 of hard segment (unit: °C): 80 + 1.2 x hard segment concentration (mass%). Hard segment coagulation temperature T2 (unit: °C): 115 + 1.2 x hard segment concentration (mass%)

Description

Polyurethane resin, molded article, and method for producing polyurethane resin

The present invention relates to a polyurethane resin, a molded article, and a method for producing a polyurethane resin.

Thermoplastic polyurethane resin (TPU) is generally a rubber elastic body obtained by the reaction of polyisocyanate, high molecular weight polyol and low molecular weight polyol, and a hard segment formed by the reaction of polyisocyanate and low molecular weight polyol, and poly And a soft segment formed by the reaction of an isocyanate and a high molecular weight polyol. By melt-molding such a thermoplastic polyurethane resin, a molded article made of a polyurethane resin can be obtained.

Specific examples of polyurethane resins include 1,4-bis (isocyanatomethyl) cyclohexane, a polycaprolactone diol having a number average molecular weight of 1000, and a polycarbonate diol having a number average molecular weight of 2000 (weight ratio 1: 1 mixture), A polyurethane elastomer obtained by reacting with 3-propanediol has been proposed (see, for example, Patent Document 1 (Example 74)).

International Publication WO2015 / 046369 Brochure

On the other hand, molded articles of polyurethane elastomers are required to have various physical properties depending on the application. For example, in the field of covers for smart devices, molding stability (mold release property), transparency, mechanical properties, stain resistance, It is required to have bloom resistance, color fastness and the like.

However, depending on the application, the polyurethane elastomer described in Patent Document 1 may not have sufficient molding stability (removal property), transparency, mechanical properties, stain resistance, bloom resistance, discoloration resistance, etc. .

The present invention relates to a polyurethane resin having both molding stability (mold removal property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance, a molded article obtained from the polyurethane resin, and such a polyurethane. It is a manufacturing method of the polyurethane resin which can manufacture resin.

The present invention [1] is a reaction of a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane with a low molecular weight polyol having a molecular weight of less than 400 and a polyol component containing a carbonyl group-containing polyol having a number average molecular weight of 400 to 1200. It is a product, and the aggregation temperature measured by a differential scanning calorimeter is not less than the aggregation temperature T _{1 of the} hard segment phase represented by the following formula, and not more than the aggregation temperature T ₂ of the hard segment phase represented by the following formula Some contain polyurethane resin.
Aggregation temperature T ₁ (unit: ° C.) of hard segment phase: 80 + 1.2 × hard segment concentration (mass%)
Aggregation temperature T ₂ (unit: ° C.) of hard segment phase: 115 + 1.2 × hard segment concentration (mass%)
The present invention [2] contains the polyurethane resin according to the above [1], wherein the concentration of the cyclic carbonyl compound not containing a hydroxyl group in the carbonyl group-containing polyol is 3% by mass or less.

The present invention [3] comprises the polyurethane resin according to the above [1] or [2], wherein the bis (isocyanatomethyl) cyclohexane contains 1,4-bis (isocyanatomethyl) cyclohexane.

The present invention [4] contains the polyurethane resin according to the above [3], wherein the 1,4-bis (isocyanatomethyl) cyclohexane contains a trans form at a ratio of 70 mol% or more and 99 mol% or less There is.

The present invention [5] is described in the above-mentioned [3] or [4], wherein the content ratio of 1,4-bis (isocyanatomethyl) cyclohexane to the bis (isocyanatomethyl) cyclohexane is 85% by mass or more. Contains polyurethane resin.

The present invention [6] includes a molded article comprising the polyurethane resin according to any one of the above [1] to [5].

The present invention [7] includes the molded article according to the above-mentioned [6], which is a cover of a smart device.

The present invention [8] reacts a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, a low molecular weight polyol having a molecular weight of less than 400, and a polyol component containing a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less. And a heat treatment step of heat treating the primary product to obtain a polyurethane resin, wherein the heat treatment conditions in the heat treatment step are 50 ° C. or more and 100 ° C. or less, 3 days or more and 10 days or less And a method of producing a polyurethane resin.

In the polyurethane resin of the present invention and the molded article thereof, a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less is used as a raw material (high molecular weight polyol).
That is, the number average molecular weight of the high molecular weight polyol is limited so as not to be excessively large, whereby the urethane group concentration of the polyurethane resin is improved.

And, the polyurethane resin of the present invention and the molded article thereof have the aggregation temperature of the hard segment phase adjusted appropriately, and as a result, the molding stability (mold release property), transparency, mechanical properties, stain resistance, resistance to staining It is possible to combine bloom resistance and color fastness.

Moreover, according to the method for producing a polyurethane resin of the present invention, the primary product obtained by reacting a specific polyisocyanate component and a polyol component is heat-treated under predetermined conditions. Therefore, the aggregation temperature of the hard segment phase of the resulting polyurethane resin can be adjusted appropriately. As a result, it is possible to obtain a polyurethane resin having both molding stability (mold release property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

The polyurethane resin of the present invention is, for example, a thermoplastic polyurethane resin, and as described later, it is obtained by reacting a polyisocyanate component and a polyol component, and then heat treating (heating and curing).

In other words, the polyurethane resin is a reaction product of a polyisocyanate component and a polyol component.

The polyisocyanate component contains bis (isocyanatomethyl) cyclohexane as an essential component.

Examples of bis (isocyanatomethyl) cyclohexane include 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane. Preferably, the molding stability of the polyurethane resin (removal property) And 1,4-bis (isocyanatomethyl) cyclohexane having a symmetrical structure from the viewpoint of improving mechanical properties, stain resistance and discoloration resistance.

That is, bis (isocyanatomethyl) cyclohexane preferably contains 1,4-bis (isocyanatomethyl) cyclohexane.

The content ratio of 1,4-bis (isocyanatomethyl) cyclohexane to bis (isocyanatomethyl) cyclohexane is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, more preferably Is 80% by mass or more, particularly preferably 85% by mass or more, and usually 100% by mass or less.

As 1,4-bis (isocyanatomethyl) cyclohexane, cis-1,4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis-1,4 isomer) and trans-, 4-bis (isocyanate) are exemplified. There is a stereoisomer of natomethyl) cyclohexane (hereinafter referred to as trans 1,4 form), and in the present invention, 1,4-bis (isocyanatomethyl) cyclohexane is a trans 1,4 form, for example, 60 Mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 85 mol% or more, for example, 99.8 mol% or less, preferably 99 mol% or less, more preferably , 96 mol% or less, more preferably 90 mol% or less. In other words, since 1,4-bis (isocyanatomethyl) cyclohexane is 100 mol% in total of trans 1,4 form and cis 1,4 form, cis 1,4 form is, for example, 0.2 mole. % Or more, preferably 1 mol% or more, more preferably 4 mol% or more, more preferably 10 mol% or more, for example, 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol % Or less, more preferably 15 mol% or less.

If the content ratio of the transformers 1 and 4 is at least the above lower limit, it is possible to improve the molding stability, mechanical properties, stain resistance and discoloration resistance. In addition, when the content ratio of the transformers 1 and 4 is less than or equal to the above upper limit, mechanical properties, transparency, bloom resistance, and discoloration resistance can be improved.

Bis (isocyanatomethyl) cyclohexane can be produced, for example, by the method described in International Publication WO2009 / 051114.

In addition, bis (isocyanatomethyl) cyclohexane can also be prepared as a modified product, as long as the excellent effects of the present invention are not impaired.

Examples of modified products of bis (isocyanatomethyl) cyclohexane include multimers of bis (isocyanatomethyl) cyclohexane (such as dimers (eg, uretdione modified products), trimers (eg, isocyanurate modified products, iminooxadiazine dione). Such as modified products), biuret modified products (for example, biuret modified products produced by reaction of bis (isocyanatomethyl) cyclohexane with water), allophanate modified products (for example, bis (isocyanatomethyl) cyclohexane and monovalent compounds Allophanate modified products produced by reaction with alcohol or dihydric alcohol), polyol modified products (eg polyol modified product produced by reaction of bis (isocyanatomethyl) cyclohexane with trihydric alcohol (adduct) etc.) Oxia It is produced by decarboxylation condensation reaction of a chondrion-modified product (eg, oxadiazinetrione produced by reaction of bis (isocyanatomethyl) cyclohexane with carbon dioxide gas), a carbodiimide-modified product (eg, bis (isocyanatomethyl) cyclohexane And carbodiimide-modified products).

In addition, the polyisocyanate component may contain, as an optional component, other polyisocyanates such as aliphatic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates and the like, as long as the excellent effects of the present invention are not impaired. Can.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate , 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene Triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl Octane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω , Ω'-diisocyanate, lysine isocyanato methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, bis (4- Isocyanate-n-butylidene) pentaerythritol, 2,6-diisocyanatomethyl caproate and the like.

