JP2018193564A - Polyurethane - Google Patents

Abstract

Disclosed is a polyurethane which has excellent flexibility and can be easily produced. A polyurethane comprising a structural unit derived from a polycarbonate polyol containing a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from a diol having 6 carbon atoms having an alkyl side chain. The molar ratio of the structural unit derived from 2-methyl-1,3-propanediol and the structural unit derived from a diol having 6 carbon atoms having an alkyl side chain is the former / the latter = 80/20 to 20/80. It is preferable. The polycarbonate polyol is preferably a reaction product of 2-methyl-1,3-propanediol, a C6-diol having an alkyl side chain, and a carbonate compound. [Selection figure] None

Description

  The present invention relates to a polyurethane which is excellent in flexibility and can be easily produced, a production method thereof, a composition containing the polyurethane, a polycarbonate polyol useful for the production of the polyurethane, and the like.

  Polyurethanes can be adjusted in chemical and physical properties by appropriately combining the polymer polyols, polyisocyanates, chain extenders, etc. used, so that paints, adhesives, sealants, elastomers, spandex (elastic fibers), As synthetic or artificial leather, ink binder, rigid foam, flexible foam, etc., it is widely used from soft use to hard use.

  Conventionally, polyester polyols and polyether polyols have been used as the above-mentioned polymer polyols that serve as soft segments of polyurethane. Of these, polyester polyols such as adipate have poor hydrolysis resistance, so polyurethanes using them have limitations in use, such as surface cracks and mold growth in a relatively short period of time. I received it. On the other hand, polyurethane using polyether polyol has good hydrolysis resistance, but has a problem of poor weather resistance and oxidation deterioration resistance.

  As a solution to these problems, polyurethane using a polycarbonate polyol is known. For example, Patent Document 1 describes that a polycarbonate diol obtained by using a polyhydric alcohol having a side chain having 3 to 20 carbon atoms and 1,6-hexanediol is used for the production of a urethane resin. ing. Patent Document 2 describes that a specific polycarbonate polyol using a diol having a branched alkyl side chain is used in the production of a main component of a two-component reactive polyurethane adhesive.

JP-A-2-49025 JP 2010-138291 A

  A polyurethane using a conventionally known polycarbonate polyol has room for further improvement in terms of flexibility. In addition, conventionally known polycarbonate polyols may be solid at room temperature, and handleability may be inferior when polyurethane is produced.

  Accordingly, an object of the present invention is to provide a polyurethane that is excellent in flexibility and can be easily produced, a method for producing the polyurethane, and a composition containing the polyurethane. Another object of the present invention is to provide a polycarbonate polyol having excellent handling properties useful for the production of the polyurethane.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a specific diol having an alkyl side chain in combination with 2-methyl-1,3-propanediol having a branched structure itself. It was found that the polycarbonate polyol has excellent handleability, and when the polycarbonate polyol is used, a polyurethane having excellent flexibility can be easily produced and the above-mentioned object can be achieved. The present invention was completed through repeated studies.

That is, the present invention relates to the following [1] to [9].
[1] A polyurethane containing a structural unit derived from a polycarbonate polyol containing a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from a C6-diol having an alkyl side chain.
[2] The molar ratio between the structural unit derived from 2-methyl-1,3-propanediol and the structural unit derived from a diol having 6 carbon atoms having an alkyl side chain is the former / the latter = 80/20 to 20 / The polyurethane according to [1], which is 80.
[3] The polyurethane according to [1] or [2], wherein the polycarbonate polyol is a reaction product of 2-methyl-1,3-propanediol, a diol having an alkyl side chain and a carbon number 6 diol and a carbonate compound.
[4] The polyurethane according to [3], wherein the carbonate compound is ethylene carbonate.
[5] The polyurethane according to any one of [1] to [4], wherein the diol having an alkyl side chain and having 6 carbon atoms is 3-methyl-1,5-pentanediol.
[6] The method for producing a polyurethane according to any one of [1] to [5], wherein the diol has 6 structural units derived from 2-methyl-1,3-propanediol and an alkyl side chain. The manufacturing method including the process of making the polycarbonate polyol containing the structural unit derived from, polyisocyanate, and the chain extender react.
[7] A composition comprising the polyurethane according to any one of [1] to [5].
[8] A polycarbonate polyol comprising a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from a diol having 6 carbon atoms having an alkyl side chain.
[9] The molar ratio of the structural unit derived from 2-methyl-1,3-propanediol and the structural unit derived from a diol having 6 carbon atoms having an alkyl side chain is the former / the latter = 80/20 to 20 / The polycarbonate polyol according to [8], which is 80.

