KR20200041348A - Polyurethane resin, molded article, and method for manufacturing polyurethane resin - Google Patents

Abstract

To the reaction product of a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane and a polyol component comprising 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. In this case, the aggregation temperature measured by the differential scanning calorimeter is at least the aggregation temperature T ₁ on the hard segment represented by the calculation formula, and the aggregation temperature T ₂ on the hard segment indicated by the calculation formula.
Aggregation temperature T ₁ on the hard segment (unit: ℃): 80 + 1.2 × hard segment concentration (% by mass)
Aggregation temperature T ₂ on the hard segment (unit: ℃): 115 + 1.2 × hard segment concentration (mass%)

Description

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

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

Thermoplastic polyurethane resins (TPU) are generally rubber elastomers obtained by reaction of polyisocyanates, high molecular weight polyols and low molecular weight polyols, and are formed by reaction of polyisocyanates and low molecular weight polyols. It has a hard segment to be formed, and a soft segment formed by the reaction of polyisocyanate and high molecular weight polyol. A molded article made of a polyurethane resin can be obtained by melt-molding such a thermoplastic polyurethane resin.

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

International Publication WO2015 / 046369 pamphlet

On the other hand, molded products of polyurethane resins require various properties depending on their use, for example, in the field of smart devices, such as cover, molding stability (deformation), transparency, mechanical properties, contamination resistance, bloom resistance It is required to have both sex and discoloration resistance.

However, the polyurethane resin described in Patent Document 1 may not have sufficient molding stability (deformation), transparency, mechanical properties, fouling resistance, bloom resistance, and discoloration resistance depending on the application.

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

The present invention [1] is a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, a low molecular weight polyol having a molecular weight of less than 400, and a polyol containing a carbonyl group having a number average molecular weight of 400 or more and 1200 or less. It is the reaction product of the polyol component containing, and the aggregation temperature measured by the differential scanning calorimeter is the aggregation temperature of the hard segment phase T ₁ or more represented by the following calculation formula, and the aggregation temperature of the hard segment phase represented by the following calculation formula Polyurethane resin which is T ₂ or less is included.

Aggregation temperature T ₁ on the hard segment (unit: ℃): 80 + 1.2 × hard segment concentration (% by mass)

Aggregation temperature T ₂ on the hard segment (unit: ℃): 115 + 1.2 × hard segment concentration (mass%)

The present invention [2] includes 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.

In the present invention [3], the poly according to [1] or [2], wherein the bis (isocyanatomethyl) cyclohexane contains 1,4-bis (isocyanatomethyl) cyclohexane. Contains urethane resin.

In the present invention [4], the polyurete according to the above [3], wherein the 1,4-bis (isocyanatomethyl) cyclohexane contains a trans body in a proportion of 70 mol% or more and 99 mol% or less. It contains phosphorus resin.

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

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

The present invention [7] includes the molded article described in [6] above, which is a cover of a smart device.

The present invention [8] is a polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, a low molecular weight polyol having a molecular weight of less than 400, and a polyol containing a carbonyl group having a number average molecular weight of 400 or more and 1200 or less. It comprises a reaction step of obtaining a primary product by reacting a polyol component containing, 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 for producing a polyurethane resin.

As the raw material (high molecular weight polyol), the polyurethane resin and the molded article of the present invention are carbonyl group-containing polyols having a number average molecular weight of 400 or more and 1200 or less.

That is, the number average molecular weight of the high molecular weight polyol is limited so as not to be excessively large, whereby the concentration of the urethane group in the polyurethane resin is improved.

In addition, the polyurethane resin of the present invention and its molded article have a moderately adjusted aggregation temperature on the hard segment, and as a result, molding stability (deformation), transparency, mechanical properties, contamination resistance, bloom resistance and discoloration. You can have sex.

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 on the hard segment of the obtained polyurethane resin can be appropriately adjusted. As a result, a polyurethane resin having both molding stability (deforming property), transparency, mechanical properties, fouling resistance, bloom resistance and discoloration resistance can be obtained.

The polyurethane resin of the present invention is, for example, a thermoplastic polyurethane resin, and as described later, the polyisocyanate component and the polyol component are reacted, and then subjected to heat treatment (heat curing). Is obtained by

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, preferred. It is a symmetrical structure of 1,4-bis (isocyanatomethyl) cyclohexane, from the viewpoint of improving the molding stability (deformation), mechanical properties, stain resistance and discoloration resistance of the polyurethane resin. Can be mentioned.

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, it is 70% by mass or more, more preferably 80% by mass or more, particularly preferably 85% by mass or more, and usually 100% by mass or less.

To 1,4-bis (isocyanatomethyl) cyclohexane, cis-1,4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis 1,4 form), and trans-1, There is a stereoisomer of 4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,4 form), and in the present invention, 1,4-bis (isocyanatomethyl) cyclohexane is trans 1,4 body, 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, It is preferably contained in a proportion of 99 mol% or less, more preferably 96 mol% or less, and more preferably 90 mol% or less. In other words, since the total amount of 1,4-bis (isocyanatomethyl) cyclohexane is 1,4 trans and 1,4 cis, 100 mol%, cis 1,4 is, for example, , 0.2 mol% 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 It is contained in a proportion of 20 mol% or less, more preferably 15 mol% or less.

When the content ratio of the trans 1,4 body is more than the above lower limit, it is possible to improve the molding stability, mechanical properties, stain resistance and discoloration resistance. In addition, if the content ratio of the trans 1,4 body is equal to or less than 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 the international publication WO2009 / 051114 pamphlet or the like.

Moreover, bis (isocyanatomethyl) cyclohexane can also be prepared as a modified substance in the range which does not inhibit the excellent effect of this invention.

As a modified product of bis (isocyanatomethyl) cyclohexane, for example, a multimer of bis (isocyanatomethyl) cyclohexane (dimer (for example, uretdione modified material), Trimers (e.g., isocyanurate-modified substances, iminooxadiazinedione-modified substances, etc.), biuret-modified substances (e.g., bis (isocyanatomethyl) cyclohexane and water) Biuret modified products produced by the reaction, etc., allophanate modified products (for example, allophanate produced from the reaction of bis (isocyanatomethyl) cyclohexane and monohydric alcohol or dihydric alcohol) Modified substance, etc.), polyol modified substance (e.g., polyol modified substance (adduct) produced from the reaction of bis (isocyanatomethyl) cyclohexane and trivalent alcohol), oxadiazinetrione modified substance ( For example, rain (Isocyanatomethyl) cyclohexane and oxadiazine triions produced by the reaction of carbon dioxide gas, carbodiimide modified products (e.g., bis (isocyanatomethyl) cyclohexane decarbonization) Carbodiimide modified products produced by a condensation reaction, etc.) and the like.

In addition, the polyisocyanate component has other polyisocyanates, for example, aliphatic polyisocyanates, aromatic polyisocyanates, and aromatics, in the range that does not impair the excellent effects of the present invention. Aliphatic polyisocyanate, etc. can be contained as an arbitrary component.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate. Cyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate Cyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Anate, 1,6,11-undecamethylene triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl jade Tane, 2,5 , 7-trimethyl-1,8-diisocyanate-5-isocyanatomethyl octein, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4- Butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocya Nate hexanoate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate, bis (4-isocyanate-n-butylidene) pentaerythritol, 2,6-dia And isocyanate methyl caproate.

Moreover, alicyclic polyisocyanate (except bis (isocyanatomethyl) cyclohexane) is contained in aliphatic polyisocyanate.