Aliphatic polyisocyanates also include alicyclic polyisocyanates (excluding bis (isocyanatomethyl) cyclohexane).

Alicyclic polyisocyanates (except bis (isocyanatomethyl) cyclohexane) include, for example, isophorone diisocyanate (IPDI), trans, trans-, trans, cis-, cis, cis-dicyclohexylmethane diisocyanate and mixtures thereof (Hydrogenated MDI), 1,3- or 1,4-cyclohexane diisocyanate and mixtures thereof, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexyl Methane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo [2,2,1] -heptane, its isomer 2,6-diisocyanatomethylbicyclo [2,2,1] -hepta (NBDI), 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) ) -6-Isocyanatomethylbicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2] , 1] -heptane, 2-isocyanatomethyl 3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopro ) -6- (2-isocyanatoethyl) - bicyclo - [2,2,1] - heptane, and the like.

Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI), 4,4'-diphenylmethane diisocyanate, 2,4 These include '-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and any isomer mixture of these diphenylmethane diisocyanates (MDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, naphthalene diisocyanate (NDI) and the like.

As the aromatic aliphatic polyisocyanate, for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), etc. Can be mentioned.

These other polyisocyanates can be used alone or in combination of two or more.

Moreover, other polyisocyanates can also be prepared as a modified body in the range which does not inhibit the outstanding effect of this invention.

Examples of modified products of other polyisocyanates include multimers (dimers, trimers, etc.) of other polyisocyanates, biuret modified products, allophanate modified products, polyol modified products, oxadiazine trione modified products, carbodiimide modified products etc. It can be mentioned.

The content ratio in the case of containing other polyisocyanate is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, more preferably, based on the total amount of the polyisocyanate component. It is at most 15% by mass, particularly preferably at most 10% by mass.

As the polyisocyanate component, preferably, bis (isocyanatomethyl) cyclohexane is used alone. More preferably, 1,4-bis (isocyanatomethyl) cyclohexane is used alone.

In the present invention, the polyol component is a compound containing two or more hydroxyl groups in the molecule.

The polyol component includes a low molecular weight polyol having a molecular weight of less than 400 and a carbonyl group-containing polyol having a molecular weight of 400 to 1200, preferably, essentially a low molecular weight polyol having a molecular weight of less than 400 and a carbonyl having a molecular weight of 400 to 1200 It consists of a group containing polyol.

When the polyol component has a molecular weight distribution, a number average molecular weight is employed. Moreover, in such a case, the number average molecular weight can be determined by measurement by GPC method, the hydroxyl value of each component of the polyol component, and the formulation (the same applies hereinafter).

Examples of low molecular weight polyols include compounds (monomers) having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and less than 400. Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol (1,4-butanediol, 1,4-BD), 1,3-butylene glycol, 1, C2-4 alkanediols such as 2-butylene glycol, for example, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl Pentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and their Mixture, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene 3,8-diol, bisphenol A and its hydrogenated product, dihydric alcohols such as diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, etc. For example, trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine, for example, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin, for example, pentahydric alcohols such as xylitol, such as sorbitol and mannitol, Hexahydric alcohols such as alithol, iditol, dalcitol, altolitol, inositol, dipentaerythritol etc., eg, a tetrahydric alcohol such as perseitol, eg, an octahydric alcohol such as sucrose And polyhydric alcohols such Lumpur and the like.

Moreover, as a low molecular weight polyol, a polyoxyalkylene polyol in which an alkylene oxide (ethylene oxide, propylene oxide) having a carbon number of 2 to 3 is addition-reacted to have the above molecular weight using the above polyhydric alcohol as an initiator Also included are random and / or block copolymers.

These low molecular weight polyols can be used alone or in combination of two or more.

The low molecular weight polyol preferably includes a dihydric alcohol, more preferably a C2 to C4 alkanediol, still more preferably 1,4-butanediol.

When the low molecular weight polyol is as described above, a molded article (described later) having excellent mechanical properties can be obtained.

The molecular weight of the low molecular weight polyol is, for example, 50 or more, preferably 70 or more, and less than 400, preferably 300 or less.

If the molecular weight of the low molecular weight polyol is in the above range, a molded article (described later) excellent in mechanical properties can be obtained.

The carbonyl group-containing polyol is a high molecular weight compound (preferably a polymer) having one or more carbonyl groups and two or more hydroxyl groups in the molecule.

Specific examples of the carbonyl group-containing polyol include carbonyl group-containing macro polyols such as polyester polyols and polycarbonate polyols.

Examples of polyester polyols include polycondensates obtained by reacting the above-described low molecular weight polyols with polybasic acids under known conditions.

Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid Saturated aliphatic dicarboxylic acids such as azelaic acid and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; eg orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, for example, dimer acids, hydrogenated dimer acids, other carboxylic acids such as hetonic acid, and derivatives thereof Anhydrides such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride And 2-alkyl anhydride (C12 to C18) succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids and the like, for example, oxalic acid dichloride, adipic acid dichloride, sebacic acid Dichloride etc. are mentioned.

Further, as polyester polyols, for example, plant-derived polyester polyols, specifically, hydroxyl group-containing vegetable oil fatty acids (for example, castor oil fatty acids containing licinoleic acid, 12-hydroxystearic acid, using the low molecular weight polyol described above as an initiator) Vegetable oil base polyester polyol etc. which are obtained by carrying out the condensation reaction of hydroxycarboxylic acids, such as hydrogenated castor oil fatty acid etc. which contain C), under well-known conditions.

Further, as the polyester polyol, for example, lactones such as ε-caprolactone, γ-valerolactone and the like, for example, L-lactide, D- and the like, using the above-mentioned low molecular weight polyol (preferably dihydric alcohol) as an initiator Polycaprolactone polyols, polyvalerolactone polyols, and lactone-based polyester polyols such as those obtained by copolymerizing the above-mentioned dihydric alcohol, which are obtained by ring-opening polymerization of lactides and the like such as lactide and the like, and the like can be mentioned.

As the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate or phenyl carbonate having the above-mentioned low molecular weight polyol (preferably, the above-mentioned dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5- Amorphous polycarbonate polyols obtained by copolymerizing a ring-opening polymer with a dihydric alcohol such as pentanediol, 3-methyl-1,5-pentanediol or 1,6-hexanediol may, for example, be mentioned.

These carbonyl group-containing polyols can be used alone or in combination of two or more.

By using a carbonyl group-containing polyol, various physical properties such as contamination resistance can be improved as compared to the case of using a polyol not containing a carbonyl group (for example, a carbonyl group-free polyol such as polyether polyol).

More specifically, when using a polyol not containing a carbonyl group (for example, a carbonyl group-free polyol such as a polyether polyol) in place of the carbonyl group-containing polyol, such as sweat or oil and fat attached to the surface of the polyurethane resin It is inferior to the contamination resistance (soiling resistance), for example, the dirt penetrates into the inside of the polyurethane resin. Therefore, problems occur in applications (eg, smart device applications, etc.) where contamination resistance (sink resistance) is required.

On the other hand, when a carbonyl group-containing polyol is used, a polyurethane resin having excellent contamination resistance (soiling resistance) can be obtained, and various applications (eg, smart devices) for which contamination resistance (sinking resistance) is required And the like).

Further, by using a carbonyl group-containing polyol, it is possible to further improve the molding stability, the mechanical properties, the bloom resistance and the color fastness.

Further, as the carbonyl group-containing polyol, in view of improving mechanical strength, stain resistance (sinking resistance) and discoloration resistance, polyester polyol is more preferably mentioned, and particularly preferably low molecular weight polyol and polybasic acid. Examples include polycondensates with acids and polycaprolactone polyols.

The number average molecular weight of the carbonyl group-containing polyol is 400 or more, preferably 600 or more, as described above, particularly from the viewpoint of molding stability and mechanical properties, and, among others, bloom resistance, stain resistance and resistance From the viewpoint of color-changing properties, as described above, it is 1200 or less, preferably 1100 or less, more preferably 1000 or less.

When the number average molecular weight of the carbonyl group-containing polyol is in the above-mentioned range, it is possible to combine molding stability (removal property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

The number average molecular weight of the carbonyl group-containing polyol is more preferably 700 or more, particularly preferably 800 or more from the viewpoint of improving molding stability and mechanical strength.

The number average molecular weight of the carbonyl group-containing polyol is more preferably 900 or less, particularly preferably 800 or less, from the viewpoint of improving stain resistance and color fastness.

The number average molecular weight of the carbonyl group-containing polyol indicates the number average molecular weight of a single type of carbonyl group-containing polyol and does not indicate the number average molecular weight of a mixture of multiple types of carbonyl group-containing polyols.

In addition, other carbonyl group-containing polyols (carbonyl group-containing polyols having a number average molecular weight of less than 400, and a number average molecular weight together with a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less) within the range not inhibiting the excellent effects of the present invention. Carbonyl group-containing polyols having a molecular weight of more than 1200 can also be used.

