JPWO2019069802A1 - Polyurethane resin, molded products, and methods for manufacturing polyurethane resin - Google Patents

Abstract

The reaction product of a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane and a polyol component containing 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 or more and 1200 or less was measured by a differential scanning calorimeter. The agglomeration temperature is equal to or higher than the agglomeration temperature T1 of the hard segment phase represented by the formula and equal to or lower than the agglomeration temperature T2 of the hard segment phase represented by the formula. Hard segment phase aggregation temperature T1 (unit: ° C): 80 + 1.2 x hard segment concentration (mass%) Hard segment phase aggregation temperature T2 (unit: ° C): 115 + 1.2 x hard segment concentration (mass%)

Description

The present invention relates to a polyurethane resin, a molded product, 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 is composed of a hard segment formed by the reaction of polyisocyanate and low molecular weight polyol and poly. It includes a soft segment formed by the reaction of isocyanate and high molecular weight polyol. By melt-molding such a thermoplastic polyurethane resin, a molded product made of a polyurethane resin can be obtained.

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

International Publication WO2015 / 046369 Pamphlet

On the other hand, molded products of polyurethane elastomer are required to have various physical properties depending on the application. For example, in fields such as covers for smart devices, molding stability (demoldability), transparency, mechanical properties, stain resistance, etc. It is required to have both bloom resistance and discoloration resistance.

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

The present invention relates to a polyurethane resin having molding stability (demolding property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance, a molded product obtained from the polyurethane resin, and such polyurethane. It is a method for producing a polyurethane resin capable of producing a resin.

The present invention [1] is a reaction between 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. It is a product, and the aggregation temperature measured by the differential scanning calorimeter is the aggregation temperature T ₁ or more of the hard segment phase shown by the following formula and the aggregation temperature T ₂ or less of the hard segment phase shown by the following formula. Contains a polyurethane resin.
Aggregation temperature of hard segment phase T ₁ (Unit: ° C): 80 + 1.2 × Hard segment concentration (mass%)
Aggregation temperature of hard segment phase T ₂ (unit: ° C): 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 containing no hydroxyl group in the carbonyl group-containing polyol is 3% by mass or less.

In the present invention [3], 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 compound in a proportion of 70 mol% or more and 99 mol% or less. There is.

The present invention [5] according to the above [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 product containing the polyurethane resin according to any one of the above [1] to [5].

The present invention [7] includes the molded product according to the above [6], which is a cover for a smart device.

In the present invention [8], a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane is reacted 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 or more and 1200 or less. It comprises a reaction step of obtaining a primary product and a heat treatment step of heat-treating the primary product to obtain a polyurethane resin, and the heat treatment conditions in the heat treatment step are 50 ° C. or higher and 100 ° C. or lower, 3 days or more and 10 days or less. It includes a method for producing a polyurethane resin.

In the polyurethane resin of the present invention and its molded product, 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, which improves the urethane group concentration of the polyurethane resin.

In the polyurethane resin of the present invention and its molded product, the aggregation temperature of the hard segment phase is appropriately adjusted, and as a result, molding stability (demoldability), transparency, mechanical properties, stain resistance, and stain resistance are adjusted. It can have both bloom property and discoloration resistance.

Further, according to the method for producing a polyurethane resin of the present invention, a 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 obtained polyurethane resin can be appropriately adjusted. As a result, it is possible to obtain a polyurethane resin having molding stability (demolding 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 is obtained by reacting a polyisocyanate component with a polyol component and then heat-treating (heat curing) as described later.

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

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

Examples of the bis (isocyanatomethyl) cyclohexane include 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane, and the molding stability (demolding property) of the polyurethane resin is preferable. ), 1,4-Bis (isocyanatomethyl) cyclohexane having a symmetrical structure can be mentioned from the viewpoint of improving mechanical properties, stain resistance and discoloration resistance.

That is, the 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, still more preferable. Is 80% by mass or more, particularly preferably 85% by mass or more, and usually 100% by mass or less.

1,4-Bis (isocyanatomethyl) cyclohexane includes cis-1,4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis 1,4) and trans-, 4-bis (isocyanatomethyl). There is a steric isomer of natomethyl) cyclohexane (hereinafter referred to as trans 1,4), and in the present invention, 1,4-bis (isocyanatomethyl) cyclohexane has trans 1,4, for example, 60. More than mol%, preferably 70 mol% or more, more preferably 80 mol% or more, still 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, 1,4-bis (isocyanatomethyl) cyclohexane has 100 mol% of trans 1,4 and cis 1,4, so 1,4 cis, for example, 0.2 mol. % Or more, preferably 1 mol% or more, more preferably 4 mol% or more, still 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.

When the content ratio of the transformers 1 and 4 is at least the above lower limit, the molding stability, mechanical properties, stain resistance and discoloration resistance can be improved. Further, when the content ratio of the transformers 1 and 4 is not more than the above upper limit, the mechanical properties, transparency, bloom resistance and discoloration resistance can be improved.

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

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 the modified product of bis (isocyanatomethyl) cyclohexane include a multimer of bis (isocyanatomethyl) cyclohexane (dimer (for example, uretdione modified product)), trimmer (for example, isocyanurate modified product, iminooxadiazidinedione). Denatured products (such as modified products), biuret modified products (for example, biuret modified products produced by the reaction of bis (isocyanatomethyl) cyclohexane with water), allophanate modified products (for example, bis (isocyanatomethyl) cyclohexane and monovalent). Alofanate modified product produced by reaction with alcohol or dihydric alcohol, polyol modified product (for example, polyol modified product (additional product) produced by reaction of bis (isocyanatomethyl) cyclohexane with trihydric alcohol), Decarbonation condensation reaction of oxadiazine trione modified product (for example, oxadiazine trione produced by reaction of bis (isocyanatomethyl) cyclohexane with carbon dioxide gas), carbodiimide modified product (for example, bis (isocyanatomethyl) cyclohexane) Carbodiimide modified product produced by the above) and the like.

In addition, the polyisocyanate component shall contain other polyisocyanates such as aliphatic polyisocyanate, aromatic polyisocyanate, aromatic aliphatic polyisocyanate, etc. as optional components as long as the excellent effects of the present invention are not impaired. Can be done.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, and 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-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis ( Isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysocyanate isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6 -Diisocyanate hexanoate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate, bis (4-isocyanate-n-butylidene) pentaerythritol, 2,6-diisocyanate methyl caproate and the like can be mentioned.