As an alicyclic polyisocyanate (except bis (isocyanatomethyl) cyclohexane), for example, isophorone diisocyanate (IPDI), trans, trans-, trans, cis-, And 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'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocy Anate, 2,5-diisocyanatomethylbicyclo [2,2,1] -heptane, its isomer 2,6-diisocyanatomethylbicyclo [2,2,1] -hep Tane (NBDI), 2-isocyanatomethyl-2- (3-isocyane Itopropyl) -5-isocyanatomethylbicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyane Itomethylbicyclo- [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-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, etc. Can be mentioned.

Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI ), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and these di And any isomer mixture of phenylmethane diisocyanate (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-tetramethyl xylylene dia And isocyanates or mixtures thereof (TMXDI).

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

In addition, other polyisocyanates may be prepared as a modified material within a range not inhibiting the excellent effect of the present invention.

Examples of other polyisocyanate modified products include, for example, other polyisocyanate multimers (dimers, trimers, etc.), biuret modified products, allophanate modified products, and polyol modified products, And oxadiazine triion modified products, carbodiimide modified products, and the like.

The content ratio in the case of containing other polyisocyanates is, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass with respect to the total amount of polyisocyanate components. % Or less, more preferably 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 contains a low molecular weight polyol having a molecular weight of less than 400 and a polyol containing a molecular weight of 400 or more and 1200 or less, and preferably, essentially contains a low molecular weight polyol having a molecular weight of less than 400 and a carbonyl group having a molecular weight of 400 or more and 1200 or less. It is made of polyol.

On the other hand, when the polyol component has a molecular weight distribution, a number average molecular weight is employed. In addition, in such a case, the number average molecular weight can be determined by measurement by GPC method or hydroxyl value of each component of the polyol component and prescription (hereinafter the same applies).

As a low molecular weight polyol, the compound (monomer) which has 2 or more hydroxyl groups in a molecule | numerator and has a molecular weight of 50 or more and less than 400 is mentioned, for example. Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol (1,4-butanediol, 1,4-BD ), C2-C4 alkanediol such as 1,3-butylene glycol, 1,2-butylene glycol, for example, 1,5-pentanediol, 1,6-hexanediol , Neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptein, alkanes (C7 to C20) di All, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A and its hydrogenated products, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-benzenediol , Dihydric alcohols such as 1,3-benzenediol and 1,4-benzenediol, for example, glycerin, trimethylolpropane, trieye Trihydric alcohols such as propanolamine, for example, tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, for example, pentahydric alcohols such as xylitol, for example sorbitol, mannitol Hexavalent alcohols such as Alitol, Iditol, Dulcitol, Altritol, Inositol, and Dipentaerythritol, for example, Hexavalent alcohols such as Perseitol, for example, 8-valent alcohols such as sucrose And polyhydric alcohols.

In addition, as the low molecular weight polyol, a polyoxyalkylene polyol (random and / or block) in which the above-mentioned polyhydric alcohol is used as an initiator and an addition reaction of alkylene oxide (ethylene oxide, propylene oxide) having 2 to 3 carbon atoms to the above molecular weight is achieved. Copolymers).

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

As the low-molecular-weight polyol, preferably, a dihydric alcohol, more preferably C2 to C4 alkanediol, and more preferably 1,4-butanediol is mentioned.

If the low molecular weight polyol is the 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.

When the molecular weight of the low molecular weight polyol is within the above range, a molded article (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.

Examples of the carbonyl group-containing polyol include carbonyl group-containing macropolyols such as polyester polyols and polycarbonate polyols.

As a polyester polyol, the polycondensate obtained by making said low molecular weight polyol and polybasic acid react under known conditions, for example is mentioned.

As polybasic acid, for example, oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethyl Saturated aliphatic dicarboxylic acids such as glutaric acid, azelaic acid, and sebacic acid, for example, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, such as orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, for example, alicyclic dicarboxylic acids such as hexahydrophthalic acid, such as dimer acid, hydrogenated dimer acid, and other carboxylic acids such as hetic acid, and acid anhydrides derived from these carboxylic acids , For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12 to C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and further these carboxylates Acid halide derived from an acid such as, for example, there may be mentioned oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride.

Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, the low molecular weight polyol described above as an initiator, a hydroxyl group-containing vegetable oil fatty acid (for example, castor containing ricinoleic acid) And vegetable oil-based polyester polyols obtained by condensation reaction of hydroxycarboxylic acids such as free fatty acids and hydrogenated castor oil fatty acids containing 12-hydroxystearic acid under known conditions.

Further, as the polyester polyol, for example, the above-mentioned low molecular weight polyol (preferably divalent alcohol) as an initiator, for example, lactones such as ε-caprolactone, γ-valerolactone, and the like For example, polycaprolactone polyols, polyvalerolactone polyols obtained by ring-opening polymerization of lactides such as L-lactide and D-lactide, and lactone-based polyesters such as copolymerization of the divalent alcohols therewith And polyols.

As the polycarbonate polyol, for example, the ring-opening polymerization product of ethylene carbonate or phenyl carbonate using the low-molecular-weight polyol (preferably the divalent alcohol) as an initiator, for example, 1,4-butanediol, 1 And an amorphous polycarbonate polyol obtained by copolymerization of a divalent alcohol such as, 5-pentanediol, 3-methyl-1,5-pentanediol or 1,6-hexanediol, and a ring-opening polymerization product. have.

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

By using a carbonyl group-containing polyol, various physical properties such as fouling resistance can be improved compared to a case where a polyol not containing a carbonyl group (for example, a polyol containing no carbonyl group such as polyether polyol) is used. .

More specifically, when a polyol that does not contain a carbonyl group (for example, a polyol that does not contain a carbonyl group such as polyether polyol) is used instead of the carbonyl group-containing polyol, it is attached to the surface of the polyurethane resin. Pollution resistance (permeation resistance) is inferior, such as contamination such as sweat and oil permeating into the polyurethane resin. Therefore, a problem arises in a use (e.g., a smart device use) in which contamination resistance (permeability) is required.

On the other hand, when a carbonyl group-containing polyol is used, it is possible to obtain a polyurethane resin excellent in fouling resistance (permeation resistance), and various uses (for example, smart device use) requiring fouling resistance (permeability) Etc.).

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

Further, as the carbonyl group-containing polyol, from the viewpoint of improving mechanical strength, fouling resistance (permeation resistance) and discoloration resistance, polyester polyols are more preferable, particularly preferably low molecular weight polyols and polybasic acids. And polycaprolactone polyols.

The number average molecular weight of the carbonyl group-containing polyol is 400 or more, and preferably 600 or more, as described above, particularly in view of molding stability and mechanical properties, and furthermore, particularly in terms of bloom resistance, fouling resistance, and discoloration resistance. , As described above, 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 within the above range, it is possible to combine molding stability (deformation), transparency, mechanical properties, stain resistance, bloom resistance, and discoloration resistance.

Further, 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 the molding stability and mechanical strength.

In addition, 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 the stain resistance and discoloration resistance.

In addition, the number average molecular weight of the carbonyl group-containing polyol represents 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.

Moreover, in the range which does not impair the excellent effect of the present invention, together with the carbonyl group-containing polyol having a number average molecular weight of 400 or more and 1200 or less, other carbonyl group-containing polyols (carbonyl group-containing polyols having a number average molecular weight of less than 400, and water) It is also possible to use carbonyl group-containing polyols having an average molecular weight exceeding 1200).

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

In addition, the carbonyl group-containing polyol may contain a cyclic carbonyl compound that does not contain a hydroxyl group (hereinafter sometimes referred to as "a cyclic carbonyl compound without a hydroxyl group").