  ADVANTAGE OF THE INVENTION According to this invention, the polyurethane which is excellent in a softness | flexibility and can be manufactured easily, its manufacturing method, and the composition containing the said polyurethane are provided. Moreover, according to this invention, the polycarbonate polyol excellent in the handleability useful for manufacture of the said polyurethane etc. is provided.

  Hereinafter, the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

<Polyurethane>
The polyurethane of the present invention is a diol having 6 carbon atoms having a structural unit derived from 2-methyl-1,3-propanediol (hereinafter sometimes referred to as “diol (a)”) and an alkyl side chain (hereinafter referred to as “diol”). And a structural unit derived from a polycarbonate polyol containing a structural unit derived from “diol (b)”. By including the structural unit derived from the specific polycarbonate polyol, the polyurethane of the present invention is excellent in flexibility and can be easily produced.

  The polyurethane of the present invention can be obtained by reacting the above-mentioned polycarbonate polyol and polyisocyanate, and can be preferably obtained by reacting the above-described polycarbonate polyol, polyisocyanate and chain extender.

-Polycarbonate polyol Said polycarbonate polyol contains the structural unit derived from diol (a) and the structural unit derived from diol (b). That is, the polycarbonate polyol is typically a copolymer containing a structural unit derived from the diol (a), a structural unit derived from the diol (b), and a carbonate unit, and two per molecule. It has the above (preferably two) hydroxyl groups. The hydroxyl group is preferably present at at least a part of the molecular chain terminals, and more preferably at substantially all molecular chain terminals.

  Examples of the diol (b) include 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol (hereinafter sometimes abbreviated as “MPD”), 2,2-dimethyl- Examples include 1,3-butanediol, 2,2-dimethyl-1,4-butanediol, 3,3-dimethyl-1,2-butanediol, and 2,3-dimethyl-1,4-butanediol. These may be used individually by 1 type and may use 2 or more types together.

  As the diol (b), MPD is preferable from the viewpoint of handling of the obtained polycarbonate polyol and imparting flexibility to the polyurethane.

  The molar ratio of the structural unit derived from the diol (a) to the structural unit derived from the diol (b) in the structural unit derived from the polycarbonate polyol in the resulting polyurethane is in terms of the flexibility of the resulting polyurethane. Therefore, the former / the latter is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and further preferably 55/45 to 45/55.

  The structural unit derived from the polycarbonate polyol and, in turn, the polycarbonate polyol in the resulting polyurethane may further include a structural unit derived from a diol other than the diol (a) and the diol (b). The structural unit derived from the other diol is preferably 10 mol% or less based on the total number of moles of the structural unit derived from the diol (a) and the structural unit derived from the diol (b).

  The structural unit derived from the polycarbonate polyol, and thus the polycarbonate polyol in the resulting polyurethane, may further include a structural unit derived from a polyol having three or more hydroxyl groups. Examples of the polyol include trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, and the like, among which triol having three hydroxyl groups is preferable. When the polycarbonate polyol contains a structural unit derived from the polyol having three or more hydroxyl groups, a polyfunctionalized polycarbonate polyol having three or more hydroxyl groups per molecule can be obtained. The structural unit derived from the polyol having three or more hydroxyl groups may cause gelation due to crosslinking if it is contained in an excessive amount. Therefore, the structural unit derived from the diol (a) and the diol (b ), Preferably 5 mol% or less, more preferably 2 mol% or less, and from the viewpoint of polyfunctionalization, 0.1 mol% or more. It is preferable that

  The number average molecular weight of the polycarbonate polyol is preferably 300 or more, more preferably 400 or more, further preferably 500 or more, and preferably 10,000 or less, 8,000 or less. Is more preferably 5,000 or less, and particularly preferably 3,000 or less. When the number average molecular weight is not less than the above lower limit, a polyurethane excellent in flexibility can be obtained. Moreover, when the number average molecular weight is not more than the above upper limit, the molding processability of polyurethane is improved. In addition, the number average molecular weight of polycarbonate polyol can be calculated based on the hydroxyl value described later in Examples.