Further, the aliphatic polyisocyanate includes an alicyclic polyisocyanate (excluding bis (isocyanatomethyl) cyclohexane).

Examples of alicyclic polyisocyanates (excluding bis (isocyanatomethyl) cyclohexane) include isophorone diisocyanate (IPDI), trans, trans-, trans, cis-, and cis, cis-dicyclohexylmethanediisocyanate and mixtures thereof. (Hydrocyanate MDI), 1,3- or 1,4-cyclohexanediisocyanate and mixtures thereof, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, methylcyclohexanediisocyanate, 2,2'-dimethyldicyclohexyl Methandiisocyanate, diisocyanate dimerate, 2,5-diisocyanatomethylbicyclo [2,2,1] -heptane, its isomer 2,6-diisocyanatomethylbicyclo [2,2,1] -heptane ( 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-isocyanatopropyl) -6- (2-isocyanatopropyl) Natoethyl) -bicyclo- [2,2,1] -heptane and the like can be mentioned.

Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and an isomer mixture (TDI) of these tolylene diisocyanates, 4,4'-diphenylmethane diisocyanate, 2,4. Included are'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and any isomer mixture (MDI) of these diphenylmethane diisocyanates, toluidine diisocyanate (TODI), paraphenylenediocyanate, naphthalenediocyanate (NDI) and the like.

Examples of the aromatic aliphatic polyisocyanate include 1,3- or 1,4-xylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylene diisocyanate or a mixture thereof (TMXDI), and the like. Can be mentioned.

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

In addition, other polyisocyanates can be prepared as modified products as long as they do not impair the excellent effects of the present invention.

Examples of other modified polyisocyanates include multimers of other polyisocyanates (dimer, trimmer, etc.), biuret modified products, allophanate modified products, polyol modified products, oxadiazine trione modified products, carbodiimide modified products, and the like. Can be mentioned.

When other polyisocyanates are contained, the content ratio is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably, with respect to the total amount of the polyisocyanate components. It is 15% by mass or less, particularly preferably 10% by mass or less.

As the polyisocyanate component, bis (isocyanatomethyl) cyclohexane is preferably 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 comprises 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 or more and 1200 or less, preferably essentially a low molecular weight polyol having a molecular weight of less than 400 and a carbonyl having a molecular weight of 400 or more and 1200 or less. It consists of a group-containing polyol.

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

Examples of the low molecular weight polyol 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, such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl Pentandiol, 3,3-dimethylol heptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and theirs. Mixture, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A and its hydroxides, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2- Dihydric alcohols such as benzenediol, 1,3-benzenediol, 1,4-benzenediol, for example, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetramethylolmethane (pentaerythritol), di Tetravalent alcohols such as glycerin, for example pentahydric alcohols such as xylitol, for example hexahydric alcohols such as sorbitol, mannitol, aitol, iditol, darsitol, altritor, inositol, dipentaerythritol, for example, heptaerythritol and the like For example, polyhydric alcohols such as octavalent alcohols such as sucrose can be mentioned.

As the low molecular weight polyol, a polyoxyalkylene polyol (polyoxyalkylene polyol) obtained by addition-reacting an alkylene oxide (ethylene oxide, propylene oxide) having 2 to 3 carbon atoms with the above polyhydric alcohol as an initiator so as to have the above molecular weight. Includes random and / or block copolymers) and the like.

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

Examples of the low molecular weight polyol include a dihydric alcohol, more preferably C2-C4 alkanediol, and even more preferably 1,4-butanediol.

If the low molecular weight polyol is the above, a molded product (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, less than 400, preferably 300 or less.

When the molecular weight of the low molecular weight polyol is within the above range, a molded product (described later) having excellent 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 a carbonyl group-containing macropolypoly such as a polyester polyol and a polycarbonate polyol.

Examples of the polyester polyol include a polycondensate obtained by reacting the above-mentioned low molecular weight polyol with a polybasic acid under known conditions.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Saturated aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, for example, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, for example, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid. Derived from aromatic dicarboxylic acids such as acids, eg, alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, and those carboxylic acids. Acid anhydrides such as oxalic acid anhydride, succinic acid anhydride, maleic anhydride, phthalic acid anhydride, 2-alkyl anhydride (C12 to C18) succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, and their carboxylic acids. Examples thereof include acid halides derived from acids and the like, such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, the above-mentioned low molecular weight polyol as an initiator, a hydroxyl group-containing vegetable oil fatty acid (for example, lysinoleic acid-containing castor oil fatty acid, 12-hydroxystearic acid). Examples thereof include a vegetable oil-based polyester polyol obtained by subjecting a hydroxycarboxylic acid such as (hydrogenated castor oil fatty acid, etc.) containing the above to a condensation reaction under known conditions.

Further, as the polyester polyol, for example, using the above-mentioned low molecular weight polyol (preferably dihydric alcohol) as an initiator, lactones such as ε-caprolactone and γ-valerolactone, and for example, L-lactide and D- Examples thereof include polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactides such as lactide, and lactone-based polyester polyols obtained by copolymerizing them with the above dihydric alcohol.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate or phenyl carbonate using the above-mentioned low molecular weight polyol (preferably the above-mentioned dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-. Examples thereof include an amorphous polycarbonate polyol obtained by copolymerizing a dihydric alcohol such as pentandiol, 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

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 stain resistance can be improved as compared with the case of using a carbonyl group-free polyol (for example, a carbonyl group-free polyol such as a polyether polyol).

More specifically, when a carbonyl group-free polyol (for example, a carbonyl group-free polyol such as a polyether polyol) is used instead of the carbonyl group-containing polyol, sweat, oils and fats adhering to the surface of the polyurethane resin, etc. It is inferior in stain resistance (penetration resistance), such as dirt penetrating inside the polyurethane resin. Therefore, problems occur in applications that require stain resistance (penetration resistance) (for example, smart device applications).

On the other hand, when a carbonyl group-containing polyol is used, a polyurethane resin having excellent stain resistance (penetration resistance) can be obtained, and various applications (for example, smart devices) that require stain resistance (penetration resistance) are required. It can be suitably used for various purposes.

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

Further, as the carbonyl group-containing polyol, polyester polyol is more preferably mentioned from the viewpoint of improving mechanical strength, stain resistance (penetration resistance) and discoloration resistance, and particularly preferably low molecular weight polyol and polybase. Examples thereof 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 particularly bloom resistance, stain resistance and stain resistance. From the viewpoint of discoloration, as described above, it is 1200 or less, preferably 1100 or less, and more preferably 1000 or less.