The hydroxyl group-free cyclic carbonyl compound is a cyclic organic compound containing a carbonyl group in a molecule and having no hydroxyl group, for example, cyclic esters (eg, ε-caprolactone, γ-valerolactone, etc.) Lactones, for example, lactides such as L-lactide and D-lactide), cyclic amides (for example, lactams such as β-lactam, γ-lactam, δ-lactam, etc.) and the like. .

The cyclic carbonyl compounds not containing these hydroxyl groups may be used alone or in combination of two or more.

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

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

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

In addition, the concentration of the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol can be adjusted by known purification methods such as stripping, distillation, and extraction.

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, and more preferably 2 It is mass% or less, for example, 0 mass% or more, preferably exceeds 0 mass%, more preferably 0.1 mass% or more, and more preferably 0.3 mass% or more.

When the hydroxyl group-free cyclic carbonyl compound in the carbonyl group-containing polyol is within the above range, mechanical properties and bloom resistance can be improved in particular, and furthermore, molding stability (deforming), transparency, stain resistance, and discoloration It can improve the sex.

On the other hand, 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, based on the total amount of the carbonyl group-containing polyol, for example, 5 mol% or more, preferably 7 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, for example, 75 mol% or less, preferably 65 mol% or less, more preferably 50 mol% or less. In addition, the low molecular weight polyol is, for example, 25 mol% or more, preferably 35 mol% or more, more preferably 50 mol% or more, for example, 95 mol% or less, preferably 93 mol% or less , More preferably 90 mol% or less, and more preferably 85 mol% or less.

In addition, the polyol component may contain other polyols (polyols other than low molecular weight polyols and carbonyl group-containing polyols). As another polyol, polyether polyol, polyolefin polyol, etc. are mentioned, for example.

Other polyols are, 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 with respect to the total amount of the polyol component.

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

The reaction step is a step of reacting the polyisocyanate component with the 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 employed. From the viewpoint of improving various physical properties, a prepolymer method is preferably employed.

Specifically, in the prepolymer method, first, a polyisocyanate component and a macropolyol (carbonyl group-containing polyol) are reacted to synthesize an isocyanate group terminal 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) have a reaction temperature of, for example, 50 ° C or higher, for example, 250 ° C or lower, Preferably, the reaction is performed at 200 ° C or lower, for example, 0.5 hour or longer, for example, 15 hours or lower.

In solution polymerization, a polyisocyanate component and a macropolyol (carbonyl group-containing polyol) are added to the organic solvent, and the reaction temperature is, for example, 50 ° C or higher, for example, 120 ° C or lower, preferably 100 ° C. Below, for example, it reacts for 0.5 hour 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, methyl acetate, ethyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate Alkyl esters, such as n-hexane, n-heptane, and octane aliphatic hydrocarbons, such as cyclohexane and methyl cyclohexane, alicyclic hydrocarbons, such as , Aromatic hydrocarbons such as toluene, xylene, and ethyl benzene, such as methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol Glycol ether esters such as methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, for example, Ethers such as diethyl ether, tetrahydrofuran and dioxane, for example, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide and dichloroethane And polar aprotons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphorylamide.

Moreover, in the said polymerization reaction, if necessary, well-known urethanation catalysts, such as an amine and an organometallic compound, can be added.

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

Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide , Organotin compounds such as dibutyltin maleate, dibutyltin dyneodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, for example, lead octanoate, Organic lead compounds such as lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, and organic copper compounds such as copper octenate, for example Examples thereof include organic bismuth compounds such as bismuth octanoate (bismuth octylate) and bismuth neodecanoate, and preferably octyl There may be mentioned a tin, bismuth octylate.

Moreover, as a urethane catalyst, potassium salts, such as potassium carbonate, potassium acetate, and potassium octylate, are mentioned, for example.

These urethanation catalysts may be used alone or in combination of two or more.

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

Moreover, in the said polymerization reaction, when an unreacted polyisocyanate component and an organic solvent are used, an organic solvent can be removed by well-known removal means, such as distillation and extraction, for example.

In the prepolymer synthesis process, the mixing ratio of each component is the equivalent ratio of the isocyanate group in the polyisocyanate component to the hydroxyl group in the macropolyol (carbonyl group-containing polyol) (isocyanate group / hydroxyl group). , For example, 1.3 or more, preferably 1.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, further preferably 8 or less.

More specifically, the blending ratio of each component in the prepolymer synthesis step is preferably, for example, 5 parts by mass or more of the polyisocyanate component with respect to 100 parts by mass of the macropolyol (carbonyl group-containing polyol). It is 10 parts by mass or more, more preferably 15 parts by mass or more, and 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 mass% or more, preferably 3.0 mass% or more, more preferably 5.0 mass% or more, from the viewpoint of mechanical strength and contamination resistance, further Preferably 8.0 mass% or more, for example, 30.0 mass% or less, preferably 19.0 mass% or less, more preferably 16.0 mass% or less, more preferably 12.0 mass% or less in terms of transparency The components are reacted until. Thereby, an isocyanate group terminal prepolymer can be obtained.

On the other hand, the isocyanate group content (isocyanate group content ratio) can be determined by a titration method using di-n-butylamine or a known method such as FT-IR analysis.

Subsequently, in this method, the primary product of the polyisocyanate component and the polyol component is obtained by reacting the isocyanate group terminal prepolymer obtained above with a low molecular weight polyol (stretching step).

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

Then, in the chain extension step, the isocyanate group terminal prepolymer and the low molecular weight polyol are reacted by polymerization methods such as bulk polymerization 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 It is an hour or more, for example, 72 hours or less, preferably 48 hours or less.

In addition, the compounding ratio of each component is the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group in the isocyanate group terminal prepolymer to the hydroxyl group in the low molecular weight polyol, for example, 0.75 or more, Preferably it is 0.9 or more, for example, 1.3 or less, Preferably it is 1.1 or less.

More specifically, the blending ratio of each component in the chain extension step is, for 100 parts by weight of the isocyanate group terminal prepolymer, a low molecular weight polyol, for example, 1.0 part by mass or more, preferably 2.0 parts by mass Part or more, 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.

In addition, in the re-stretching step, in order to adjust the hard segment concentration (described later) of the resulting polyurethane resin, in addition to the low-molecular-weight polyol, a macropolyol (carbonyl group-containing polyol) may be blended in an appropriate ratio.

Moreover, in this reaction, the urethane catalyst mentioned above can be added as needed. The urethane catalyst may be blended into the isocyanate group terminal prepolymer and / or low molecular weight polyol, or may be blended separately upon mixing.

In addition, when the one-shot method is employed as a method for obtaining the primary product, the polyisocyanate component and the polyol component (including a macropolyol (containing a carbonyl group-containing polyol) and a low molecular weight polyol) are included in the polyol component. The equivalent ratio of the isocyanate group in the polyisocyanate component to the hydroxyl group (isocyanate group / hydroxyl group) is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, for example For example, at a ratio of 1.2 or less, preferably 1.1 or less, and more preferably 1.08 or less, they are simultaneously blended and stirred and mixed.

In addition, the stirring and mixing are, for example, in an inert gas (for example, nitrogen) atmosphere, and the reaction temperature is, for example, 40 ° C or higher, preferably 100 ° C or higher, for example, 280 ° C or lower, Preferably, at 260 ° C or lower, the reaction time is, for example, 30 seconds or more and 1 hour or less.

In addition, when stirring and mixing, the urethane catalyst or the organic solvent described above can be added in an appropriate ratio, if necessary.