The other carbonyl group-containing polyol is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less with respect to 100 parts by mass of the carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less. Especially preferably, it is 0 mass part.

In addition, the carbonyl group-containing polyol may contain a cyclic carbonyl compound containing no hydroxyl group (hereinafter sometimes referred to as a "hydroxyl-free cyclic carbonyl compound").

The hydroxyl group-free cyclic carbonyl compound is a cyclic organic compound containing a carbonyl group in the molecule and having no hydroxyl group, and examples thereof include cyclic esters (eg, lactones such as ε-caprolactone, γ-valerolactone, etc.) For example, L-lactide, lactide such as D-lactide and the like), cyclic amide (eg, lactam such as β-lactam, γ-lactam, δ-lactam and the like) and the like can be mentioned.

These cyclic carbonyl compounds containing no hydroxyl group may be used alone or in combination of two or more.

The hydroxyl-free cyclic carbonyl compound may be obtained as a side reaction product and may be contained in the polyester polyol, for example, when the above-mentioned polyester polyol is produced by the reaction of a low molecular weight polyol and a polybasic acid.

In addition, when a hydroxyl-free cyclic carbonyl compound is produced, for example, by the above-described polycaprolactone polyol by ring-opening polymerization of lactones, it is possible to use poly as a raw material component (or its multimer) remaining without ring-opening polymerization reaction. It may be contained in caprolactone polyol.

The hydroxyl-free cyclic carbonyl compound is obtained, for example, as a side reaction product when the above polycarbonate polyol is produced by the reaction of ethylene carbonate or phenyl carbonate with a low molecular weight polyol, and is contained in the polycarbonate polyol. May be

Further, the concentration of the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol can be adjusted by a known purification method such as a stripping method, a distillation method, or an extraction method.

The concentration of the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol is, for example, 5% by mass or less, preferably 3% by mass or less, more preferably 2.5% by mass or less, still more preferably 2% by mass Or less, for example, 0% by mass or more, preferably more than 0% by mass, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more.

If the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol is in the above-mentioned range, the mechanical physical properties and the bloom resistance can be particularly improved, and further, the molding stability (removal property), transparency, Contamination resistance and discoloration resistance can be improved.

When the carbonyl group-containing polyol contains a hydroxyl group-free cyclic carbonyl compound, the carbonyl group-containing polyol is a carbonyl group-containing polyol composition.

In the polyol component, the content ratio of the low molecular weight polyol and the carbonyl group-containing polyol is, for example, 5 mol% or more, preferably 7 mol% or more, more preferably 10 with respect to the total amount thereof. It is at least 15 mol%, for example, at most 75 mol%, preferably at most 65 mol%, more preferably at most 50 mol%. The low molecular weight polyol is, for example, 25 mol% or more, preferably 35 mol% or more, more preferably 50 mol% or more, and for example, 95 mol% or less, preferably 93 mol% or less, more preferably Is 90 mol% or less, more preferably 85 mol% or less.

The polyol component can also contain other polyols (polyols excluding low molecular weight polyols and polyols containing carbonyl groups). Examples of other polyols include polyether polyols and polyolefin polyols.

The other polyol is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0% by mass, based on the total amount of the polyol components.

And a polyurethane resin is obtained by the manufacturing method of a polyurethane resin provided with a reaction process and a heat treatment process as shown below.

The reaction step is a step of reacting the above-mentioned polyisocyanate component and the above-mentioned polyol component to obtain a primary product (reaction product before heat treatment).

In order to make each said component (polyisocyanate component, polyol component) react, well-known methods, such as a one-shot method and a prepolymer method, are employ | adopted, for example. From the viewpoint of improving various physical properties, preferably, a prepolymer method is employed.

Specifically, in the prepolymer method, first, a polyisocyanate component and a macro polyol (carbonyl group-containing polyol) are reacted to synthesize an isocyanate group-terminated prepolymer (prepolymer synthesis step).

In the prepolymer synthesis step, the polyisocyanate component and the macropolyol (carbonyl group-containing polyol) are reacted by a polymerization method such as bulk polymerization or solution polymerization.

In bulk polymerization, for example, under a nitrogen stream, the polyisocyanate component and the macropolyol (carbonyl group-containing polyol) are reacted at a reaction temperature of, for example, 50.degree. C. or more, for example, 250.degree. C. or less, preferably 200.degree. The reaction is performed for 0.5 hours or more, for example, 15 hours or less.

In solution polymerization, a polyisocyanate component and a macropolyol (carbonyl group-containing polyol) are added to an organic solvent, and the reaction temperature is, for example, 50 ° C. or more, for example, 120 ° C. or less, preferably 100 ° C. or less, for example The reaction is performed for 0.5 hours or more, for example, 15 hours or less.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, for example, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, n- Aliphatic hydrocarbons such as hexane, n-heptane, octane, etc., for example, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane etc., for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene etc., eg methyl cellosolve acetate , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-meth Glycol ether esters such as cyclohexyl acetate, ethyl 3-ethoxy propionate, etc., for example, ethers such as diethyl ether, tetrahydrofuran, dioxane etc., such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, Halogenated aliphatic hydrocarbons such as methylene iodide and dichloroethane, for example, polar non-protons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide Be

Moreover, in said polymerization reaction, well-known urethanization catalysts, such as amines and an organometallic compound, can be added as needed, for example.

As amines, for example, tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, for example, quaternary ammonium salts such as tetraethylhydroxyammonium, for example, imidazole, And imidazoles such as 2-ethyl-4-methylimidazole.

As the organic metal compound, for example, tin acetate, tin octylate (tin octylate), tin oleate, tin laurate, dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin di mercaptide, dibutyl tin maleate, dibutyl tin Organotin compounds such as tin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octanoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, For example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octenate, for example, organic bismuth compounds such as bismuth octanoate (bismuth octylate), bismuth neodecanoate and the like can be mentioned. Tin octylate, octyl bismuth.

Furthermore, as the urethanization catalyst, for example, potassium salts such as potassium carbonate, potassium acetate, potassium octylate and the like can be mentioned.

These urethanization catalysts can be used alone or in combination of two or more.

The addition ratio of the urethanization catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to the total 10000 parts by mass of the polyisocyanate component and the macropolyol (carbonyl group-containing polyol). For example, it is 1 part by mass or less, preferably 0.5 part by mass or less.

In the polymerization reaction, the unreacted polyisocyanate component and the organic solvent when an organic solvent is used can be removed by a known removal means such as distillation or extraction.

In the prepolymer synthesis step, the compounding ratio of each component is, for example, 1.3 or more as the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the polyisocyanate component to the hydroxyl group in the macropolyol (carbonyl group-containing polyol) Preferably, it is 1.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, still more preferably 8 or less.

More specifically, the blending ratio of each component in the prepolymer synthesis step is, for example, 5 parts by mass or more, preferably 10 parts by mass of the polyisocyanate component with respect to 100 parts by mass of the macro polyol (carbonyl group-containing polyol). It is 15 parts by mass or more, for example, 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 90 parts by mass or less.

And, in this method, the isocyanate group content is, for example, 1.0% by mass or more, preferably 3.0% by mass or more, more preferably 5.0% by mass or more, from the viewpoint of mechanical strength and stain resistance Or more, more preferably 8.0% by mass or more, for example, 30.0% by mass or less, preferably 19.0% by mass or less, more preferably 16.0% by mass or less, from the viewpoint of transparency Preferably, the above components are reacted until reaching 12.0% by mass or less. Thereby, an isocyanate group end prepolymer can be obtained.

The isocyanate group content (isocyanate group content) can be determined by a known method such as titration with di-n-butylamine or FT-IR analysis.

Next, in this method, the isocyanate group-terminated prepolymer obtained as described above is reacted with a low molecular weight polyol to obtain a primary product of a polyisocyanate component and a polyol component (chain elongation step).

That is, in this method, the low molecular weight polyol is a chain extender.

Then, in the chain extension step, the isocyanate group-terminated prepolymer and the low molecular weight polyol are reacted by a polymerization method such as bulk polymerization described above or solution polymerization described above.

The reaction temperature is, for example, room temperature or more, preferably 50 ° C. or more, for example, 200 ° C. or less, preferably 150 ° C. or less, and the reaction time is, for example, 5 minutes or more, preferably 1 hour or more, for example 72 hours or less, preferably 48 hours or less.

In addition, the compounding ratio of each component is, for example, 0.75 or more, preferably 0.9, as the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the isocyanate group-terminated prepolymer to the hydroxyl group in the low molecular weight polyol. The above, for example, 1.3 or less, preferably 1.1 or less.

More specifically, the blending ratio of each component in the chain elongation step is, for example, 1.0 parts by mass or more, preferably 2.0 parts by mass of low molecular weight polyol with respect to 100 parts by mass of isocyanate group-terminated prepolymer. It is at least 3.0 parts by mass, more preferably at most 50 parts by mass, preferably at most 40 parts by mass, more preferably at most 30 parts by mass.