  The polycarbonate polyol can be obtained as a reaction product by reacting the diol (a), the diol (b) and the carbonate compound. In the reaction, the other diol and / or the polyol having three or more hydroxyl groups may be used in combination.

  Examples of the carbonate compound include alkylene carbonate, dialkyl carbonate, diaryl carbonate and the like. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 5-methyl-1,3-dioxane-2-one, 1,2-butylene carbonate, 1,3-butylene carbonate, Examples include 1,2-pentylene carbonate. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and di-n-butyl carbonate. Examples of the diaryl carbonate include diphenyl carbonate. The carbonate compound may be a compound capable of forming a carbonate such as haloformate or carbonyl halide. A carbonate compound may be used individually by 1 type, and may use 2 or more types together.

  As the carbonate compound, alkylene carbonate and dialkyl carbonate are preferable, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and di-n-butyl carbonate are more preferable because of reactivity and availability. Ethylene carbonate is more preferable because it can be obtained more efficiently.

In the production of polycarbonate polyol, a catalyst may be added to promote the reaction. The type of the catalyst is not particularly limited. For example, alkali metals such as alkali metal or alkaline earth metal alcoholates, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and organic acid salts. Or alkaline earth metal compounds. Here, examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium.
Further, as the catalyst, other catalysts other than alkali metal or alkaline earth metal compounds can be used. Examples of such other catalysts include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, and indium. , Tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, ytterbium, and other simple metals other than alkaline metals and alkaline earth metals, inorganic salts, organic compounds, and the like. Examples of the metal organic compound include metal alcoholates and organic acid salts.

  In the production of the polycarbonate polyol, the catalyst may be used alone or in combination of two or more. Among these, from the viewpoints of reactivity and influence on the subsequent urethanization reaction, simple metals other than alkali metals and alkaline earth metals, inorganic salts, and organic compounds are preferable, and titanium, zirconium, tin, lead, ytterbium are preferable. Are more preferable, organic compounds of titanium, zirconium, tin, lead and ytterbium are more preferable, and organic acid salts (acetates and the like) of titanium, zirconium, tin, lead and ytterbium are particularly preferable.

  When a polycarbonate polyol is produced using the above catalyst, the catalyst may remain in the obtained polycarbonate polyol. The content of the catalyst in the polycarbonate polyol is preferably 0.0001 to 0.05% by mass based on the mass of the polycarbonate polyol as the amount of the metal element measured using ICP. It is more preferable that it is 0.02 mass%. If the content of the catalyst is in the above range, the influence on the urethanization reaction using the polycarbonate polyol is small.

  The catalyst used in the production of the polycarbonate polyol may be treated with a phosphorus compound. Examples of the phosphorus compound include phosphoric acid triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate; methyl acid phosphate, ethyl acid Phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate Atylene Glucol Acid Phosphate Acid phosphates such as 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate; triphenyl phosphite, trisnonylphenyl phosphate, tricresyl phosphate Phyto, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl Phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis (2-ethylhexyl) Idrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, bis (decyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl Phosphorous esters such as pentaerythritol diphosphite and tris (2,4-di-tert-butylphenyl) phosphite; phosphoric acid; phosphorous acid; hypophosphorous acid and the like. A phosphorus compound may be used individually by 1 type, and may use 2 or more types together.

  When the above treatment with a phosphorus compound is performed, the phosphorus compound may remain in the obtained polycarbonate polyol. The content of the phosphorus compound in the polycarbonate polyol is preferably 0.0001 to 0.05% by mass based on the mass of the polycarbonate polyol as the content of the phosphorus element (P) measured using ICP. 0.0005 to 0.02 mass% is more preferable. If the content of the phosphorus compound is in the above range, in the production of polyurethane, it becomes possible to eliminate the influence of the catalyst used in the production of polycarbonate polyol, and when the obtained polyurethane is used for applications such as paints. The phosphorus compound is less likely to affect the physical properties of the coating film.