When the number average molecular weight of the carbonyl group-containing polyol is within the above range, it can have molding stability (demolding 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, and 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, and particularly preferably 800 or less, from the viewpoint of improving stain resistance and discoloration resistance.

Further, 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 a plurality of types of carbonyl group-containing polyols.

Further, as long as the excellent effect of the present invention is not impaired, a carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less, and other carbonyl group-containing polyols (carbonyl group-containing polyol having a number average molecular weight of less than 400, and a number average A carbonyl group-containing polyol having a molecular weight exceeding 1200) can also be used.

The other carbonyl group-containing polyol has, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less. It is particularly preferably 0 parts by mass.

Further, the carbonyl group-containing polyol may contain a cyclic carbonyl compound containing no hydroxyl group (hereinafter, may be 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 is, for example, a cyclic ester (for example, a lactone such as ε-caprolactone or γ-valerolactone). For example, L-lactide, lactide such as D-lactide), cyclic amide (for example, lactam such as β-lactam, γ-lactam, δ-lactam, etc.) and the like can be mentioned.

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

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

Further, the hydroxyl group-free cyclic carbonyl compound is, for example, poly as a raw material component (or a multimer thereof) that remains without ring-opening polymerization reaction when the above-mentioned polycaprolactone polyol is produced by ring-opening polymerization of lactones. May be contained in caprolactone polyol.

Further, the hydroxyl group-free cyclic carbonyl compound is obtained as a side reaction product when, for example, the above-mentioned 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 occur.

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. For example, it is 0% by mass or more, preferably more than 0% by mass, more preferably 0.1% by mass or more, 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 range, mechanical properties and bloom resistance can be improved, and further, molding stability (demolding property), transparency, and the like can be achieved. It is possible to improve stain resistance and discoloration resistance.

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 of the carbonyl group-containing polyol with respect to the total amount thereof. It is mol% or more, more preferably 15 mol% or more, for example, 75 mol% or less, preferably 65 mol% or less, and more preferably 50 mol% or less. 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.

In addition, the polyol component can contain other polyols (polypolymers excluding low molecular weight polyols and carbonyl group-containing polyols). 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.

Then, the polyurethane resin is obtained by a method for producing a polyurethane resin including a reaction step and a heat treatment step, as shown below.

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

In order to react each of the above components (polyisocyanate component, polyol component), for example, a known method such as a one-shot method or a prepolymer method is adopted. From the viewpoint of improving various physical properties, the prepolymer method is preferably adopted.

Specifically, in the prepolymer method, first, a polyisocyanate component and a macropolyol (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 a macropolyester (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 reaction temperature of the polyisocyanate component and the macropolyol (carbonyl group-containing polyol) is, for example, 50 ° C. or higher, for example 250 ° C. or lower, preferably 200 ° C. or lower, for example. , 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 higher, for example 120 ° C. or lower, preferably 100 ° C. or lower, for example. The reaction is carried out 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, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example, n-. Aliper hydrocarbons such as hexane, n-heptane, octane, eg, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, eg aromatic hydrocarbons such as toluene, xylene, ethylbenzene, 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-methoxybutyl acetate, ethyl-3-ethoxypropionate and other glycol ether esters. Classes, such as ethers such as diethyl ether, tetrahydrofuran, dioxane, for example, halide aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, for example. Examples thereof include polar aprotons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide.

Further, in the above polymerization reaction, for example, a known urethanization catalyst such as amines or an organometallic compound can be added, if necessary.

Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organic metal compound include tin acetate, tin octylate (tin octylate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyl. Organic tin compounds such as tin dineodecanoate, dioctyl tin dimercaptide, dioctyl tin dilaurylate, dibutyl tin dichloride, eg organic lead compounds such as lead octanate, lead naphthenate, eg organic nickel compounds such as nickel naphthenate, For example, an organic cobalt compound such as cobalt naphthenate, for example, an organic copper compound such as copper octate, for example, an organic bismuth compound such as bismuth octate (bismuth octylate), bismuth neodecanoate, and the like, preferably octyl. Examples include tin acid acid and bismuth octylate.

Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.

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 part by mass or more, preferably 0.01 part by mass or more, based on 10000 parts by mass of the total amount 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.

Further, in the above polymerization reaction, the unreacted polyisocyanate component and, when an organic solvent is used, the organic solvent can be removed by a known removing 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). It is preferably 1.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

More specifically, the blending ratio of each component in the prepolymer synthesis step is such that the polyisocyanate component is, for example, 5 parts by mass or more, preferably 10 parts by mass with respect to 100 parts by mass of the macropolyol (carbonyl group-containing polyol). More than parts, more preferably 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.

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. Therefore, 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, further from the viewpoint of transparency. Preferably, the above components are reacted until they reach 12.0% by mass or less. As a result, an isocyanate group-terminated prepolymer can be obtained.

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

Then, in this method, the isocyanate group-terminated prepolymer obtained above is reacted with a low molecular weight polyol to obtain a primary product of a polyisocyanate component and a polyol component (chain extension 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 the above-mentioned bulk polymerization or the above-mentioned solution polymerization.

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

The blending ratio of each component is, for example, 0.75 or more, preferably 0.9 or more, 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. As mentioned above, for example, it is 1.3 or less, preferably 1.1 or less.

More specifically, the blending ratio of each component in the chain extension step is such that the low molecular weight polyol is, for example, 1.0 part by mass or more, preferably 2.0 part by mass with respect to 100 parts by mass of the isocyanate group-terminated prepolymer. More than parts, more preferably 3.0 parts by mass or more, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

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

Further, in this reaction, the above-mentioned urethanization catalyst can be added, if necessary. The urethanization catalyst can be blended with the isocyanate group-terminated prepolymer and / or the low molecular weight polyol, or can be blended separately at the time of mixing them.

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

Further, in this stirring and mixing, for example, under an atmosphere of an inert gas (for example, nitrogen), the reaction temperature is, for example, 40 ° C. or higher, preferably 100 ° C. or higher, for example, 280 ° C. or lower, preferably 260 ° C. or lower. The reaction time is, for example, 30 seconds or more and 1 hour or less.

Further, at the time of stirring and mixing, the above-mentioned urethanization catalyst and organic solvent can be added at an appropriate ratio, if necessary.

The heat treatment step is a step of heat-treating the above-mentioned primary product to obtain a secondary product (reaction product after heat treatment, that is, 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 allowing it to stand at a predetermined heat treatment temperature for a predetermined heat treatment period, and then dried if necessary.