The heat treatment process is a process of heat-treating the primary product to obtain a secondary product (reaction product after heat treatment, that is, a polyurethane resin that is a reaction product).

In the heat treatment step, the primary product obtained in the above-described reaction step is heat-treated by standing at a predetermined heat treatment temperature for a predetermined heat treatment period, and then dried as 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, molding stability (deforming) is inferior, and mechanical strength and contamination resistance are also inferior.

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

On the other hand, if the heat treatment temperature is within the above range, it is excellent in molding stability (deformation), transparency, bloom resistance, and discoloration resistance, and can further have mechanical properties and contamination resistance.

As a heat treatment period, it is 3 days or more, Preferably it is 4 days or more, More preferably, it is 5 days or more, More preferably, it is 6 days or more, For example, it is 10 days or less, Preferably it is 9 days or less , More preferably, it is 8 days or less.

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

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

On the other hand, if the heat treatment period is within the above range, molding stability (deformation), transparency, bloom resistance, and discoloration resistance are excellent, and furthermore, mechanical properties and contamination resistance can be combined.

Thereby, a polyurethane resin can be obtained.

On the other hand, in the polyurethane resin, if necessary, known additives, for example, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (carbodiimide compounds, etc.), further plasticizers, antiblocking agents, Release agents, pigments, dyes (such as blueing agents), lubricants (such as fatty acid amide-based lubricants), fillers, rust inhibitors, fillers, and the like can be added. These additives can be added when mixing each component, during synthesis, or after synthesis.

The antioxidant is not particularly limited, and known antioxidants (for example, listed in the BASF Japan catalog) are more specifically, for example, phenolic antioxidants and hindered phenolic antioxidants. And the like.

The heat-resistant stabilizer is not particularly limited, and well-known heat-resistant stabilizers (for example, listed in the BASF Japan catalog), and more specifically, for example, phosphorus-based heat stabilizers, lactone-based heat stabilizers, And a sulfur-based heat stabilizer.

The ultraviolet absorber is not particularly limited, and known ultraviolet absorbers (eg, listed in the BASF Japan catalog) can be exemplified, and more specifically, for example, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet rays And absorbents and benzophenone-based ultraviolet absorbers.

The light stabilizer is not particularly limited, and known light stabilizers (eg, listed in the catalog made by ADEKA) can be mentioned. More specifically, for example, benzoate light stabilizers, hindered amine light stabilizers And the like.

Each of these additives is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, such as 3.0% by mass or less, preferably 2.0% by mass or less with respect to the polyurethane resin, respectively. Is added.

In addition, in the method for producing such 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 number average molecular weight of 400 or more. The polyol component containing the carbonyl group-containing polyol of 1200 or less is reacted, and the obtained primary product is heat-treated under predetermined conditions.

Therefore, the polyurethane resin obtained by such a manufacturing method can have both molding stability (deformation), transparency, mechanical properties, fouling resistance, bloom resistance and discoloration resistance.

Specifically, the polyurethane resin is a hard segment formed by the reaction of a polyisocyanate component and a low molecular weight polyol, and a polyisocyanate component and a carbonyl group-containing polyol (number average molecular weight of 400 or more) It has a soft segment formed by the reaction of a carbonyl group-containing polyol of 1200 or less).

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, more preferably 20% by mass or more, particularly preferably 25 mass% or more, for example, 55 mass% or less, preferably 50 mass% or less, more preferably 45 mass% or less, more preferably 40 mass% or less, particularly preferably 35 mass% or less .

When the hard segment concentration of the polyurethane resin is within the above range, molding stability (deformation), transparency, mechanical properties, stain resistance, bloom resistance, and discoloration resistance of the resulting molded article (to be described later) can be improved.

On the other hand, 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 (input) of each component. (See the examples below).

In addition, in this polyurethane resin, the aggregation temperature of the polyurethane resin corresponds to the aggregation temperature on the hard segment in the polyurethane resin, and the aggregation temperature T ₁ or higher on the hard segment represented by the following calculation formula, in addition, the agglomeration temperature T ₂ less on the hard segment represented by the following formula.

Aggregation temperature T ₁ on the hard segment (unit: ℃): 80 + 1.2 × hard segment concentration (% by mass)

Aggregation temperature T ₂ on the hard segment (unit: ℃): 115 + 1.2 × hard segment concentration (mass%)

When the aggregation temperature is above the lower limit (T ₁ ), since the cohesive force on the hard segment is not excessively weak, molding stability (deforming) and mechanical properties are excellent.

In addition, when the aggregation temperature is equal to or less than the upper limit (T ₂ ), since the cohesive force on the hard segment is not excessively high, transparency and discoloration resistance and further bloom resistance are excellent.

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

On the other hand, the above calculation formula is not a theoretical formula, but an empirical formula (experimental formula) obtained by measuring the aggregation temperature of a polyurethane resin having various 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, even more preferably 105 ° C or higher, particularly preferably 110 It is more than ℃, for example, 200 ° C or less, preferably 180 ° C or less, more preferably 170 ° C or less, more preferably 160 ° C or less, particularly preferably 155 ° C or less.

When the aggregation temperature of the polyurethane resin is greater than or equal to the above lower limit, molding stability (deformation) and mechanical properties can be improved, and when the aggregation temperature of the polyurethane resin is below the upper limit, transparency and discoloration resistance, Furthermore, the bloom resistance can be improved.

On the other hand, the aggregation temperature of the polyurethane resin can be measured by differential scanning calorimetry (DSC measurement) based on the conditions of Examples.

In more detail, since the 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 is more resistant to contamination (compared to the case of using a polyol containing no carbonyl group). Impregnation) can be improved.

Moreover, 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 thereof is used. It is a small amount that does not inhibit the excellent effect of the invention. Therefore, the cohesive force on the hard segment of the primary product is relatively low, and as a result, molding stability and mechanical properties are relatively low.

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

However, even in the case of heat treatment, depending on the heat treatment conditions, the cohesive force on the hard segment may be excessively high, leading to a decrease in transparency, discoloration resistance, and bleeding resistance.

On the other hand, by adjusting the heat treatment conditions within the above range, the cohesive force on the hard segment can be appropriately improved, and the reduction in transparency, discoloration resistance, and bleeding resistance can be suppressed.

As described above, by appropriately adjusting the cohesive force on the hard segment, a polyurethane resin having both molding stability (deformation), transparency, mechanical properties, bloom resistance and discoloration resistance can be obtained.

On the other hand, the cohesive force on the hard segment corresponds to the coagulation temperature. Therefore, when the aggregation temperature on the hard segment is within the above range (T ₁ to T ₂ ), a polyurethane resin excellent in molding stability (deformation), transparency, mechanical properties, bloom resistance and discoloration resistance can be obtained. have.

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

In addition, the present invention includes a molded article comprising the above-described polyurethane resin. The molded article is molded from a polyurethane resin.

The molded article is, for example, the above-mentioned polyurethane resin, a known molding method, for example, thermocompression molding and injection molding using a specific mold, or extrusion molding using a sheet winding apparatus, for example, melting It can be obtained by molding into various shapes such as a pellet shape, a plate shape, a fiber shape, a strand shape, a film shape, a sheet shape, a pipe shape, a hollow shape, and a box shape by a thermoforming processing method such as spinning molding. have.

In addition, the obtained molded article can have molding stability (deformation), transparency, mechanical properties, fouling resistance, bloom resistance and discoloration resistance.