Further, in the chain elongation step, in order to adjust the hard segment concentration (described later) of the polyurethane resin to be obtained, in addition to the low molecular weight polyol, a macropolyol (carbonyl group-containing polyol) can be blended at an appropriate ratio. .

Furthermore, in this reaction, the above-mentioned urethanization catalyst can be added as needed. The urethanization catalyst can be blended into the isocyanate group-terminated prepolymer and / or the low molecular weight polyol, or can be blended separately when mixing them.

When the one-shot method is adopted as a method for obtaining the above primary product, a polyisocyanate component, a polyol component (including a macropolyol (carbonyl group-containing polyol) and a low molecular weight polyol), and a polyol component The equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the polyisocyanate component to the hydroxyl group in the mixture is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, for example, 1 .2 or less, preferably 1.1 or less, more preferably 1.08 or less, and simultaneously compounded and stirred.

The stirring and mixing may be performed, for example, under an inert gas (for example, nitrogen) atmosphere, at a reaction temperature of, for example, 40.degree. C. or more, preferably 100.degree. C. or more, for example, 280.degree. The reaction time is, for example, 30 seconds or more and 1 hour or less.

Moreover, at the time of stirring and mixing, the above-mentioned urethanization catalyst and the organic solvent can be added at an appropriate ratio, as needed.

The heat treatment step is a step of heat treating the primary product to obtain a secondary product (a reaction product after heat treatment, ie, a polyurethane resin which is a reaction product).

In the heat treatment step, the primary product obtained in the above reaction step is heat-treated by leaving it for a predetermined heat treatment period at a predetermined heat treatment temperature, and then dried if necessary.

The heat treatment temperature is, for example, 50 ° C. or more, preferably 60 ° C. or more, more preferably 70 ° C. or more, and for example, 100 ° C. or less, preferably 90 ° C. or less.

When the heat treatment temperature is less than the above-mentioned lower limit, it is inferior to molding stability (mold removability), and also inferior to mechanical strength and stain resistance.

Moreover, when the heat processing temperature exceeds the said upper limit, it is inferior to transparency, bloom resistance, discoloration resistance, etc.

On the other hand, when the heat treatment temperature is in the above-mentioned range, the molding stability (removal property), the transparency, the bloom resistance and the color fastness are excellent, and furthermore, the mechanical properties and the stain resistance can be combined.

The heat treatment period is, for example, 3 days or more, preferably 4 days or more, more preferably 5 days or more, more preferably 6 days or more, for example, 10 days or less, preferably 9 days or less, more Preferably, it is 8 days or less.

When the heat treatment period is less than the above-mentioned lower limit, it is inferior to molding stability (mold removability), and also inferior to mechanical strength and stain resistance.

In addition, when the heat treatment period exceeds the above-mentioned upper limit, it is inferior to transparency, bloom resistance, discoloration resistance and the like.

On the other hand, when the heat treatment period is in the above-mentioned range, the molding stability (removal property), the transparency, the bloom resistance and the color fastness are excellent, and furthermore, the mechanical properties and the stain resistance can be combined.

Thereby, a polyurethane resin can be obtained.

The polyurethane resin may, if necessary, be a known additive, such as an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a hydrolysis inhibitor (such as a carbodiimide compound), and a plasticizer. Antiblocking agents, mold release agents, pigments, dyes (such as bluing agents), lubricants (such as fatty acid amide lubricants), fillers, rust inhibitors, fillers and the like can be added. These additives can be added during mixing of the components, during synthesis or after synthesis.

The antioxidant is not particularly limited and is not particularly limited, and examples thereof include known antioxidants (for example, described in a catalog made by BASF Japan), and more specifically, for example, phenolic antioxidants, hindered And dephenolic antioxidants.

The heat-resistant stabilizer is not particularly limited, and examples thereof include known heat-resistant stabilizers (for example, described in a catalog made by BASF Japan). More specifically, for example, phosphorus-based processing heat stabilizers, lactone-based processing heat stability Agents, sulfur processing heat stabilizers and the like.

The UV absorber is not particularly limited, and examples thereof include known UV absorbers (for example, described in catalogs manufactured by BASF Japan). More specifically, for example, benzotriazole-based UV absorbers, triazine-based UV absorbers And benzophenone-based ultraviolet absorbers.

The light stabilizers are not particularly limited, and include known light stabilizers (for example, described in the catalog made by ADEKA), and more specifically, for example, benzoate-based light stabilizers, hindered amine-based light stabilizers, etc. It can be mentioned.

Each of these additives is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, for example, 3.0% by mass or less, preferably 2.0% by mass or less, based on the polyurethane resin. Is added at a rate of

And in such a polyurethane resin production method, it contains a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, a low molecular weight polyol having a molecular weight of less than 400, and a carbonyl group-containing polyol having a number average molecular weight of 400 to 1200. The polyol component is reacted, and the obtained primary product is heat-treated under predetermined conditions.

Therefore, the polyurethane resin obtained by such a production method can have both molding stability (mold releasability), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

Specifically, the above-mentioned polyurethane resin comprises a hard segment formed by the reaction of a polyisocyanate component and a low molecular weight polyol, a polyisocyanate component and a carbonyl group-containing polyol (carbonyl group-containing polyol having a number average molecular weight of 400 to 1200). And a soft segment formed by the reaction of

The hard segment concentration of the polyurethane resin is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more For example, the content is 55% by mass or less, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less.

If the hard segment concentration of the polyurethane resin is within the above range, the molding stability (removal property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance of the resulting molded article (described later) are improved. It can be done.

The concentration of the hard segment of the polyurethane resin (the hard segment formed by the reaction of the polyisocyanate component and the low molecular weight polyol) can be calculated, for example, from the blending ratio (preparation) of each component (Examples described later) reference.).

Further, in this polyurethane resin, the aggregation temperature of the polyurethane resin corresponds to the aggregation temperature of the hard segment phase in the polyurethane resin, and the aggregation temperature T ₁ or more of the hard segment phase shown by the following calculation formula, and the following calculation formula Or lower than the aggregation temperature T ₂ of the hard segment phase shown by
Aggregation temperature T ₁ (unit: ° C.) of hard segment phase: 80 + 1.2 × hard segment concentration (mass%)
Aggregation temperature T ₂ (unit: ° C.) of hard segment phase: 115 + 1.2 × hard segment concentration (mass%)
When the aggregation temperature is at least the above lower limit (T ₁ ), the cohesion of the hard segment phase is not excessively weak, so that the molding stability (removal property) and mechanical properties are excellent.

In addition, when the aggregation temperature is equal to or lower than the upper limit (T ₂ ), the cohesion of the hard segment phase is not excessively high, and therefore, the transparency and the color fastness, and the bloom resistance are excellent.

Therefore, the polyurethane resin whose aggregation temperature is in the above-mentioned range is excellent in molding stability (removal property), transparency, mechanical properties, blooming resistance and discoloration resistance.

In addition, said calculation formula is not a theoretical formula but is an empirical formula (experimental formula) calculated | required by measuring the aggregation temperature of the polyurethane resin excellent in various physical properties.

Specifically, the aggregation temperature of the polyurethane resin is, for example, 75 ° C. or more, preferably 90 ° C. or more, more preferably 100 ° C. or more, still more preferably 105 ° C. or more, particularly preferably 110 ° C. or more For example, the temperature is 200 ° C. or less, preferably 180 ° C. or less, more preferably 170 ° C. or less, still more preferably 160 ° C. or less, particularly preferably 155 ° C. or less.

If the aggregation temperature of the polyurethane resin is not less than the above lower limit, the molding stability (removal property) and the mechanical properties can be improved, and if the aggregation temperature of the polyurethane resin is not more than the above upper limit, the transparency and the resistance It is also possible to improve the discoloration resistance and further the bloom resistance.

The aggregation temperature of the polyurethane resin can be measured by differential scanning calorimetry (DSC measurement) in accordance with the conditions of the examples.

More specifically, since the above polyurethane resin uses a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less as a raw material, it has stain resistance (smear resistance) compared to the case of using a polyol not containing a carbonyl group. Can be improved.

Furthermore, while the above polyurethane resin uses a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1,200 or less as a raw material, a polyol having a number average molecular weight exceeding 1,200 is not used as a raw material, Is a small amount that does not inhibit the excellent effect of. Therefore, the cohesion of the hard segment phase of the primary product becomes relatively low, and as a result, the molding stability and mechanical properties become relatively low.

On the other hand, by performing the heat treatment as described above, the cohesion of the hard segment phase can be improved, and the molding stability and mechanical properties can be improved.

However, even when heat treatment is performed, depending on the heat treatment conditions, the cohesion of the hard segment phase may become excessively high, which may cause a decrease in transparency, discoloration resistance, bleed resistance and the like.