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

When the heat treatment temperature is less than the above lower limit, the molding stability (demolding property) is inferior, and the mechanical strength and stain resistance are also inferior.

Further, when the heat treatment temperature exceeds the above upper limit, the transparency, bloom resistance, discoloration resistance and the like are inferior.

On the other hand, when the heat treatment temperature is within the above range, it is excellent in molding stability (demolding property), transparency, bloom resistance and discoloration resistance, and can also have mechanical physical properties and stain resistance.

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

When the heat treatment period is less than the above lower limit, the molding stability (demolding property) is inferior, and the mechanical strength and stain resistance are also inferior.

Further, when the heat treatment period exceeds the above upper limit, the transparency, bloom resistance, discoloration resistance and the like are inferior.

On the other hand, when the heat treatment period is within the above range, it is excellent in molding stability (demolding property), transparency, bloom resistance and discoloration resistance, and can also have mechanical physical properties and stain resistance.

Thereby, a polyurethane resin can be obtained.

If necessary, the polyurethane resin contains known additives such as antioxidants, heat-resistant stabilizers, ultraviolet absorbers, light-resistant stabilizers, hydrolysis inhibitors (carbodiimide compounds, etc.), and plasticizers. , Antiblocking agents, mold release agents, pigments, dyes (brewing agents, etc.), lubricants (fatty acid amide-based lubricants, etc.), fillers, rust preventives, fillers, etc. can be added. These additives can be added during mixing, synthesis or post-synthesis of each component.

Examples of the antioxidant include, and are not particularly limited, known antioxidants (for example, described in the catalog manufactured by BASF Japan), and more specifically, for example, phenolic antioxidants and hinders. Examples include dophenolic antioxidants.

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

The ultraviolet absorber is not particularly limited, and examples thereof include known ultraviolet absorbers (for example, described in the catalog manufactured by BASF Japan). More specifically, for example, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. , Benzophenone-based ultraviolet absorbers and the like.

The light-resistant stabilizer is not particularly limited, and examples thereof include known light-resistant stabilizers (for example, described in the ADEKA catalog), and more specifically, for example, benzoate-based light stabilizers and hindered amine-based light stabilizers. 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

In such a method for producing a polyurethane resin, 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 or more and 1200 or less are included. The obtained primary product is heat-treated under predetermined conditions by reacting with the polyol component.

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

Specifically, the above polyurethane resin has 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 or more and 1200 or less). It has 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. Yes, for example, 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.

When the hard segment concentration of the polyurethane resin is within the above range, the molding stability (demolding property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance of the obtained molded product (described later) are improved. Can be made to.

The concentration of the hard segment (hard segment formed by the reaction of the polyisocyanate component and the low molecular weight polyol) of the polyurethane resin 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 of the hard segment phase shown by the following formula is T ₁ or more and the following formula. or less agglomeration temperature T ₂ of the hard segment phase indicated by.
Aggregation temperature of hard segment phase T ₁ (Unit: ° C): 80 + 1.2 × Hard segment concentration (mass%)
Aggregation temperature of hard segment phase T ₂ (unit: ° C): 115 + 1.2 × hard segment concentration (mass%)
When the cohesive temperature is equal to or higher than the above lower limit (T ₁ ), the cohesive force of the hard segment phase is not excessively weak, so that the molding stability (demolding property) and mechanical properties are excellent.

Further, when the agglomeration temperature is not more than the above upper limit (T ₂ ), the agglomeration force of the hard segment phase is not excessively high, so that the transparency, discoloration resistance, and bloom resistance are excellent.

Therefore, the polyurethane resin having the aggregation temperature in the above range is excellent in molding stability (demolding property), transparency, mechanical properties, bloom resistance and discoloration resistance.

The above calculation formula is not a theoretical formula, but an empirical formula (empirical formula) obtained by measuring the aggregation temperature of a polyurethane resin having excellent various physical properties.

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

When the aggregation temperature of the polyurethane resin is at least the above lower limit, molding stability (demolding property) and mechanical properties can be improved, and when the aggregation temperature of the polyurethane resin is at least the above upper limit, transparency and resistance It is also possible to improve discoloration and bloom resistance.

The aggregation temperature of the polyurethane resin can be measured by differential scanning calorimetry (DSC measurement) based on 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 (penetration resistance) as compared with the case of using a carbonyl group-free polyol. (Sex) can be improved.

Further, 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, while a polyol having a number average molecular weight of more than 1200 is not used as a raw material, or the amount used is the present invention. It is a small amount that does not interfere with the excellent effect of. Therefore, the cohesive force of the hard segment phase of the primary product becomes relatively low, and as a result, the molding stability and the mechanical properties become relatively low.

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

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

On the other hand, by adjusting the heat treatment conditions within the above range, the cohesive force of the hard segment phase can be appropriately improved, and deterioration of transparency, discoloration resistance, and bleed resistance can be suppressed.

By appropriately adjusting the cohesive force of the hard segment phase in this way, it is possible to obtain a polyurethane resin having molding stability (demolding property), transparency, mechanical properties, bloom resistance and discoloration resistance.

The cohesive force of the hard segment phase corresponds to the cohesive temperature. Therefore, if the aggregation temperature of the hard segment phase is within the above range (T ₁ or more and T ₂ or less), a polyurethane resin having excellent molding stability (demolding property), transparency, mechanical properties, bloom resistance and discoloration resistance can be used. Obtainable.

In this way, the polyurethane resin can have molding stability (demolding property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

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

Molded products include, for example, the above-mentioned polyurethane resin, heat compression molding and injection molding using a known molding method, for example, a specific mold, extrusion molding using a sheet winding device, for example, melt spinning molding and the like. It can be obtained by molding into various shapes such as pellet shape, plate shape, fibrous shape, strand shape, film shape, sheet shape, pipe shape, hollow shape, and box shape by the heat molding method of.

The obtained molded product can have molding stability (demolding property), transparency, mechanical properties, stain resistance, bloom resistance and discoloration resistance.

Further, in the above description, the polyurethane resin of the present invention and the method for producing the same are the thermoplastic polyurethane resin and the method for producing the same, but the polyurethane resin of the present invention and the method for producing the same are the thermosetting polyurethane resin and the method for producing the same. Can also be applied to.

In the thermosetting polyurethane resin and the method for producing the same, for example, the above-mentioned isocyanate group-terminated prepolymer, dihydric alcohol (1,4-butanediol, etc.) and trihydric alcohol (trimethylolpropane, etc.), and known fragrances are used. After reacting with a group diamine or the like (reaction step), for example, casting molding is performed, the obtained molded product is heat-treated under the above conditions (heat treatment step). Thereby, a thermosetting polyurethane resin and a molded product made of the thermosetting polyurethane resin can be obtained.