In addition, in the above description, the polyurethane resin of the present invention and its manufacturing method are thermoplastic polyurethane resin and its manufacturing method, but the polyurethane resin of the present invention and its manufacturing method are thermosetting polyurethane. It can also be applied to a resin and its manufacturing method.

In the thermosetting polyurethane resin and its manufacturing method, for example, the isocyanate group terminal prepolymer, dihydric alcohol (such as 1,4-butanediol) and trihydric alcohol (trimethylolpro) Pane, etc.), further, a known aromatic diamine or the like is reacted (reaction step), for example, after molding, the obtained molded product is heat-treated under the above conditions (heat treatment step). Thereby, the molded article which consists of a thermosetting polyurethane resin and its thermosetting polyurethane resin can be obtained.

In addition, the thermosetting polyurethane resin and its manufacturing method, and furthermore, molded articles made of the thermosetting polyurethane resin also have molding stability (deforming), transparency, mechanical properties, contamination resistance, bloom resistance and discoloration resistance. I have it.

Therefore, the molded article can be suitably used in the fields in which the above-mentioned various physical properties are required, and particularly 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 smart phone, a tablet computer (tablet PC), and a slate computer (slate PC).

Such a smart device is usually formed so that a resin cover can be detachably attached, and such a cover has molding stability (deformation), transparency, mechanical properties, fouling resistance, bloom resistance and discoloration resistance. Is required. Therefore, the molded article of the above polyurethane resin is suitably used as a cover for a smart device.

In addition, the molded article can be widely used industrially other than the above-mentioned uses, specifically, for example, transparent rigid plastics, coating materials, adhesives, adhesives, waterproofing materials, potting agents, inks, binders, films (for example For example, films such as paint protection films, chipping films, sheets, bands (for example, bands such as watch bands, for example, electric belts for automobiles, belts such as various industrial conveying belts (conveyor belts), tubes) (For example, other parts such as medical tubes and catheters, tubes such as air tubes, hydraulic tubes, wire tubes, hoses such as fire hoses, etc.), blades, speakers, sensors, LEDs for high brightness Encapsulant, organic EL member, solar power member, robot member, android member, wearable member, medical supplies, hygiene products, cosmetic products, food packaging member, sports goods, leisure goods, medical supplies, care Supplies, housing department Ash, acoustic member, lighting member, chandelier, exterior lamp, sealing material, encapsulating material, cork, packing, anti-vibration, anti-vibration, isolation member, soundproof member, daily necessities, sundries, cushion, bedding, stress absorber, stress relieving material, automobile interior Exterior parts, railway members, aircraft members, optical members, members for OA devices, sundries surface protection members, semiconductor encapsulants, self-healing materials, health equipment, eyeglass lenses, toys, cable sheaths, wire harnesses, telecommunication cables, automotive wiring , Industrial products such as computer wiring, curl cord, care products such as sheet, film, sports goods, leisure goods, miscellaneous goods, anti-vibration / isolating materials, shock absorbers, optical materials, films such as light guide films, automotive parts, surface protection sheets , Decorative sheet, transfer sheet, tape member such as semiconductor protective tape, golf ball member, tennis racket string, agricultural film, wallpaper, anti-fogging agent, non-woven fabric, mattress or sofa furniture items, etc. Medical supplies such as lined or shoulder pads, medical supplies such as paper diapers, napkins, and medical tape cushions, cosmetics, sanitary products such as face wash puffs and pillows, shoe products such as soles (outsoles), midsoles, cover materials, and more Body pressure dispersing products such as pads and cushions for vehicles, door trims, instrument panels, gear knobs and other hand-touching materials, electric refrigerators and building insulation materials, shock absorbers such as shock absorbers, filling materials, vehicle handles, automobile interior parts, It is suitably used in vehicle products such as automobile exterior members, semiconductor manufacturing products such as chemical mechanical polishing (CMP) pads, and the like.

Furthermore, the molded article described above includes a covering material (film, sheet, belt, wire, electric wire, metal rotating equipment, a covering material such as a wheel, a drill, etc.), a thread or a fiber (a thread used in tubes, tights, spats, sportswear, swimsuits, etc.) Or composite fiber), extrusion molding applications (for guts such as tennis and badminton, and extrusion molding materials thereof), slash molding products in the form of powder by micropelletization, artificial leather, skin, sheets, coating rolls (steel, etc.) Cover rolls), sealants, rollers, gears, balls, bat covers or core materials (golf balls, basketball balls, tennis balls, volleyball balls, soft balls, bat covers or core materials (they are foam molded from polyurethane resin) May be in one form)), mats, ski equipment, boots, tennis equipment, grips (grips for golf clubs or motorcycles), rack boots, wipers, seat cushion members, care products films, 3D printer moldings, textiles Reinforcing material (tan Reinforcement materials for fibers such as fibrin, lignin, kenaf, nanocellulose fiber, glass fiber), safety goggles, sunglasses, eyeglass frames, ski goggles, swimming goggles, contact lenses, gas assisted foamed moldings, shock absorbers, CMP polishing Pads, dampers, bearings, dust covers, cutting valves, chipping rolls, high-speed rolling rollers, tires, watches, wearable bands, etc., are suitably used in applications requiring resilience or wear resistance by repeated stretching and compression deformation. .

Example

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. On the other hand, "parts" and "%" are on a mass basis unless otherwise specified. In addition, specific numerical values, such as a compounding ratio (content ratio), a physical property value, and a parameter used in the following description, are described in the above "Specific contents for carrying out the invention", and the compounding ratio corresponding to them (containing Ratio), physical property values, parameters, etc., can be replaced with the upper limit value (a value defined as "below", "less than") or a lower limit value (a value defined as "above", "over").

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, trade name; Takenate 600, manufactured by Mitsui Chemicals

MDI: diphenylmethane diisocyanate, trade name; Cosmonate PH, manufactured by Mitsui Chemical SKC

<Polyol containing carbonyl group (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 / g

b-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 / g

b-3) PBA # 750 (number average molecular weight 750): polybutylene adipate (polyester polyol) synthesized by the method described in Production Example 7, hydroxyl value = 149.5 mgKOH / g

b-4) PBA # 800 (number average molecular weight 800): polybutylene adipate (polyester polyol) synthesized by the method described in Production Example 7, hydroxyl value = 140.2 mgKOH / g

b-5) PBA # 1000 (number average molecular weight 1000): polybutylene adipate (polyester polyol), trade name; Takerak U-2410, hydroxyl value = 112.2 mgKOH / g, manufactured by Mitsui Chemicals

b-6) PBA # 2000 (number average molecular weight 2000): polybutylene adipate (polyester polyol), trade name; Takerak U-2420, hydroxyl value = 56.2mgKOH / g, manufactured by Mitsui Chemicals

b-7) PCL # 1000 (number average molecular weight 1000): polycaprolactone polyol, trade name; PLACCEL210N, hydroxyl value = 112.1 mgKOH / g, manufactured by Daicel

b-8) PCD # 1000 (number average molecular weight 1000): polycarbonate polyol, trade name; ETERNACOL UH-100, hydroxyl value = 112.2 mgKOH / g, manufactured by Ube Heungsan

b-9) PCD # 2000 (number average molecular weight 2000): polycarbonate polyol, trade name; ETERNACOL UH-200D, hydroxyl value = 55.9 mgKOH / g, manufactured by Ube Heungsan

b-10) PEA # 550 (number average molecular weight 550): polyethylene adipate (polyester polyol), trade name; Takerak U-550, hydroxyl value = 204.0 mgKOH / g, manufactured by Mitsui Chemicals

b-11) PEA # 1000 (number average molecular weight 1000): polyethylene adipate (polyester polyol), trade name; Nippon 4002, hydroxyl value = 112.2 mgKOH / g, manufactured by Tosoh Corporation

b-12) PBS # 1000 (number average molecular weight 1000): polybutylene succinate (polyester polyol) synthesized by the method described in Production Example 8, hydroxyl value = 112.2 mgKOH / 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

<Low molecular weight polyol (c)>

1,4-BD: 1,4-butanediol, trade name; 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation

1,3-PDO: 1,3-propanediol, trade name; Sustera TM propanediol, manufactured by DuPont

<Urethaneization catalyst>

Tin-based catalyst: tin (II) octylate, trade name; Star Knock, manufactured by API Corporation

<Catalyst thinner>

Diisononyl adipate: Product name: DINA, manufactured by Daihachi Chemical Industries, Ltd.