On the other hand, by adjusting the heat treatment conditions to the above-mentioned range, it is possible to appropriately improve the cohesion of the hard segment phase and to suppress the decrease of the transparency, the color fastness and the bleeding resistance.

As described above, by appropriately adjusting the cohesion of the hard segment phase, it is possible to obtain a polyurethane resin having both molding stability (removal property), transparency, mechanical properties, bloom resistance and discoloration resistance.

The cohesion of the hard segment phase corresponds to the aggregation temperature. Therefore, if the aggregation temperature is above the range of the hard segment phase (T ₁ or T ₂ or less), molding stability (mold releasability), transparency, mechanical properties, resistance to bloom and discoloration resistance in excellent polyurethane resin You can get it.

In this way, the above-mentioned polyurethane resin can have both molding stability (removal property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

The present invention also includes a molded article containing the above-described polyurethane resin. The molded article is molded from a polyurethane resin.

The molded product may be, for example, the above-mentioned polyurethane resin by a known molding method, for example, heat compression molding and injection molding using a specific mold, or extrusion molding using a sheet winding device, for example, melt spin molding According to the thermoforming processing method of the present invention, it can be obtained, for example, by forming into various shapes such as pellet, plate, fiber, strand, film, sheet, pipe, hollow and box.

And the obtained molded article can be combined with molding stability (mold-removal property), transparency, mechanical property, stain resistance, bloom resistance and discoloration resistance.

In the above description, the polyurethane resin of the present invention and the method for producing the same are a thermoplastic polyurethane resin and a method for producing the same, but the polyurethane resin of the present invention and a method for producing the same are a thermosetting polyurethane resin and a method for producing the same It can be applied to

In the thermosetting polyurethane resin and the method for producing the same, for example, the above-mentioned isocyanate group-terminated prepolymer, a dihydric alcohol (such as 1,4-butanediol) and a trihydric alcohol (such as trimethylolpropane), and further known fragrances Group diamine or the like (reaction step), for example, after cast molding, the obtained molded product is heat-treated under the above conditions (heat treatment step). Thereby, a molded article comprising a thermosetting polyurethane resin and the thermosetting polyurethane resin can be obtained.

And, such a thermosetting polyurethane resin and a method for producing the same, and a molded article made of the thermosetting polyurethane resin are also suitable for molding stability (mold releasability), transparency, mechanical properties, stain resistance, and bloom resistance. Combination of resistance and color fastness.

Therefore, the molded article can be suitably used in the field where the various physical properties described above are required, and in particular, can be suitably used as a cover of a smart device.

More specifically, the smart device is a multifunctional information processing terminal, and examples thereof include a smartphone, a tablet computer (tablet PC), and a slate computer (slate PC).

Such a smart device is usually formed so as to be able to remove a resin cover, and such a cover has mold stability (removal property), transparency, mechanical properties, stain resistance, Bloom resistance and discoloration resistance are required. Therefore, the molded article of the above-mentioned polyurethane resin is suitably used as a cover of a smart device.

In addition, the molded articles can be widely used industrially besides the above-mentioned applications, and specifically, for example, transparent hard plastics, coating materials, adhesives, adhesives, waterproof materials, potting agents, inks , Binders, films (for example, films such as paint protection films, chipping films), sheets, bands (for example, bands such as watch bands, for example, transmission belts for automobiles, belts such as conveyor belts for various industries (conveyor belts)) , Tubes (for example, medical tubes, catheters, etc., air tubes, hydraulic tubes, tubes such as electric wire tubes, hoses such as fire hoses), blades, speakers, sensors, LED seals for high brightness Agent, organic EL member, photovoltaic member, robot member, android Materials, wearables, clothing products, sanitary products, cosmetic products, food packaging materials, sports products, leisure products, medical products, care products, housing components, acoustic components, lighting components, chandeliers, exterior lights, sealing materials, sealing materials , Cork, packing, anti-vibration / seismic / vibration-isolating member, sound-insulation member, household goods, sundries, cushions, bedding, stress-absorbing material, stress-relieving material, interior / exterior parts of cars, railway members, aircraft members, optical members, OA Equipment members, sundries surface protection members, semiconductor sealants, self-healing materials, health appliances, eyeglass lenses, toys, cable sheaths, wire harnesses, telecommunications cables, automobile wires, computer wires, industrial products such as curl cords, sheets, Nursing products such as films, sports goods, leisure goods, various miscellaneous goods, vibration and vibration isolation materials, shock absorbers, optical materials, light guide films Which films, auto parts, surface protection sheets, decorative sheets, transfer sheets, tape members such as semiconductor protection tapes, golf ball members, tennis racquet strings, agricultural films, wallpaper, antifogging agents, non-woven fabrics, mattresses, sofas, etc. Furniture supplies, clothing products such as bra and shoulder pads, medical supplies such as disposable diapers, napkins, medical tape cushioning materials, cosmetics, sanitary products such as facial puffs and pillows, soles (outsole), midsoles, cover materials Shoe products such as, body pressure dispersion products such as pads and cushions for vehicles, door trims, instrument panels, gear knobs and other touching members, shock absorbers such as electric refrigerator and building insulation, shock absorbers etc. Absorbent material, filler, handle of vehicle, automobile interior member, automobile exterior member, etc. The present invention is suitably used in the following vehicle articles, semiconductor manufacturing articles such as chemical mechanical polishing (CMP) pads, and the like.

Furthermore, the above-mentioned molded articles can be coated materials (films, sheets, belts, wires, electric wires, metal rotating devices, wheels, drills, etc.), yarns and fibers (tubes, tights, spats, sportswear, Yarns and composite fibers used in swimwear etc., extrusion applications (extinution applications for tennis, batton and other bats and their convergence materials), slush molded articles in powder form by micropelletization, artificial leather, skin, Sheets, coated rolls (coated rolls such as steel), sealants, rollers, gears, balls, bat covers or core materials (golf balls, basketballs, tennis balls, volleyballs, softballs, bats, etc.) It may be in the form of foam molded polyurethane resin))), , Ski products, boots, tennis products, grips (grips for golf clubs and motorcycles), rack boots, wipers, seat cushion members, films for care products, 3D printer molded products, fiber reinforced materials (carbon fibers, lignin, kenaf) , Fiber reinforced materials such as nano cellulose fiber, glass fiber), safety goggles, sunglasses, glasses frame, ski goggles, swimming goggles, contact lenses, gas-assisted foam moldings, shock absorbers, CMP polishing pads, dumbars, bearings, It is suitably used for dust covers, cutting valves, chipping rolls, high-speed rotating rollers, tires, watches, wearable bands, and other applications requiring recovery and wear resistance due to repeated expansion and contraction, compression deformation, and the like.