Further, such a thermosetting polyurethane resin, a method for producing the same, and a molded product made of the thermosetting polyurethane resin also have molding stability (demolding property), transparency, mechanical properties, stain resistance, and bloom resistance. It has both property and discoloration resistance.

Therefore, the molded product can be suitably used in the above-mentioned fields where various physical properties are required, and in particular, can be suitably used as a cover for 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 smart devices are usually formed with a removable resin cover, which is provided with molding stability (demoldability), transparency, mechanical properties, stain resistance, etc. Bloom resistance and discoloration resistance are required. Therefore, the above-mentioned polyurethane resin molded product is preferably used as a cover for a smart device.

In addition to the above-mentioned applications, molded products can be widely used industrially. Specifically, for example, transparent hard plastics, coating materials, adhesives, adhesives, cushioning materials, potting agents, and inks. , Binders, films (for example, paint protection films, films such as chipping films), sheets, bands (for example, bands such as watch bands, for example, transmission belts for automobiles, belts for various industrial transport belts (conveyor belts)) , Tubes (for example, parts such as medical tubes and catheters, as well as tubes such as air tubes, hydraulic tubes and electric wire tubes, for example, hoses such as fire hose), blades, speakers, sensors, LED sealing for high brightness Agents, organic EL parts, solar power generation parts, robot parts, android parts, wearable parts, clothing parts, sanitary goods, cosmetics, food packaging parts, sports goods, leisure goods, medical goods, nursing care goods, housing parts, acoustics Members, lighting members, chandeliers, outdoor lights, sealing materials, sealing materials, corks, packings, anti-vibration / seismic control / seismic isolation members, soundproofing members, daily necessities, miscellaneous goods, cushions, bedding, stress absorbing materials, stress relaxing materials, automobiles Interior / exterior parts, railway parts, aircraft parts, optical parts, OA equipment parts, miscellaneous goods surface protection members, semiconductor cushioning materials, self-healing materials, health appliances, glasses lenses, toys, cable sheaths, wire harnesses, telecommunications cables , Automotive wiring, computer wiring, industrial supplies such as curl cords, nursing care products such as sheets and films, sports products, leisure products, various miscellaneous goods, anti-vibration / vibration isolation materials, shock absorbers, optical materials, films such as light guide films , Auto parts, surface protective sheet, decorative sheet, transfer sheet, tape member such as semiconductor protective tape, golf ball member, string for tennis racket, agricultural film, wallpaper, antifogging agent, non-woven fabric, furniture such as mattress and sofa Supplies, clothing supplies such as brassieres and shoulder pads, medical supplies such as paper diapers, napkins, and cushioning materials for medical tape, cosmetics, sanitary supplies such as face wash puffs and pillows, shoe soles (outsole), midsole, cover materials, etc. Shoe supplies, body pressure distribution products such as pad and cushion for vehicles, hand-touchable materials such as door trims, instrument panels, gear knobs, heat insulating materials for electric refrigerators and buildings, shock absorbers such as shock absorbers , Cushioning materials, vehicle handles, automobile interior parts, automobile exterior parts, etc. It is suitably used in vehicle supplies, semiconductor manufacturing supplies such as chemical mechanical polishing (CMP) pads, and the like.

Furthermore, the above-mentioned molded products include covering materials (coating materials for films, sheets, belts, wires, electric wires, metal rotating equipment, wheels, drills, etc.), threads and fibers (tubes, tights, spats, sportswear, etc.). Threads and composite fibers used for swimwear, etc.), extrusion molding applications (extrusion molding applications such as goggles such as tennis and badminton and their convergence materials), slush molded products in powder form by micropelletization, artificial leather, skin, etc. Covers or core materials for seats, coated rolls (coated rolls such as steel), sealants, rollers, gears, balls, bats (goggles, basketball, tennis balls, volleyball, soft balls, bats, etc.) It may be in the form of foam molding of polyurethane resin.)), Mats, ski equipment, boots, tennis equipment, grips (grips for golf clubs and motorcycles), rack boots, wipers, seat cushion members, films for nursing care products. , 3D printer molded products, fiber reinforcement materials (fiber reinforcement materials such as carbon fiber, lignin, kenaf, nanocellulose fiber, glass fiber), safety goggles, sunglasses, glasses frame, ski goggles, swimming goggles, contact lenses, gas assist Foam molded products, shock absorbers, CMP polishing pads, dampers, bearings, dust covers, cutting valves, chipping rolls, high-speed rotating rollers, tires, watches, wearable bands, etc., recoverability and wear resistance due to repeated expansion and contraction, compression deformation, etc. Is preferably used in applications that require