There is no restriction | limiting in particular in the specific manufacturing method of a polycarbonate polyol, It is aimed by making the diol (a) and diol (b) and carbonate compound to be used react in one step with other arbitrary components as needed. A polycarbonate polyol may be obtained, or a low-molecular-weight polycarbonate polyol may be obtained once, and then the degree of polymerization may be further increased to obtain the target polycarbonate polyol.
As a more specific production method in the latter case, for example, the following method may be mentioned. That is, first, a diol (a) and a diol (b) and the polyol component containing the above-mentioned other diol and / or the polyol having three or more hydroxyl groups used as necessary, and a carbonate compound, the former / The latter is mixed at a molar ratio of 20/1 to 1/10, and the first stage reaction is performed at 100 to 250 ° C. under normal pressure or reduced pressure to obtain a reaction product containing a low molecular weight polycarbonate polyol. Here, when dimethyl carbonate or diethyl carbonate is used as the carbonate compound, the resulting methanol or ethanol can be removed as a mixture with dimethyl carbonate or diethyl carbonate to obtain a low molecular weight polycarbonate polyol. Similarly, when ethylene carbonate is used as the carbonate compound, the resulting ethylene glycol can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate polyol. Next, as the second-stage reaction, the first-stage reaction product is heated at 160 to 250 ° C. under reduced pressure to remove unreacted polyol component and carbonate compound, and low molecular weight polycarbonate polyol. To obtain the desired polycarbonate polyol having a predetermined molecular weight.

  The above-mentioned polycarbonate polyol can easily be produced as a polyurethane that easily becomes a liquid at room temperature and has excellent handleability and excellent flexibility. The present invention includes such a polycarbonate polyol. In addition, you may use the said polycarbonate polyol for uses other than manufacture of a polyurethane.

  In the production of polyurethane, only the above-described polycarbonate polyol of the present invention may be used as the polymer polyol, but other polycarbonate polyols, polyester polyols, polyether polyols, etc. other than the polycarbonate polyol of the present invention are used. You may use together 1 type (s) or 2 or more types of polymer polyols other than a polyol. The proportion of the polycarbonate polyol of the present invention in the polymer polyol used for the production of polyurethane is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass or more. More preferably, it may be 100% by mass.

-Polyisocyanate Examples of the polyisocyanate used in the production of polyurethane include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), crude TDI, diphenylmethane-4,4'- Diisocyanate (MDI), crude MDI, naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, etc. Aromatic diisocyanate: 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexanedi Isocyanate aliphatic (hydrogenated XDI) and the like or cycloaliphatic diisocyanate; these isocyanates isocyanurate-modified products, carbodiimide-modified products, and the like biuret-modified products. These polyisocyanates may be used alone or in combination of two or more.

-Chain extender In the production of polyurethane, a chain extender can be further used as a copolymerization component according to desired physical properties. As the chain extender, any chain extender conventionally used in the production of polyurethane can be used, and for example, a low molecular polyol, polyamine, water and the like can be used.
As the low-molecular polyol, for example, a polyol having a molecular weight of less than 300 can be used, and more specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol. 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p -Hydroxyphenyl) propane and the like. Examples of the polyamine include ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, diphenyldiamine, and diaminodiphenylmethane. These chain extenders may be used individually by 1 type, and may use 2 or more types together.

-Polyurethane production method There is no particular restriction on the polyurethane production method, and these are reacted by using the above-mentioned polycarbonate polyol, polyisocyanate and, if necessary, a chain extender and employing a known urethanization reaction technique. Can be manufactured. As the reaction temperature in the urethanization reaction for producing polyurethane, although depending on the reaction form, for example, a temperature within a range from room temperature to 200 ° C. can be employed.
Polyurethane may be produced by any one of the one-shot method and the prepolymer method. For example, when a chain extender is used, each component used in the reaction may be reacted together to produce the target polyurethane. First, the polycarbonate polyol and the polyisocyanate are mixed, and the molar equivalent of the polyisocyanate is excessive. A urethane prepolymer having an isocyanate terminal may be produced by reacting under the following conditions, and then the target polyurethane may be produced by increasing the molecular weight by reacting the urethane prepolymer with a chain extender.