Next, the present invention will be described based on Production Examples, Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by these. In addition, "part" and "%" are mass references | standards unless there is particular mention. In addition, specific numerical values such as mixing ratios (content ratios), physical property values, parameters, etc. used in the following description are the mixing ratios corresponding to those described in the above-mentioned “embodiments for carrying out the invention” Substitutes the upper limit (numerical value defined as "below", "less than") or lower limit (numerical value defined as "above", "excess"), etc. of the corresponding description such as content ratio), physical property value, parameters be able to.
1) Raw material <Polyisocyanate component (a)>
1,4-BIC: 1,4-bis (isocyanatomethyl) cyclohexane 1,3-BIC synthesized by the method described in Preparation Examples 1 to 5 described below: 1,3-bis (isocyanatomethyl) cyclohexane, commercial item Name: Takenate 600, manufactured by Mitsui Chemicals, Inc. MDI: Diphenylmethane diisocyanate, trade name; Cosmonate PH, manufactured by Mitsui Chemicals SKC, Inc. <Carbonyl group-containing polyol (b)>
b-1) PBA # 300 (number average molecular weight 300): polybutylene adipate (polyester polyol) synthesized by the method described in Preparation Example 7, hydroxyl value = 373.8 mg KOH / gb-2) PBA # 500 (number average molecular weight 500): Polybutylene adipate (polyester polyol) synthesized by the method described in Production Example 7, hydroxyl value 224.2 mg KOH / gb-3) PBA # 750 (number average molecular weight 750): The method described in Production Example 7 Synthesized polybutylene adipate (polyester polyol), hydroxyl value 149.5 mg KOH / gb-4) PBA # 800 (number average molecular weight 800): polybutylene adipate synthesized by the method described in Preparation Example 7 (polyester polyol), hydroxyl group Value 140.2 mg KOH / gb-5) PBA # 1000 ( Average molecular weight 1000): Polybutylene adipate (polyester polyol), trade name: Takelac U-2410, hydroxyl value = 122.2 mg KOH / g, Mitsui Chemical Co., Ltd. b-6) PBA # 2000 (number average molecular weight 2000): Polybutylene Adipate (polyester polyol), trade name: Takelac U-2420, hydroxyl value = 56.2 mg KOH / g, Mitsui Chemicals, Inc. b-7) PCL # 1000 (number average molecular weight 1000): polycaproctone polyol, trade name; PLACCEL 210 N Hydroxyl number = 112.1 mg KOH / g, made by Daicel b-8) PCD # 1000 (number average molecular weight 1000): Polycarbonate polyol, trade name; ETERANCOL UH-100, Hydroxyl number = 112.2 mg KOH / g, Ube Industries, Ltd. Made b-9) P D # 2000 (number average molecular weight 2000): Polycarbonate polyol, trade name; ETERANCOL UH-200D, hydroxyl value = 55.9 mg KOH / g, Ube Industries b-10) PEA # 550 (number average molecular weight 550): polyethylene adipate (Polyester polyol), trade name; Takelac U-550, hydroxyl value = 204.0 mg KOH / g, Mitsui Chemicals, Inc. b-11) PEA # 1000 (number average molecular weight 1000): polyethylene adipate (polyester polyol), trade name; Nipporan 4002, hydroxyl value = 112.2 mg KOH / g, Tosoh b-12) PBS # 1000 (number average molecular weight 1000): polybutylene succinate (polyester polyol) synthesized by the method described in Production Example 8, hydroxyl group Price = 112.2 mg OH / g
<Carbonyl-free polyol (b ')>
b-13) PTMEG (number average molecular weight 1000): polytetramethylene ether glycol, trade name; PTG 1000, hydroxyl value = 112.0 mg KOH / g, manufactured by Hodogaya Chemical Co., Ltd. <low molecular weight polyol (c)>
1,4-BD: 1,4-butanediol, trade name: 1,4-butanediol,
Mitsubishi Chemical Corporation 1,3-PDO: 1,3-propanediol, trade name; SusteraTM propanediol, manufactured by DuPont <Urethanization catalyst>
Tin-based catalyst: tin (II) octylate, trade name; STANOCT, manufactured by AP Corporation <Catalyst diluent>
Diisononyl adipate: Trade name: DINA, Daihachi Chemical Industry Co., Ltd. <Stabilizer>
Antioxidant: Hindered phenolic compound, trade name: Irganox 245, manufactured by BASF Japan, UV absorber: Benzotriazole compound, trade name: Tinuvin 234, light stabilizer manufactured by BASF Japan, light stabilizer: hindered amine compound, trade name; LA- 72, Hydrolysis inhibitor manufactured by ADEKA: Carbodiimide compound, trade name; Stabacol I-LF, manufactured by LANXESS, <dye>
Anthraquinone bluing agent: trade name; Plast Blue 8514, manufactured by Arimoto Chemical Industries, Ltd. << Determination of hydroxyl group-free cyclic carbonyl compound >>
The optionally stripped carbonyl group-free polyol or the carbonyl group-containing polyol was precisely weighed 0.2 g and dissolved in 10 mL of a dichloromethane solution to which di-n-butyl phthalate (DBP) was added as an internal standard.

This solution was subjected to GC-MS / FID measurement under the following conditions, and the hydroxyl-free cyclic carbonyl compound was assigned to the retention time described below in the obtained GC-MS spectrum. And content (mass%) by DBP conversion was computed from FID detection area ratio.
Measuring device: Agilent 7890A / 5975C MSD / FID
Column: VF 5 ms
Carrier gas: He (pressure control mode: 23.602 psi)
Oven temperature: 100 ° C (2 min) → 10 ° C / min → 300 ° C (23 min) [Total = 45 min]
Injection method: splitless injection inlet temperature: 300 ° C
Detection method: FID
[Assignment of GC-MS spectrum]
<Polybutylene adipate (polyester polyol)>
24. Cyclic ester formed from one molecule of adipic acid and one molecule of 1,4-butanediol: 10.7 minutes Cyclic ester formed from two molecules of adipic acid and two molecules of 1,4-butanediol: 24. Cyclic ester formed from three or more molecules of adipic acid and three or more molecules of 1,4-butanediol: not detected due to high boiling point.
<Polyethylene adipate (polyester polyol)>
Cyclic ester formed from one molecule of adipic acid and one molecule of ethylene glycol: 7.6 minutes, two molecules of adipic acid cyclic ester formed from two molecules of ethylene glycol: 20.4 minutes, three molecules or more of adipic acid And cyclic esters formed from three or more molecules of ethylene glycol: not detected due to high boiling point.
<Polybutylene succinate (polyester polyol)>
21. Cyclic ester formed from one molecule of succinic acid and one molecule of 1,4-butanediol: 8.0 minutes Cyclic ester formed from two molecules of succinic acid and two molecules of 1,4-butanediol: 21. Cyclic ester formed from 2/3 molecules or more of succinic acid and 3 molecules or more of 1,4-butanediol: not detected due to high boiling point.
<Polycaprolactone diol>
Caprolactone monomer: 5.8 minutes caprolactone dimer: 13.2 minutes caprolactone trimer: 21.0 minutes tetramer or more of caprolactone: not detected due to high boiling point.
<Polycarbonate diol>
Cyclic polycarbonate compound formed from 2 molecules of carbonate group and 2 molecules of 1,6-hexanediol: 17.2 min. 3 molecules or more of carbonate groups and 3 or more molecules of 1,6-hexanediol formed cyclic polycarbonate Compound: 26.1 minutes Cyclic polycarbonate compound formed from four or more molecules of carbonate group and four or more molecules of 1,6-hexanediol: Not detected due to high boiling point.

2) Production of polyurethane resin <Production of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI)>
Production Example 1 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (1) (hereinafter referred to as 1,4-BIC (1)))
After filling a petroleum can with nitrogen purge of 1,4-BIC (2) described in the below-mentioned Production Example 2, it was allowed to stand for 2 weeks in an incubator at 1 ° C. The obtained coagulated material was filtered under reduced pressure using a membrane filter of 4 μm mesh quickly to remove the liquid phase portion to obtain a solid phase portion. The above operation was repeated on the solid phase portion to obtain 1,4-BIC (1). The purity by gas chromatography measurement of 1,4-BIC (1) was 99.9%, the hue by APHA measurement was 5, and the trans / cis ratio by ¹³ C-NMR measurement was 99.5 / 0.5. The hydrolyzable chlorine concentration (hereinafter referred to as HC concentration) was 18 ppm.

Production Example 2 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (2) (hereinafter referred to as 1,4-BIC (2)))
According to the description of Production Example 6 in JP-A-2014-55229, 92% of 1,4-bis (aminomethyl) cyclohexane having a purity of 99.5% or more and a trans / cis ratio of 98/2 is collected. Obtained at a rate.

Thereafter, according to the description of Production Example 1 of JP-A-2014-55229, a cold two-stage phosgenation method is carried out under pressure using this 1,4-bis (aminomethyl) cyclohexane as a raw material, , 382 parts by mass of 4-BIC (2) were obtained.

The purity by gas chromatography measurement of the obtained 1,4-BIC (2) was 99.9%, the hue by APHA measurement was 5, and the trans / cis body ratio by ¹³ C-NMR measurement was 98/2. . The HC concentration was 18 ppm.

Production Example 3 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (3) (hereinafter referred to as 1,4-BIC (3)))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe, 789 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later 211 parts by mass of (6) was charged, and stirred at room temperature for 1 hour under a nitrogen atmosphere. The purity by gas chromatography measurement of the obtained 1,4-BIC (3) was 99.9%, the hue by APHA measurement was 5, and the trans / cis ratio by ¹³ C-NMR measurement was 86/14. The HC concentration was 19 ppm.

Production Example 4 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (4) (hereinafter referred to as 1,4-BIC (4)))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe, 561 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later 439 mass parts of (6) were charged, and it stirred at room temperature under nitrogen atmosphere for 1 hour. The purity by gas chromatography measurement of the obtained 1,4-BIC (4) was 99.9%, the hue by APHA measurement was 5, and the trans / cis ratio by ¹³ C-NMR measurement was 73/27. The HC concentration was 20 ppm.

Production Example 5 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (5) (hereinafter referred to as 1,4-BIC (5)))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introducing pipe, 474 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later 526 parts by mass of (6) was charged, and stirred at room temperature for 1 hour under a nitrogen atmosphere. The purity by gas chromatography measurement of the obtained 1,4-BIC (5) was 99.9%, the hue by APHA measurement was 5, and the trans / cis ratio by ¹³ C-NMR measurement was 68/32. The HC concentration was 21 ppm.

Production Example 6 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane (6) (hereinafter referred to as 1,4-BIC (6)))
Using 1,4-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) having a trans / cis ratio of 41/59 as determined by ¹³ C-NMR measurement as a raw material, Production Example 1 of JP-A-2014-55229 According to the description, 388 parts by weight of 1,4-BIC (6) were obtained.

The purity by gas chromatography measurement of the obtained 1,4-BIC (6) was 99.9%, the hue by APHA measurement was 5, and the trans / cis body ratio by ¹³ C-NMR measurement was 41/59. . The HC concentration was 22 ppm.