Next, the present invention will be described based on Production Examples, Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.
1) Raw material <Polyisocyanate component (a)>
1,4-BIC: 1,4-bis (isocyanatomethyl) cyclohexane synthesized by the method described in Production Examples 1 to 5 described later 1,3-BIC: 1,3-bis (isocyanatomethyl) cyclohexane, commercial product Name: Takenate 600, MDI manufactured by Mitsui Chemicals, Inc .: Diphenylmethane diisocyanate, Trade name: Cosmonate PH, manufactured by Mitsui Chemicals SKC <carbonyl group-containing polyol (b)>
b-1) PBA # 300 (number average molecular weight 300): polybutylene adipate (polyester polyol) synthesized by the method described in Production Example 7, hydroxyl value = 373.8 mgKOH / 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 mgKOH / gb-3) PBA # 750 (number average molecular weight 750): by the method described in Production Example 7. Synthesized polybutylene adipate (polyester polyol), hydroxyl value = 149.5 mgKOH / gb-4) PBA # 800 (number average molecular weight 800): Polybutylene adipate (polyester polyol) synthesized by the method described in Production Example 7, hydroxyl group Value = 140.2 mgKOH / gb-5) PBA # 1000 (number average molecular weight 1000): polybutylene adipate (polyester polyol), trade name; Takelac U-2410, hydroxyl value = 112.2 mgKOH / g, manufactured by Mitsui Chemicals, Inc. b -6) PBA # 2000 (number average molecular weight 2000): polybutylene adipate (polyester polyol), trade name; Takelac U-2420, hydroxyl value = 56.2 mgKOH / g, b-7 manufactured by Mitsui Chemicals, Inc. PCL # 1000 ( Number average molecular weight 1000): Polycaprocton polyol, trade name; PLACCEL210N, hydroxyl value = 112.1 mgKOH / g, Daicel b-8) PCD # 1000 (number average molecular weight 1000): polycarbonate polyol, trade name; ETERNAL COL UH -100, hydroxyl value = 112.2 mgKOH / g, manufactured by Ube Kosan Co., Ltd. b-9) PCD # 2000 (number average molecular weight 2000): polycarbonate polyol, trade name; ETERNCOL UH-200D, hydroxyl value = 55.9 mgKOH / g, Ube Kosan Co., Ltd. b-10) PEA # 550 (number average molecular weight 550): polyethylene adipate (polyester polyol), trade name; Takelac U-550, hydroxyl value = 204.0 mgKOH / g, Mitsui Kagaku Co., Ltd. b-11) PEA # 1000 (number average molecular weight 1000): polyethylene adipate (polyester polyol), trade name; Nipponlan 4002, hydroxyl value = 112.2 mgKOH / g, Toso Co., Ltd. b-12) PBS # 1000 (number average molecular weight 1000): manufactured Polybutylene succinate (polyester polyol) synthesized by the method described in Example 8, hydroxyl value = 112.2 m gKOH / g
<Carbonyl group-free polyol (b')>
b-13) PTMEG (number average molecular weight 1000): polytetramethylene ether glycol, trade name; PTG1000, hydroxyl value = 112.0 mgKOH / g, manufactured by Hodogaya Chemical Co., Ltd. <Low molecular weight polyol (c)>
1,4-BD: 1,4-butanediol, trade name; 1,4-butanediol,
1,3-PDO manufactured by Mitsubishi Chemical Corporation: 1,3-propanediol, trade name; Sastera TM propanediol, manufactured by DuPont <Urethane catalyst>
Tin-based catalyst: tin octylate (II), trade name; Stanoct, manufactured by IP Corporation <catalyst diluent>
Diisononyl adipate: Product name: DINA, manufactured by Daihachi Chemical Industry Co., Ltd. <Stabilizer>
Antioxidant: Hindered phenol compound, trade name; Irganox 245, BASF Japan UV absorber: Benzotriazole compound, trade name; Tinubin 234, BASF Japan light resistance stabilizer: Hinderdamine compound, trade name; LA- 72, ADEKA antioxidant: carbodiimide compound, trade name; STAVACZOR I-LF, Rankses <dye>
Anthraquinone-based bluing agent: Trade name; Plasto Blue8514, manufactured by Arimoto Chemical Industry Co., Ltd. << Quantification of hydroxyl group-free cyclic carbonyl compound >>
If necessary, stripping-treated carbonyl group-free polyol or carbonyl group-containing polyol was precisely weighed in 0.2 g and dissolved in 10 mL of dichloromethane solution to which di-n-butyl phthalate (DBP) was added as an internal standard.

This solution was measured by GC-MS / FID under the following conditions, and in the obtained GC-MS spectrum, the hydroxyl group-free cyclic carbonyl compound was assigned to the retention time described below. Then, the content (mass%) by DBP conversion was calculated from the FID detection area ratio.
Measuring device: Agent7890A / 5975C MSD / FID
Column: VF5ms
Carrier gas: He (pressure control mode: 23.602psi)
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
[Attribution of GC-MS spectrum]
<Polybutylene adipate (polyester polyol)>
Cyclic ester formed from one molecule of adipic acid and one molecule of 1,4-butanediol: 10.7 minutes Cyclic ester formed of two molecules of adipic acid and two molecules of 1,4-butanediol: 24. Cyclic ester formed from 3 or more molecules of adipic acid and 3 or more molecules of 1,4-butanediol: Not detected due to high boiling point.
<Polyethylene adipate (polyester polyol)>
Cyclic ester formed from 1 molecule of adipic acid and 1 molecule of ethylene glycol: 7.6 minutes 2 molecules of adipic acid and cyclic ester formed from 2 molecules of ethylene glycol: 20.4 minutes 3 or more molecules of adipic acid And cyclic ester formed from 3 or more molecules of ethylene glycol: Not detected due to high boiling point.
<Polybutylene succinate (polyester polyol)>
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 3 or more molecules of succinic acid and 3 or more molecules of 1,4-butanediol: Not detected due to high boiling point.
<Polycaprolactone diol>
Caprolactone monomer: 5.8 minutes Caprolactone dimer: 13.2 minutes Caprolactone trimmer: 21.0 minutes Caprolactone tetramer or more: 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 minutes Cyclic polycarbonate formed from 3 or more molecules of carbonate group and 3 or more molecules of 1,6-hexanediol Compound: 26.1 minutes Cyclic polycarbonate compound formed from 4 or more molecules of carbonate group and 4 or more molecules of 1,6-hexanediol: Not detected due to high boiling point.

2) Production of polyurethane resin <Manufacture 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)))
The 1,4-BIC (2) described in Production Example 2 described later was filled in an oil can while purging with nitrogen, and then allowed to stand in an incubator at 1 ° C. for 2 weeks. The obtained coagulated product was quickly filtered under reduced pressure using a 4 μm mesh membrane filter to remove the liquid phase portion to obtain a solid phase portion. The above operation was repeated for the solid phase portion to obtain 1,4-BIC (1). The purity of 1,4-BIC (1) measured by gas chromatography was 99.9%, the hue measured by APHA was 5, and the trans / cis ratio measured by ¹³ C-NMR 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 of JP2014-55229A, a yield of 1,4-bis (aminomethyl) cyclohexane having a purity of 99.5% or more and a trans / cis ratio of 98/2 is 92%. Obtained at a rate.

Then, in accordance with the description of Production Example 1 of Japanese Patent Application Laid-Open No. 2014-55229, a cold two-stage phosgenation method was carried out under pressure using this 1,4-bis (aminomethyl) cyclohexane as a raw material. , 4-BIC (2) was obtained in 382 parts by mass.