  The urethanization reaction may be performed using a urethanization reaction catalyst. There is no restriction | limiting in particular in the kind of the said urethanation reaction catalyst, For example, amine compounds (Tertiary amines, such as a triethylamine, N-ethylmorpholine, a triethylenediamine, a diazabicycloundecene, etc.), organotin compounds (Trimethyltin) Laurate, dibutyltin dilaurate, etc.), organic titanium compounds, organic lead compounds (lead octylate, etc.), and the like. A urethanization reaction catalyst may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of reactivity, organotin compounds are preferable, and dibutyltin dilaurate is more preferable.

  The urethanization reaction may be carried out in the substantial absence of a solvent or in the presence of a solvent. Examples of the solvent include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve, and the like. A solvent may be used individually by 1 type and may use 2 or more types together. Among these, amide solvents are preferable, and dimethylformamide is more preferable.

-Urethane (meth) acrylate The polyurethane of this invention may be urethane (meth) acrylate which has a (meth) acryloyl group in the molecule | numerator. The urethane (meth) acrylate is useful as a component constituting a photocurable composition described later. The urethane (meth) acrylate may be further reacted with a compound having a (meth) acryloyl group when reacting the above-described polycarbonate polyol, polyisocyanate and, if necessary, a chain extender, or polycarbonate polyol, It can be obtained by further reacting a compound having a (meth) acryloyl group with a polyisocyanate and, if necessary, a polyurethane having an isocyanate group obtained by reacting with a chain extender.

  In producing the polyurethane having an isocyanate group, a conventionally known production method can be employed. For example, it can be obtained by reacting polycarbonate polyol and excess polyisocyanate at 10 to 100 ° C., preferably 20 to 90 ° C., using a urethanization reaction catalyst. Here, the ratio (molar ratio) between the number of hydroxyl group equivalents of the polycarbonate polyol and the number of isocyanate group equivalents of the polyisocyanate is preferably the former / the latter = 0.25 to 1.0, preferably 0.4 to 0.7. It is more preferable that When the ratio is equal to or more than the above lower limit, it is possible to suppress the acrylate polymer finally obtained from remaining excessive isocyanate groups from being hard and brittle. Moreover, it can suppress that an isocyanate group reduces extremely and it becomes difficult to obtain the target urethane acrylate because the said ratio is below the said upper limit.

  Hydroxyalkyl (meth) acrylate can be preferably used as the compound having the (meth) acryloyl group used when the urethane (meth) acrylate is obtained by reacting with an isocyanate group-containing polyurethane. Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. The ratio of these components when the polyurethane having an isocyanate group and hydroxyalkyl (meth) acrylate are reacted is the ratio between the number of hydroxyl equivalents of hydroxyalkyl (meth) acrylate and the number of isocyanate groups equivalent of the polyurethane having isocyanate groups ( As the molar ratio), the former / the latter is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. Moreover, as reaction temperature at the time of performing the said reaction, it is preferable that it is 30-90 degreeC, and it is more preferable that it is 60-80 degreeC.

  In producing urethane (meth) acrylate by reacting a polyurethane having an isocyanate group and a compound having a (meth) acryloyl group, in order to control the radical polymerization reaction by the heat of the (meth) acryl group, A polymerization inhibitor may be added or the reaction may be performed in the presence of oxygen. Examples of the polymerization inhibitor used include orthonitrotoluene, hydroquinone, hydroquinone monomethyl ether, and copper chloride. These may be used individually by 1 type and may use 2 or more types together. The addition amount of a polymerization inhibitor can be in the range of 50-5,000 ppm with respect to the mass of the compound which has the (meth) acryloyl group used.

-Polyurethane for aqueous dispersion The polyurethane of the present invention can be made into a polyurethane for aqueous dispersion by introducing a carboxyl group or a salt thereof into the molecule. The polyurethane for an aqueous dispersion is useful as a component constituting an aqueous polyurethane dispersion (particularly, an aqueous polyurethane paint). For example, the polyurethane for an aqueous dispersion is obtained by further reacting a polyol having a carboxyl group by reacting a polycarbonate polyol, polyisocyanate and, if necessary, a chain extender as described above, with a urethane prepolymer having a carboxyl group. It can be obtained in the form of a dispersion by forming a polymer and extending the chain in an aqueous medium.