<Production of Polybutylene Adipate (b-1) to (b-4)>
Production Example 7 (Production Method of Polybutylene Adipate (Polyester Polyol))
Adipic acid and 1,4-butanediol are charged into a four-necked flask equipped with a thermometer, a stirrer, and a Liebig cooler, the temperature is raised to 180 ° C., and the polycondensation reaction is advanced under a nitrogen stream, The temperature was raised to 220 ° C. When the acid value reached 15 mg KOH / g, stanoct was added as a catalyst, and the polycondensation reaction was continued at the same temperature until the acid value reached less than 1 mg KOH / g. Then, it cooled and obtained the polybutylene adipate.

<Production of Polybutylene Succinate (b-12)>
Production Example 8 (Production Method of Polybutylene Succinate (Polyester Polyol))
Succinic acid and 1,4-butanediol are charged into a four-necked flask equipped with a thermometer, a stirrer, and a Liebig cooler, the temperature is raised to 150 ° C., and the polycondensation reaction is advanced under a nitrogen stream, The temperature was raised to 220 ° C. When the acid value reached 10 mg KOH / g, stanoct was added as a catalyst, and the polycondensation reaction was continued at the same temperature until the acid value reached less than 1 mg KOH / g. After cooling, polybutylene succinate was obtained.

<Synthesis of isocyanate group terminal prepolymer>
Synthesis Examples 1 to 8, 10 to 17, 19, 21 to 22 and 24 to 28
Stripping treatment: The carbonyl group-containing polyol (b) is charged into a four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube with a capillary, and from one port, via a Liebig cooler, to a vacuum pump. It was connected. The temperature of the carbonyl group-containing polyol (b) is raised to 100 ° C., and the pressure is reduced to 1.33 kPa (10 mgHg) or less using a vacuum pump while bubbling nitrogen from the tip of the capillary tube with a capillary, for 4 hours , Stripped.

At this time, the content of the hydroxyl group-free cyclic carbonyl compound of the carbonyl group-containing polyol (b) after the stripping treatment was measured by the above method.
Urethane Formation Reaction According to the formulation described in Tables 1 to 3, a four-necked flask provided with a polyisocyanate component (a) and a carbonyl group-containing polyol (b), a stirrer, a thermometer, a reflux tube and a nitrogen introduction tube The mixture was further charged with stabactol I-LF, which is 0.2% by mass relative to the total amount of them, and stirred at 80 ° C. for 1 hour under a nitrogen atmosphere.

Thereafter, tin octylate (trade name: Stanocto, manufactured by AP Corporation) diluted to 4% by mass in advance with DINA (manufactured by Daihachi Chemical Co., Ltd.) is used as the polyisocyanate component (a) and the carbonyl group-containing polyol (b). With respect to the total amount, it was added so as to be 5 ppm as a catalytic amount.

Then, the reaction is advanced until the isocyanate group content described in Tables 1 to 3 is reached while stirring and mixing under a nitrogen stream under temperature control of 80 ° C., and isocyanate group terminated prepolymers (a) to (h), (J) to (q), (s), (u) to (v) and (x) to (ab) were obtained.

Synthesis example 9
An isocyanate group-terminated prepolymer (i) was obtained in the same manner as in Synthesis Example 1 except that the carbonyl group-containing polyol (b) was used without stripping treatment.

Synthesis example 18
In accordance with the formulations described in Tables 1 to 3, using stabazole I-, using PTMEG (b-13, number average molecular weight 1000) which is a carbonyl group-free polyol (b ′) in place of the carbonyl group-containing polyol (b) An isocyanate group-terminated prepolymer (r) was obtained in the same manner as in Synthesis Example 1 except that LF was not used.

Synthesis example 20
Isocyanate-terminated prepolymer in the same manner as in Synthesis Example 1 except that MDI (diphenylmethane diisocyanate) was used as the polyisocyanate component (a) according to the formulation described in Tables 1 to 3 and no catalyst was used. I got (t).

Synthesis example 23
An isocyanate-terminated prepolymer (w) was obtained in the same manner as in Synthesis Example 1 except that the stripping treatment temperature and the urethanation reaction temperature were changed to 120 ° C. according to the formulations described in Tables 1 to 3.

<Synthesis of polyurethane resin>
Examples 1 to 18, 20, 22, 24 and Comparative Examples 1 to 10
The isocyanate group concentration of the isocyanate group-terminated prepolymer temperature-controlled to 80 ° C. was measured.

And, the equivalent ratio (NCO index) of the isocyanate group in the isocyanate group-terminated prepolymer to the hydroxyl group in the low molecular weight polyol is set to 1.01 with 1,4-butanediol (1,4-BD) as the low molecular weight polyol. The temperature was adjusted to 80 ° C. by weighing in a stainless steel cup.

Next, the isocyanate group-terminated prepolymer is weighed into another stainless steel cup, and 0.3 parts by mass of Irganox 245 (BASF heat stabilizer) based on the total amount of isocyanate group-terminated prepolymer and 1,4-BD, 0.1 part by mass of Tinuvin 234 (ultraviolet absorber manufactured by BASF), 0.1 part by mass of Adekastab LA-72 (ALLS manufactured by ADEKA), and 0 parts by weight of Kao Wax EB-P (fatty acid amide lubricant manufactured by Kao Chemical Co., Ltd.) 0 .1 part by weight was added to the isocyanate-terminated prepolymer.

Furthermore, Plast Blue 8514 diluted to 0.5% by mass in advance with DINA (manufactured by Daihachi Chemical Co., Ltd.) was added to the isocyanate group-terminated prepolymer so as to be 0.5 ppm as Plast Blue 8514.

In addition, an isocyanate group-terminated prepolymer such that tin octylate (trade name: stanoct, manufactured by AP Corporation) diluted to 4% by mass beforehand with DINA (made by Daihachi Chemical Co., Ltd.) becomes 10 ppm as a catalytic amount Added to

The isocyanate group-terminated prepolymer was then stirred and mixed for 3 minutes in an 80 ° C. oil bath using a high-speed stirring disper under stirring at 500-1500 rpm.

Then, 1,4-BD pre-weighed to a temperature of 80 ° C. was added to the isocyanate group-terminated prepolymer, and stirred and mixed for 3 to 10 minutes under stirring at 500 to 1500 rpm using a high speed stirring disper .

Next, the mixed solution is poured into a Teflon (registered trademark) vat preheated to 150 ° C., reacted at 150 ° C. for 2 hours, and then cooled to 100 ° C. to continue the reaction for 20 hours to obtain polyurethane resin The primary products (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) were obtained.

Next, the primary products (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) of the polyurethane resin are removed from the vat, diced with a bale cutter, and crushed The diced resin was crushed by a machine to obtain crushed pellets.

The ground pellets were then heat treated (cured, aged) at the heat treatment temperature and heat treatment period described in Tables 4 to 7 and dried at 23 ° C. for 12 hours under vacuum reduced pressure.

Then, using a single-screw extruder (model: SZW40-28MG, manufactured by Technobel), extrude and cut the strand at a screw rotation speed of 30 rpm and a cylinder temperature of 200 to 270 ° C. using the obtained crushed pellets Thus, pellets of polyurethane resins (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) were obtained.

Example 19
Pellets of polyurethane resin (AE) were obtained in the same manner as in Example 1 except that the preheating temperature of the isocyanate group-terminated prepolymer was changed to 120 ° C. according to the formulation described in Table 6.

Example 21 and Example 23
Pellets of polyurethane resin (AG) and (AI) were obtained in the same manner as in Example 1 according to the formulation described in Table 6, except that the NCO index was 0.98.

Comparative example 11
Pellets of polyurethane resin (AA) were obtained in the same manner as in Example 1 except that 1,3-propanediol (PDO) was used as a low molecular weight polyol according to the formulation described in Table 7.

Comparative Example 12
Pellets of polyurethane resin (AB) were obtained in the same manner as in Example 1 except that the catalyst was not used according to the formulation described in Table 7.

3) Molding of sample for evaluation <Method of molding polyurethane sheet>
The pellets of the obtained polyurethane resins (A) to (AJ) are preliminarily dried at 80 ° C. for 12 hours under vacuum reduced pressure, using an injection molding machine (type: NEX-140, manufactured by Nisshin Resin Co., Ltd.) Surface temperature condition at a screw rotation speed of 80 rpm, a barrel temperature of 200 to 270 ° C., a mold temperature of 20 ° C., an injection time of 10 seconds, an injection speed of 60 mm / s, a holding pressure of 50 MPa and a cooling time of 20 to 60 seconds It was injection molded to obtain a good sheet of

The obtained 1 mm thick sheet was annealed in an oven at 80 ° C. for 24 hours, and then aged for 7 days under constant temperature and humidity conditions of room temperature 23 ° C. and relative humidity 55% to obtain a polyurethane sheet .