The obtained 1,4-BIC (2) had a purity of 99.9% by gas chromatography measurement, a hue of 5 by APHA measurement, and a trans / cis form ratio of 98/2 by ¹³ C-NMR measurement. .. 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 tube, and a nitrogen introduction tube, 789 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later (6) was charged in 211 parts by mass and stirred at room temperature for 1 hour under a nitrogen atmosphere. The obtained 1,4-BIC (3) had a purity of 99.9% by gas chromatography measurement, a hue of 5 by APHA measurement, and a trans / cis ratio of 86/14 by ¹³ C-NMR measurement. 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)))
561 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube. (6) was charged in 439 parts by mass and stirred at room temperature for 1 hour under a nitrogen atmosphere. The obtained 1,4-BIC (4) had a purity of 99.9% by gas chromatography measurement, a hue of 5 by APHA measurement, and a trans / cis ratio of 73/27 by ¹³ C-NMR measurement. 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)))
474 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube. 526 parts by mass of (6) was charged, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. The obtained 1,4-BIC (5) had a purity of 99.9% by gas chromatography measurement, a hue of 5 by APHA measurement, and a trans / cis ratio of 68/32 by ¹³ C-NMR measurement. 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)))
¹³ Production Example 1 of JP-A-2014-55229, using 1,4-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) having a trans / cis ratio of 41/59 as measured by C-NMR as a raw material. According to the description, 388 parts by mass of 1,4-BIC (6) was obtained.

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

<Manufacturing of polybutylene adipates (b-1) to (b-4)>
Production Example 7 (Method for producing polybutylene adipate (polyester polyol))
Adipic acid and 1,4-butanediol were placed in a four-necked flask equipped with a thermometer, a stirrer, and a Liebig condenser, the temperature was raised to 180 ° C., and the polycondensation reaction was carried out under a nitrogen stream. The temperature was raised to 220 ° C. When the acid value reached 15 mgKOH / g, stannoct was added as a catalyst, and the polycondensation reaction was continued at the same temperature until the acid value reached less than 1 mgKOH / g. Then, it cooled and obtained polybutylene adipate.

<Manufacturing of polybutylene succinate (b-12)>
Production Example 8 (Method for producing polybutylene succinate (polyester polyol))
Succinic acid and 1,4-butanediol were placed in a four-necked flask equipped with a thermometer, a stirrer, and a Liebig condenser, the temperature was raised to 150 ° C., and the polycondensation reaction was carried out under a nitrogen stream. The temperature was raised to 220 ° C. When the acid value reached 10 mgKOH / g, stannoct was added as a catalyst, and the polycondensation reaction was continued at the same temperature until the acid value reached less than 1 mgKOH / g. Then, it cooled and obtained polybutylene succinate.

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

At this time, the content of the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol (b) after the stripping treatment was measured by the above method.
Urethaneization reaction A four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen introduction tube for the polyisocyanate component (a) and the carbonyl group-containing polyol (b) according to the formulations shown in Tables 1 to 3. Further, Stavaxol I-LF, which was 0.2% by mass based on the total amount thereof, was charged and stirred at 80 ° C. for 1 hour under a nitrogen atmosphere.

After that, tin octylate (trade name: Stanoct, manufactured by IP Corporation) diluted to 4% by mass with DINA (manufactured by Daihachi Chemical Co., Ltd.) was added to the polyisocyanate component (a) and the carbonyl group-containing polyol (b). It was added so that the amount of the catalyst was 5 ppm with respect to the total amount.

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

Synthesis example 18
In accordance with the formulations shown in Tables 1 to 3, PTMEG (b-13, number average molecular weight 1000), which is a carbonyl group-free polyol (b'), was used instead of the carbonyl group-containing polyol (b), and stavaxol I-. 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
According to the formulations shown in Tables 1 to 3, MDI (diphenylmethane diisocyanate) was used as the polyisocyanate component (a), and the same method as in Synthesis Example 1 was used except that a catalyst was not used. (T) was obtained.

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

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

Then, 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 of 1,4-butanediol (1,4-BD) as the low molecular weight polyol is 1.01. It was weighed in a stainless steel cup and the temperature was adjusted to 80 ° C.

Next, the isocyanate group-terminated prepolymer was weighed in another stainless steel cup, and 0.3 parts by mass of Irganox 245 (BASF heat-resistant stabilizer) was added to the total amount of the isocyanate group-terminated prepolymer and 1,4-BD. Chinubin 234 (BASF UV absorber) 0.1 parts by mass, Adecastab LA-72 (ADEKA HALS) 0.1 parts by mass, and Kao Wax EB-P (Kao Chemical Co., Ltd. fatty acid amid lubricant) 0 .1 part by mass was added to the isocyanate group-terminated prepolymer.

Further, Plasto Blue8514 diluted to 0.5% by mass with DINA (manufactured by Daihachi Chemical Co., Ltd.) was added to the isocyanate group-terminated prepolymer so as to be 0.5 ppm as Plasto Blue8514.

In addition, tin octylate (trade name: Stanoct, manufactured by IP Corporation) diluted to 4% by mass with DINA (manufactured by Daihachi Chemical Co., Ltd.) in advance is added to the isocyanate group-terminated prepolymer so as to have a catalytic amount of 10 ppm. Was added to.

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

Next, 1,4-BD, which was measured in advance and adjusted to 80 ° C., was added to the isocyanate group-terminated prepolymer, and the mixture was 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 was poured into a Teflon (registered trademark) vat whose temperature was adjusted to 150 ° C. in advance, reacted at 150 ° C. for 2 hours, then lowered to 100 ° C. and the reaction was continued for 20 hours to obtain a polyurethane resin. Primary products (A)-(Z), (AC)-(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 bat, cut into dice with a bale cutter, and pulverized. The dice-shaped resin was crushed with a machine to obtain crushed pellets.

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

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

Example 19
Polyurethane resin (AE) pellets were obtained in the same manner as in Example 1 except that the preheating temperature of the isocyanate group-terminated prepolymer was set to 120 ° C. according to the formulation shown 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 except that the NCO index was 0.98 according to the formulation shown in Table 6.

Comparative Example 11
Polyurethane resin (AA) pellets were obtained in the same manner as in Example 1 except that 1,3-propanediol (PDO) was used as the low molecular weight polyol according to the formulation shown in Table 7.

Comparative Example 12
Pellets of polyurethane resin (AB) were obtained in the same manner as in Example 1 except that no catalyst was used according to the formulation shown in Table 7.

3) Molding of evaluation sample <Polyurethane sheet molding method>
The obtained pellets of polyurethane resins (A) to (AJ) were previously dried under vacuum and reduced pressure at 80 ° C. for 12 hours, and then used by an injection molding machine (model: NEX-140, manufactured by Nissei Resin Industry Co., Ltd.). Surface condition under the conditions of 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 cured under constant temperature and humidity conditions of room temperature of 23 ° C. and relative humidity of 55% for 7 days to obtain a polyurethane sheet. ..