<Stabilizer>

Antioxidants: hindered phenolic compounds, trade names; Irganox 245, manufactured by BASF Japan

UV absorbers: benzotriazole compounds, trade names; Tinuvin 234, manufactured by BASF Japan

Light stabilizer: hindered amine compound, trade name; LA-72, made by ADEKA

Hydrolysis inhibitors: carbodiimide compounds, trade names; Starbaksol I-LF, manufactured by LANXESS

<Dye>

Anthraquinone-based blueing agent: trade name; Plast Blue8514, manufactured by Arimoto Chemical Industries

<< Quantification of cyclic carbonyl compounds without hydroxyl groups >>

If necessary, 0.2 g of the carbonyl group-free polyol or the carbonyl group-containing polyol, which was stripped, was weighed and dissolved in a 10 mL dichloromethane solution to which phthalic acid di-n-butyl (DBP) was added as an inner label.

This dissolved solution was subjected to GC-MS / FID measurement under the following conditions, and in the obtained GC-MS spectrum, a hydroxyl-free cyclic carbonyl compound was attributed to the retention time described below. And the content (mass%) by DBP conversion was calculated from the FID detection area ratio.

Measuring device: Agilent7890A / 5975C MSD / FID

Column: VF5ms

Carrier gas: He (pressure control mode: 23.602psi)

Oven temperature: 100 ℃ (2min) → 10 ℃ / min → 300 ℃ (23min) [Total = 45min]

Injection method: Splitless injection

Inlet temperature: 300 ℃

Detection method: FID

[GC-MS Spectrum Attribution]

<Polybutylene adipate (polyester polyol)>

Cyclic ester formed with 1 molecule of adipic acid and 1 molecule of 1,4-butanediol: 10.7 minutes

Cyclic ester formed with 2 molecules of adipic acid and 2 molecules of 1,4-butanediol: 24.3 minutes

Cyclic ester formed from 3 or more molecules of adipic acid and 3 or more molecules of 1,4-butanediol: Because of its high boiling point, it is not detected.

<Polyethylene adipate (polyester polyol)>

Cyclic ester formed with one molecule of adipic acid and one molecule of ethylene glycol: 7.6 minutes

Cyclic ester formed with 2 molecules of adipic acid and 2 molecules of ethylene glycol: 20.4 minutes

Cyclic ester formed from 3 or more molecules of adipic acid and 3 or more molecules of ethylene glycol: Not detected due to high boiling point.

<Polybutylene succinate (polyester polyol)>

Cyclic ester formed with 1 molecule of succinic acid and 1 molecule of 1,4-butanediol: 8.0 minutes

Cyclic ester formed with 2 molecules of succinic acid and 2 molecules of 1,4-butanediol: 21.2 minutes

Cyclic esters formed of three or more molecules of succinic acid and three or more molecules of 1,4-butanediol: Because of their high boiling point, they are not detected.

<Polycaprolactone diol>

Caprolactone monomer: 5.8 minutes

Caprolactone dimer: 13.2 minutes

Caprolactone Trimer: 21.0 min

More than tetramer of caprolactone: Not detected due to high boiling point.

<Polycarbonate diol>

Cyclic polycarbonate compound formed from two molecules of carbonate group and two molecules of 1,6-hexanediol: 17.2 minutes

Cyclic polycarbonate compound formed of three or more molecules of carbonate groups and three or more molecules of 1,6-hexanediol: 26.1 minutes

Cyclic polycarbonate compound formed from four or more molecules of carbonate groups and four or more molecules of 1,6-hexanediol: Because of its high boiling point, it is not detected.

2) Preparation of polyurethane resin

<Preparation of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI)>

Production Example 1 (1,4-bis (isocyanatomethyl) cyclohexane (1) (hereinafter referred to as 1,4-BIC (1)) production method)

The 1,4-BIC (2) described in Production Example 2 described later was charged in an oil can while purging with nitrogen, and then left in an incubator at 1 ° C for 2 weeks. The obtained coagulum was quickly filtered under reduced pressure using a membrane filter of 4 μm mesh to remove the liquid portion to obtain a solid portion. The above operation was repeated for the solid portion to obtain 1,4-BIC (1). The purity by gas chromatography measurement of 1,4-BIC (1) was 99.9%, the color by APHA measurement was 5, and the trans / cis ratio by ⁹ C-NMR measurement was 99.5 / 0.5. The hydrolyzable chlorine concentration (hereinafter referred to as HC concentration) was 18 ppm.

Production Example 2 (1,4-bis (isocyanatomethyl) cyclohexane (2) (hereinafter referred to as 1,4-BIC (2)))

Based on the description of Preparation Example 6 of Japanese Patent Laid-Open No. 2014-55229, a trans / ciscis ratio 98/2 of 1,4-bis (aminomethyl) cyclohexane having a purity of 99.5% or more was obtained in a yield of 92%. .

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

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

Production Example 3 (1,4-bis (isocyanatomethyl) cyclohexane (3) (hereinafter referred to as 1,4-BIC (3)))

In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 1,4-BIC (2) of Production Example 2 was 789 parts by mass, 1,4-BIC (6) of Production Example 6 described later Was charged 211 parts by mass, and stirred under a nitrogen atmosphere at room temperature for 1 hour. The resulting 1,4-BIC purity by gas chromatography measurements of (3) was 99.9%, trans / cis ratio of the color due to the 5, ¹³ C-NMR measured in APHA measurement is 86/14. HC concentration was 19ppm.

Production Example 4 (1,4-bis (isocyanatomethyl) cyclohexane (4) (hereinafter referred to as 1,4-BIC (4)))

In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 561 parts by mass of 1,4-BIC (2) of Production Example 2, 1,4-BIC (6) of Production Example 6 described later Was charged 439 parts by mass, and stirred at room temperature under nitrogen atmosphere for 1 hour. The obtained 1,4-BIC (4) had a purity of 99.9% by gas chromatography measurement and a color of APHA measurement of 5, ¹³ , and a trans / cis ratio of C / NMR measurement of 73/27. HC concentration was 20 ppm.

Production Example 5 (1,4-bis (isocyanatomethyl) cyclohexane (5) (hereinafter referred to as 1,4-BIC (5)))

To a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 1,4-BIC (2) of Production Example 2 was 474 parts by mass, 1,4-BIC (6) of Production Example 6 described later Was charged 526 parts by mass, and stirred under a nitrogen atmosphere at room temperature for 1 hour. The obtained 1,4-BIC (5) had a purity of 99.9% by gas chromatography measurement and a color of APHA measurement of 5, ¹³ , and a trans / cis ratio of C / NMR measurement of 68/32. HC concentration was 21 ppm.