4) Evaluation <Surface of sheet>
Demolding time at the time of injection molding was standardized to 15 seconds, and the surface condition of the sheet after demolding was evaluated in five stages of evaluation 5 to 1 below.
Evaluation 5: A uniform sheet with no sticking to the mold at the time of demolding and no surface roughness is obtained.
Evaluation 4: Although there is sticking of the sheet to the mold, the peeling marks on the sheet surface are less than 20% of the whole sheet.
Evaluation 3: There is sticking of the sheet to the mold, and the peeling marks on the sheet surface are 20% or more and less than 50% of the whole sheet.
Evaluation 2: There is sticking of the sheet to the mold, and peeling marks remain on 50% or more of the sheet surface.
Evaluation 1: When the mold is opened, the sheet is stuck to the molds on both sides, and the sheet is torn.

<Total light transmittance (unit:%)>
The total light transmittance (based on JIS K7105 (light source: D ₆₅ )) of a 1 mm-thick polyurethane sheet obtained by injection molding was measured using Haze Meter (manufactured by Nippon Denshoku Kogyo, model: NDH 2000).

<Tear strength (unit: kN / m)>
It measured on the conditions of tearing speed 300 mm / min using the right-angled type tear test piece manufactured according to JISK7311 (1995) from the polyurethane sheet obtained by injection molding from 1 mm thickness.

<Breaking strength (unit: MPa) and breaking elongation (unit:%)>
The measurement was performed under the conditions of a tensile speed of 300 mm / min and a distance between marked lines of 20 mm using a JIS No. 3 dumbbell-shaped test piece prepared according to JIS K7311 (1995) from a polyurethane sheet of 1 mm thickness obtained by injection molding.

<Flocculation temperature measurement of polyurethane by differential scanning calorimeter (DSC) (unit: ° C.)>
It was measured using a differential scanning calorimeter (trade name: EXSTAR 6000 PC station and DSC 220C, manufactured by SII Nano Technology Inc.).

The polyurethane sheet was cut into thin pieces of about 8 mg so as to be in close contact with an aluminum pan as much as possible. The aluminum pan was covered with a cover and crimped to obtain a measurement sample (sample). Similarly, a sample of alumina was taken as a reference sample. After setting the sample and reference in place in the cell, cool the sample to -100 ° C at a rate of 10 ° C / min under a nitrogen stream with a flow rate of 40 NmL / min, hold for 5 minutes at the same temperature, and then 10 The temperature was raised to 270 ° C at a rate of ° C / min. After further holding at 270 ° C. for 5 minutes, it was cooled to −70 ° C. at a rate of 10 ° C./min. The temperature of the exothermic peak appearing during this cooling was taken as the aggregation temperature of the polyurethane.

<Stain resistance>
A test piece of 20 × 60 mm in size was cut out from a polyurethane sheet of 1 mm in thickness, immersed in a red oil-based magic ink (made by Teranishi Chemical Industry) for 1 hour, and then washed with distilled water.
The cut cross section was observed using a digital microscope (trade name: VHX-6000, manufactured by Keyence Corporation) to measure the thickness of the soaking in the magic ink. The smaller the thickness impregnated with the magic ink, the better the stain resistance.

<Bloom resistance>
The sheet having a thickness of 1 mm obtained by injection molding was allowed to stand in an oven at 80 ° C., and the number of days until the powder blowing phenomenon generated on the sheet surface was evaluated in five stages of evaluation 5 to 1 below.
Evaluation 5: Powder blowing does not occur within 28 days of the test.
Evaluation 4: The powder blowing phenomenon occurs within 28 days of the test.
Evaluation 3: Powder blowing phenomenon occurs within 14 days of test.
Evaluation 2: The powder blowing phenomenon occurs within 7 days of the test.
Evaluation 1: The powder blowing phenomenon occurs within 3 days of the test.

<Initial color>
The yellowness b ^* of a 1 mm-thick polyurethane sheet obtained by injection molding was measured using a color difference meter (Color Ace MODEL TC-1 manufactured by Tokyo Denshoku Co., Ltd.). In addition, b ^* is generally used as an index of the hue of the polyurethane resin.

<NOx discoloration resistance>
A 20 × 60 mm size test piece was cut out of a 1 mm thick polyurethane sheet and allowed to stand in 5000 ppm NOx gas for 15 hours. After taking out the test piece, it was subjected to a moist heat test at 60 ° C. and 93% relative humidity for 96 hours.

The Δb (the amount of change of the b value) of the polyurethane sheet before and after the test was measured using a color difference meter (Color Ace MODEL TC-1, manufactured by Tokyo Denshoku Co., Ltd.). In addition, (DELTA) b is generally used as a parameter | index of the color-change property of a polyurethane resin.

<UV resistance to discoloration>
Using a QUV weathering tester (manufactured by Suga Test Instruments Co., Ltd., an ultraviolet fluorescent light weather meter FUV) with a 20 × 60 mm size cut out of a 1 mm thick polyurethane sheet and attached with an ultraviolet fluorescent light, 60 ° C., The conditions of relative humidity 10%, irradiation intensity 28 W / m ² of ultraviolet light (wavelength 270 to 720 nm) and conditions of 50 ° C., relative humidity 95%, no ultraviolet irradiation were repeated every 4 hours for 48 hours for 6 cycles.

The Δb (the amount of change of the b value) of the polyurethane sheet before and after the test was measured using a color difference meter (Color Ace MODEL TC-1, manufactured by Tokyo Denshoku Co., Ltd.). In addition, (DELTA) b is generally made into the parameter | index of polyurethane resin discoloring property.

5) Polyurethane injection molded article <Reference Example 1>
In the above-mentioned injection molding machine, the mold was changed to a smartphone cover mold.

Thereafter, using the injection molding machine, the polyurethane resin of Example 4 was used to obtain a smartphone cover having a thickness of 1 mm.

As a result of measuring the total light transmittance of the molded article, it was 91%. In addition, as a result of observing a powder blowing phenomenon (bloom) on the surface of the smartphone cover for 6 months under conditions of a room temperature of 23 ° C. and a relative humidity of 55%, no bloom was observed. Furthermore, as a result of evaluating the stain resistance (based on the above-mentioned method) to the oil-based magic ink, the thickness to which the oil-based magic ink permeated was 100 μm.

Similarly, 1 hour of red artificial sweat obtained by adding 1 ml of red aqueous dye (trade name: IP-540R) to 100 ml of artificial sweat according to JIS-L0848 (2004) After immersion, it was washed with distilled water. The cut cross section was observed using a digital microscope (trade name: VHX-6000, manufactured by Keyence Corporation), and the thickness in which the red artificial sweat was soaked was measured and was 55 μmt.

Although the above invention is provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Variations of the invention which are apparent to those skilled in the relevant art are within the scope of the following claims.

The polyurethane resin, the molded article, and the method for producing a polyurethane resin of the present invention can be suitably used, for example, in a cover of a smart device such as a smartphone, a tablet computer (tablet PC), or a slate computer (slate PC).

Claims

A polyisocyanate component comprising bis (isocyanatomethyl) cyclohexane,
A low molecular weight polyol having a molecular weight of less than 400, and a reaction product with a polyol component containing a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less,
The aggregation temperature measured by differential scanning calorimeter is
The aggregation temperature T 1 or more of the hard segment phase represented by the following formula, and
A polyurethane resin having a hard segment phase aggregation temperature T 2 or less as indicated by the following calculation formula.
Aggregation temperature T 1 (unit: ° C.) of hard segment phase: 80 + 1.2 × hard segment concentration (mass%)
Aggregation temperature T 2 (unit: ° C.) of hard segment phase: 115 + 1.2 × hard segment concentration (mass%)
The polyurethane resin according to claim 1, wherein the concentration of the cyclic carbonyl compound not containing a hydroxyl group in the carbonyl group-containing polyol is 3% by mass or less.
The polyurethane resin according to claim 1, wherein the bis (isocyanatomethyl) cyclohexane comprises 1,4-bis (isocyanatomethyl) cyclohexane.
The polyurethane resin according to claim 3, wherein the 1,4-bis (isocyanatomethyl) cyclohexane contains a trans isomer in a ratio of 70 mol% or more and 99 mol% or less.
The polyurethane resin according to claim 3, wherein a content ratio of 1,4-bis (isocyanatomethyl) cyclohexane to the bis (isocyanatomethyl) cyclohexane is 85% by mass or more.
A molded article comprising the polyurethane resin according to claim 1.
7. The molded article according to claim 6, which is a cover of a smart device.
A polyisocyanate component comprising bis (isocyanatomethyl) cyclohexane,
A reaction step of obtaining a primary product by reacting a low molecular weight polyol having a molecular weight of less than 400 and a polyol component containing a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less;
Heat treating the primary product to obtain a polyurethane resin,
The method for producing a polyurethane resin, wherein the heat treatment conditions in the heat treatment step are 50 ° C. or more and 100 ° C. or less, and 3 days or more and 10 days or less.