4) Evaluation <Sheet surface>
The demolding time during injection molding was unified to 15 seconds, and the surface condition of the sheet after demolding was evaluated in the following five stages of evaluations 5 to 1.
Evaluation 5: A uniform sheet can be obtained with no sticking to the mold at the time of demolding and no surface roughness.
Evaluation 4: The sheet is stuck to the mold, but the peeling mark on the sheet surface is less than 20% of the entire sheet.
Evaluation 3: The sheet is stuck to the mold, and the peeling mark on the sheet surface is 20% or more and less than 50% of the entire sheet.
Evaluation 2: The sheet is stuck 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:%)>
Using Haze Meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., model: NDH 2000), 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.

<Tear strength (unit: kN / m)>
From a polyurethane sheet having a thickness of 1 mm obtained by injection molding, a right-angled tear test piece prepared according to JIS K7311 (1995) was used for measurement under a condition of a tear rate of 300 mm / min.

<Breaking strength (unit: MPa) and breaking elongation (unit:%)>
From a 1 mm thick polyurethane sheet obtained by injection molding, a JIS-3 dumbbell type test piece prepared according to JIS K7311 (1995) was used for measurement under the conditions of a tensile speed of 300 mm / min and a distance between marked lines of 20 mm.

<Measurement of polyurethane aggregation temperature by differential scanning calorimetry (DSC) (unit: ° C)>
The measurement was performed using a differential scanning calorimeter (manufactured by SII Nanotechnology, trade name: EXSTAR6000 PC station and DSC220C).

A polyurethane sheet of about 8 mg was cut into thin pieces so as to be in close contact with an aluminum pan as much as possible. This aluminum pan covered with a cover and crimped was used as a measurement sample (sample). Similarly, the sample obtained by collecting alumina was used 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 of 40 NmL / min, hold at the same temperature for 5 minutes, and then 10 The temperature was raised to 270 ° C. at a rate of ° C./min. After holding at 270 ° C. for 5 minutes, the mixture was cooled to −70 ° C. at a rate of 10 ° C./min. The temperature of the exothermic peak appearing during this cooling was defined as the aggregation temperature of polyurethane.

<Stain resistance>
A test piece having a size of 20 × 60 mm was cut out from a polyurethane sheet having a thickness of 1 mm, immersed in a red oil-based marker ink (manufactured by Teranishi Chemical Industry Co., Ltd.) for 1 hour, and then washed with distilled water.
The cut cross section was observed using a digital microscope (manufactured by KEYENCE CORPORATION, trade name: VHX-6000), and the thickness soaked with the marker ink was measured. The smaller the thickness of the marker ink, the better the stain resistance.

<Bloom resistance>
A 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 the following five stages of evaluations 5 to 1.
Evaluation 5: No powder blowing phenomenon occurs within 28 days of the test.
Evaluation 4: The powder blowing phenomenon occurs within 28 days of the test.
Evaluation 3: The powder blowing phenomenon occurs within 14 days of the 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 hue>
Using a color difference meter (Color Ace MODEL TC-1 manufactured by Tokyo Denshoku Co., Ltd.), the yellowness b ^* of a 1 mm thick polyurethane sheet obtained by injection molding was measured. Note that b ^* is generally used as an index of the hue of the polyurethane resin.

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

The Δb (change in 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, Δb is generally used as an index of discoloration property of the polyurethane resin.

<UV discoloration resistance>
A test piece having a size of 20 x 60 mm is cut out from a 1 mm thick polyurethane sheet, and a QUV weathering tester (made by Suga Test Instruments Co., Ltd., UV fluorescent lamp weather meter FUV) equipped with an ultraviolet fluorescent lamp is used at 60 ° C. Conditions of relative humidity of 10% and ultraviolet (wavelength 270 to 720 nm) irradiation intensity of 28 W / m ² and conditions of 50 ° C., relative humidity of 95% and no ultraviolet irradiation were repeated every 4 hours for 48 hours for 6 cycles.

The Δb (change in 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, Δb is generally used as an index of polyurethane resin discoloration.

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

Then, using an injection molding machine, a smartphone cover having a thickness of 1 mm was obtained using the polyurethane resin of Example 4.

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

Similarly, 1 hour in a red artificial sweat solution to which 1 mL of a red aqueous dye (manufactured by KOKUYO, trade name: IP-540R) is added to 100 mL of artificial sweat according to JIS-L0848 (2004). After soaking, it was washed with distilled water. The cut cross section was observed using a digital microscope (manufactured by KEYENCE CORPORATION, trade name: VHX-6000), and the thickness of the red artificial sweat liquid soaked was measured and found to be 55 μmt.

The above invention has been provided as an exemplary embodiment of the present invention, but this is merely an example and should not be construed in a limited manner. Modifications of the present invention that are apparent to those skilled in the art are included in the claims below.

The polyurethane resin, the molded product, and the method for producing the polyurethane resin of the present invention can be suitably used in the cover of smart devices such as smartphones, tablet computers (tablet PCs), and slate computers (slate PCs).

Claims (8)

Polyisocyanate component containing bis (isocyanatomethyl) cyclohexane,
It is a reaction product 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 or more and 1200 or less.
The aggregation temperature measured by the differential scanning calorimeter is
The aggregation temperature of the hard segment phase shown by the following formula is T ₁ or higher, and
A polyurethane resin, characterized in that the aggregation temperature of the hard segment phase shown by the following formula is T ₂ or less.
Aggregation temperature of hard segment phase T ₁ (Unit: ° C): 80 + 1.2 × Hard segment concentration (mass%)
Aggregation temperature of hard segment phase T ₂ (unit: ° C): 115 + 1.2 × hard segment concentration (mass%) The polyurethane resin according to claim 1, wherein the concentration of the cyclic carbonyl compound containing no 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 contains 1,4-bis (isocyanatomethyl) cyclohexane. The polyurethane resin according to claim 3, wherein the 1,4-bis (isocyanatomethyl) cyclohexane contains a trans compound in a proportion of 70 mol% or more and 99 mol% or less. The polyurethane resin according to claim 3, wherein the content ratio of 1,4-bis (isocyanatomethyl) cyclohexane to the bis (isocyanatomethyl) cyclohexane is 85% by mass or more. A molded product, which comprises the polyurethane resin according to claim 1. The molded product according to claim 6, which is a cover for a smart device. Polyisocyanate component containing bis (isocyanatomethyl) cyclohexane,
A reaction step of 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 to obtain a primary product.
A heat treatment step of heat-treating the primary product to obtain a polyurethane resin is provided.
A method for producing a polyurethane resin, wherein the heat treatment conditions in the heat treatment step are 50 ° C. or higher and 100 ° C. or lower, 3 days or longer and 10 days or lower.