Production Example 6 (1,4-bis (isocyanatomethyl) cyclohexane (6) (hereinafter referred to as 1,4-BIC (6)))

¹³ Preparation of Japanese Patent Publication No. 2014-55229 using 1,4-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) having a trans / cis ratio of 41/59 by C-NMR measurement as a raw material. Based on the description of Example 1, 388 parts by mass of 1,4-BIC (6) was obtained.

The resulting 1,4-BIC purity by gas chromatography measurement of the (6) was found to color by 99.9%, APHA measurement is 5, trans-isomer / cis was 41/59 Chevy by ¹³ C-NMR measurement. HC concentration was 22 ppm.

<Preparation of polybutylene adipate (b-1) to (b-4)>

Production Example 7 (Method for producing polybutylene adipate (polyester polyol))

Adding adipic acid and 1,4-butanediol to a four-necked flask equipped with a thermometer, stirrer, and Liebig cooler, heated to 180 ° C, and under nitrogen flow, while undergoing a polycondensation reaction, 220 ° C Until it was heated. When the acid value reached 15 mgKOH / g, as a catalyst, starnox was added, 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.

<Preparation of polybutylene succinate (b-12)>

Production Example 8 (Method for producing polybutylene succinate (polyester polyol))

Succinic acid and 1,4-butanediol were introduced into a four-necked flask equipped with a thermometer, a stirrer, and a Liebig cooler, heated to 150 ° C, and under nitrogen flow, while undergoing a polycondensation reaction, to 220 ° C. It was heated. When the acid value reached 10 mgKOH / g, as a catalyst, starnox was added, 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 terminal prepolymer>

Synthesis Examples 1-8, 10-17, 19, 21-22 and 24-28

· Stripping treatment

The carbonyl group-containing polyol (b) was charged into a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube with a capillary, and was connected to a vacuum pump from one inlet via a Liebig cooler. The carbonyl group-containing polyol (b) was heated to 100 ° C., while bubbling nitrogen from the tip of the nitrogen introduction tube with a capillary, using a vacuum pump, the vacuum was reduced to a pressure of 1.33 kPa (10 mgHg) or lower, and 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.

Uretaining reaction

According to the prescriptions shown in Tables 1 to 3, the polyisocyanate component (a) and the carbonyl group-containing polyol (b) were charged into a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, Further, Stabaczol I-LF, which became 0.2% by mass relative to their total amount, was added, and stirred at 80 ° C for 1 hour in a nitrogen atmosphere.

Subsequently, tin octylate (trade name: Starnock, manufactured by Affia Corp.) previously diluted with DINA (manufactured by Daihachi Chemical Co., Ltd.) to 4% by mass, polyisocyanate component (a) and carbonyl group-containing polyol ( About the total amount of b), it was added so that it might be 5 ppm as a catalyst amount.

Then, the mixture was stirred and mixed under a nitrogen stream under a temperature control of 80 ° C until the reaction reached the isocyanate group contents shown in Tables 1 to 3, and the isocyanate group terminal prepolymers (a) to ( h), (j) to (q), (s), (u) to (v) and (x) to (ab).

Synthesis Example 9

An isocyanate group terminal 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

According to the prescriptions described in Tables 1 to 3, instead of the carbonyl group-containing polyol (b), PTMEG (b-13, number average molecular weight 1000), which is a carbonyl group-free polyol (b '), was used, and stabaczol I- An isocyanate group terminal 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 prescriptions shown in Tables 1 to 3, Synthesis Example 1 and except that MDI (diphenylmethane diisocyanate) was used as the polyisocyanate component (a) and no catalyst was used. In the same manner, an isocyanate group terminal prepolymer (t) was obtained.

Synthesis Example 23

According to the prescriptions shown in Tables 1 to 3, the isocyanate group terminal prepolymer (w) was obtained in the same manner as in Synthesis Example 1, except that the stripping treatment temperature and the urethane reaction temperature were 120 ° C.

<Synthesis of polyurethane resin>

Examples 1-18, 20, 22, 24 and Comparative Examples 1-10

The isocyanate group concentration of the isocyanate group terminal prepolymer temperature-controlled to 80 ° C was measured.

Then, the equivalent ratio (NCO index) of the isocyanate group in the isocyanate group end prepolymer to the hydroxyl group in the low molecular weight polyol is 1,4-butanediol (1,4-BD). It was weighed in a stainless steel cup so as to be 1.01, and the temperature was adjusted to 80 ° C.

Subsequently, the isocyanate group terminal prepolymer was weighed in another stainless steel cup, and 0.3 parts by mass of Irganox 245 (heat stabilizer manufactured by BASF), T, with respect to the total amount of isocyanate group terminal prepolymer and 1,4-BD, T 0.1 parts by weight of Nubin 234 (UV absorbent manufactured by BASF), 0.1 parts by mass of Adeka Stav LA-72 (HALS manufactured by ADEKA), and 0.1 parts by mass of Khao Wax EB-P (fatty acid amide-based lubricant manufactured by Kao Chemical), isocyanate Group terminal prepolymer.

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

In addition, tin octylate (trade name: Starnock, manufactured by Affia Corp.) previously diluted to 4% by mass by DINA (manufactured by Daihachi Chemical Co., Ltd.) was added to the isocyanate group terminal prepolymer so as to be 10 ppm as a catalyst amount. .

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

Subsequently, 1,4-BD, which was previously weighed and adjusted to 80 ° C, was added to the isocyanate group terminal prepolymer, and stirred and mixed for 3 to 10 minutes under agitation at 500 to 1500 rpm using a high-speed stirring disper. did.

Subsequently, the mixed solution was poured into a Teflon (trademark) batt previously temperature-adjusted to 150 ° C, reacted at 150 ° C for 2 hours, then cooled to 100 ° C and continued to react for 20 hours, to prepare a polyurethane resin. The primary products (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) were obtained.

Subsequently, the primary products (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) of the polyurethane resin were removed from the bat, and then die-shaped by a bale cutter. It cut | disconnected and pulverized the dice-shaped resin with a pulverizer, and pulverized pellet was obtained.

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

Thereafter, by using the obtained pulverized pellets, by extruding and cutting the strands in the range of the screw rotation speed of 30 rpm and the cylinder temperature of 200 to 270 ° C using a single screw extruder (model: SZW40-28MG, manufactured by Technobel). , Polyurethane resins (A) to (Z), (AC) to (AD), (AF), (AH) and (AJ) pellets were obtained.

Example 19

According to the prescription shown in Table 6, a pellet of a polyurethane resin (AE) was obtained in the same manner as in Example 1, except that the preheating temperature of the isocyanate group terminal prepolymer was 120 ° C.

Example 21 and Example 23

According to the prescription shown in Table 6, pellets of polyurethane resins (AG) and (AI) were obtained in the same manner as in Example 1, except that the NCO index was set to 0.98.

Comparative Example 11

According to the prescription shown in Table 7, a pellet of polyurethane resin (AA) was obtained in the same manner as in Example 1, except that 1,3-propanediol (PDO) was used as the low molecular weight polyol. .

Comparative Example 12

According to the prescription shown in Table 7, pellets of polyurethane resin (AB) were obtained in the same manner as in Example 1, except that no catalyst was used.

3) Formation of sample for evaluation

<Forming Method of Polyurethane Sheet>

The pellets of the obtained polyurethane resins (A) to (AJ) were dried in advance at 80 ° C. under vacuum reduced pressure for 12 hours, using an injection molding machine (model: NEX-140, manufactured by Nissei Resin Co., Ltd.), With a screw rotation speed of 80 rpm and a barrel temperature of 200 to 270 ° C, a sheet having a good surface condition was obtained under conditions of 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. So, it was injection molded.

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

4) Evaluation

<Surface properties of sheet>

The demolding time at the time of injection molding was unified to 15 seconds, and the surface state of the sheet after demolding was evaluated in 5 steps of the following evaluations 5 to 1.

Evaluation 5: A uniform sheet having no sticking to the mold at the time of demolding and no surface roughness was obtained.

Evaluation 4: Although the sheet was adhered to the mold, the peeling marks on the sheet surface were less than 20% of the entire sheet.

Evaluation 3: There is sticking of the sheet to the mold, and the peeling marks on the surface of the sheet are 20% or more and less than 50% of the entire 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 was opened, the sheets were attached to the molds on both sides, and the sheet was torn.

<All light transmittance (unit:%)>

The total light transmittance (according to JIS K7105 (light source: D ₆₅ )) of a 1 mm thick polyurethane sheet obtained by injection molding was measured using a Haze Meter (manufactured by Nippon Denshoku Industries, model: NDH 2000).

<Tear strength (unit: kN / m)>

From a polyurethane sheet having a thickness of 1 mm obtained by injection molding, it was measured under a tearing rate of 300 mm / min using a right-angle tearing test piece prepared according to JIS K7311 (1995).

<Break strength (unit: MPa) and elongation at break (unit:%)>

From a 1 mm thick polyurethane sheet obtained by injection molding, it was measured under the conditions of a tensile speed of 300 mm / min and a distance between marks of 20 mm using a JIS-3 dumbbell-shaped test piece produced according to JIS K7311 (1995).

<Measurement of aggregation temperature of polyurethane by differential scanning calorimetry (DSC) (unit: ℃)>

It measured using differential scanning calorimeter (made by S-I Nano Technology, brand name: EXSTAR6000 PC station, and DSC220C).

Polyurethane sheet was collected by cutting it into thin pieces to make the shape as close as possible to an aluminum pan of about 8 mg. The aluminum pan was covered with a crimped sample as a measurement sample (sample). Similarly, alumina was taken as a reference sample. After setting the sample and reference to a predetermined position in the cell, the sample was cooled to -100 ° C at a rate of 10 ° C / min under a nitrogen flow of 40 NmL / min, and maintained at the same temperature for 5 minutes, followed by 10 ° C / It heated up to 270 degreeC at the rate of 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 defined as the aggregation temperature of polyurethane.

<Pollution 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 oily magic ink (manufactured by Teranishi Chemical Industries) for 1 hour, and then washed with distilled water.

The cut cross section was observed using a digital microscope (produced by Giens Corporation, product name: VHX-6000), and the thickness impregnated with magic ink was measured. The smaller the thickness impregnated with magic ink, the better the stain resistance.

<Bloom resistance>

The sheet having a thickness of 1 mm obtained by injection molding was left in an oven at 80 ° C., and the number of days leading to the preservation phenomenon occurring on the sheet surface was evaluated in five steps of the following evaluations 5 to 1.

Evaluation 5: Within 28 days of the test, no odor was generated.

Evaluation 4: Preparative phenomena occur within 28 days of the test.

Evaluation 3: Preparative phenomena occur within 14 days of the test.

Evaluation 2: An aliquot occurs within 7 days of the test.

Evaluation 1: Preparatory phenomena occur within 3 days of the test.

<Initial color>

The yellowness b ^* of the 1 mm thick polyurethane sheet obtained by injection molding was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., Color Ace MODEL TC-1). On the other hand, b ^* is generally regarded as an index of the color 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 left standing in 5000 ppm of NOx gas for 15 hours. After the test piece was taken out, it was subjected to a moist heat test for 96 hours at 60 ° C and a relative humidity of 93%.

The Δb (the amount of change in the b value) of the polyurethane sheet before and after the test was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., color ace MODEL TC-1). On the other hand, Δb is generally regarded as an indicator of discoloration of the polyurethane resin.

<UV discoloration resistance>

A 20 × 60 mm test piece was cut out from a 1 mm thick polyurethane sheet, and using a QUV weathering tester (manufactured by Suga Test Instruments, UV Fluorescent Light Weather Meter FUV) equipped with an ultraviolet fluorescent lamp, 60 ° C., relative humidity of 10%. , Conditions of irradiation intensity of 28 W / m ² of ultraviolet light (wavelength 270 to 720 nm) and conditions of 50 ° C., relative humidity of 95%, and no ultraviolet irradiation were repeated every 4 hours, over 48 hours, for 6 cycles.

The Δb (the amount of change in the b value) of the polyurethane sheet before and after the test was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., color ace MODEL TC-1). On the other hand, Δb is generally regarded as an index of discoloration of the polyurethane resin.

5) Polyurethane injection molding

<Reference Example 1>

In the above injection molding machine, the mold was changed to a smartphone cover type.

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

When the total light transmittance of the molded article was measured, it was 91%. Further, under the conditions of room temperature 23 ° C. and relative humidity of 55%, as a result of observing the odor (bloom) on the surface of the smartphone cover for 6 months, no bloom was observed. In addition, as a result of evaluating the stain resistance (based on the method described above) for the oily magic ink, the thickness of the oily magic ink penetrating was 100 μm.

Similarly, for 100 mL of artificial sweat according to JIS-L0848 (2004), after immersing for 1 hour in a red artificial sweat solution to which 1 mL of red aqueous dye (Kokuyoze, brand name: IP-540R) was added, , Washed with distilled water. The cut cross section was observed using a digital microscope (produced by GENS, brand name: VHX-6000), and the thickness of the red artificial sweat solution was measured. As a result, it was 55 μmt.

In addition, although the said invention was provided as embodiment of the example of this invention, this is only a mere illustration and it should not interpret it limitedly. Variations of the invention that are apparent to those skilled in the art are included in the later claims.

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

Claims (8)

A polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, and
A polyol component comprising 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.
Is the reaction product of
The aggregation temperature measured by differential scanning calorimeter,
The aggregation temperature T ₁ or more on the hard segment represented by the following calculation formula, and
Aggregation temperature T ₂ or less on the hard segment represented by the following calculation formula
Polyurethane resin, characterized in that.
Aggregation temperature T ₁ on the hard segment (unit: ℃): 80 + 1.2 × hard segment concentration (% by mass)
Aggregation temperature T ₂ on the hard segment (unit: ℃): 115 + 1.2 × hard segment concentration (mass%) According to claim 1,
The concentration of the cyclic carbonyl compound not containing a hydroxyl group in the carbonyl group-containing polyol is 3% by mass or less.
Polyurethane resin, characterized in that. According to claim 1,
The bis (isocyanatomethyl) cyclohexane contains 1,4-bis (isocyanatomethyl) cyclohexane
Polyurethane resin, characterized in that. The method of claim 3,
The 1,4-bis (isocyanatomethyl) cyclohexane contains a trans body in a proportion of 70 mol% or more and 99 mol% or less
Polyurethane resin, characterized in that. The method of claim 3,
The content ratio of 1,4-bis (isocyanatomethyl) cyclohexane to bis (isocyanatomethyl) cyclohexane is 85% by mass or more
Polyurethane resin, characterized in that. It comprises the polyurethane resin of Claim 1.
A molded article, characterized in that. The method of claim 6,
Smart device cover-in
A molded article, characterized in that. A polyisocyanate component containing bis (isocyanatomethyl) cyclohexane, and
A reaction step of obtaining a primary product by reacting a polyol component comprising 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,
It is provided with a heat treatment process to obtain a polyurethane resin by heat treatment of the primary product,
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.
Characterized in that, a method for producing a polyurethane resin.