  Examples of the polyol having a carboxyl group used in producing a urethane prepolymer having a carboxyl group include dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Is mentioned.

  Moreover, as a chain extender used when extending the urethane prepolymer having a carboxyl group, for example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4 -Butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, Amine compounds such as piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycol ( Polyethylene Diol compound of glycol) and the like; and water. These may be used alone or in combination of two or more. Among these, an amine compound is preferable and a primary diamine compound is more preferable.

  The carboxyl group in the polyurethane obtained by chain extension as described above may be in the form of a salt with a neutralizing agent or the like, or may be in the form of a salt. Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, and pyridine. Organic amines; inorganic alkali compounds such as sodium hydroxide and potassium hydroxide; ammonia and the like. Among these, organic amines are preferable, tertiary amines are more preferable, and triethylamine is more preferable.

  In producing a polyurethane for an aqueous dispersion, amides such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone may be added as a film-forming aid contained in the resulting dispersion.

As a specific method for producing the polyurethane for an aqueous dispersion, for example, the following four steps (1) to (4) may be mentioned.
(1) A step of obtaining a urethane prepolymer having a carboxyl group by reacting a polycarbonate polyol, polyisocyanate, a polyol having a carboxyl group and, if necessary, a chain extender.
(2) The process of neutralizing the carboxyl group in the urethane prepolymer which has a carboxyl group with a neutralizing agent.
(3) A step of dispersing the neutralized urethane prepolymer in an aqueous medium.
(4) A step of reacting the dispersed urethane prepolymer with a chain extender.
In addition, you may perform the said process (3) and (4) simultaneously. Moreover, after dispersing a urethane prepolymer in solvents other than water, it can also be set as a desired aqueous polyurethane dispersion by further mixing with water and then distilling off the solvent.

<< Composition containing polyurethane >>
The polyurethane of the present invention may be used for various applications as it is, or may be used for various applications in the form of a composition containing the polyurethane. There is no restriction | limiting in particular in components other than the polyurethane contained in the said composition, According to various uses etc., it can select suitably. Examples of components other than the polyurethane include a heat stabilizer, a light stabilizer, an anti-aging agent, a plasticizer, an inorganic filler, a lubricant, a colorant, a foaming agent, a flame retardant, and silicone oil. These components may be used individually by 1 type, and may use 2 or more types together. There is no restriction | limiting in particular in content of the polyurethane in the composition of this invention, For example, it can be 20 mass% or more, and it is good also as 50 mass% or more, 80 mass% or more, and also 95 mass% or more.

-Heat stabilizer Examples of the heat stabilizer include phosphorus stabilizers, phenol stabilizers, sulfur-containing stabilizers, tin stabilizers, and the like. Examples of the phosphorus stabilizer include phosphoric acid or phosphorous acid alkyl ester, aryl ester, alkylaryl ester or aralkyl ester, hypophosphorous acid derivative, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpenta Examples include erythritol diphosphite and dialkyl bisphenol A diphosphite. Examples of the phenol-based stabilizer include hindered phenol compounds. Examples of the sulfur-containing stabilizer include thioether stabilizers, dithioate stabilizers, mercaptobenzimidazole stabilizers, thiocarbanilide stabilizers, and thiodipropionic acid esters. Examples of the tin stabilizer include tin malate and dibutyl tin monoxide. These stabilizers may be used individually by 1 type, and may use 2 or more types together. Among these heat stabilizers, from the viewpoint of improving heat stability, a phenol-based stabilizer is preferable, a hindered phenol compound is more preferable, and “Irganox 1010” (trade name: manufactured by Ciba Geigy), “Irganox 1520” (trade name) : Manufactured by Ciba Geigy Corporation) is more preferable. The content of the stabilizer in the composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of polyurethane. More preferably, it is 2-2 mass parts.

-Light stabilizer Examples of the light stabilizer include benzotriazole-based light stabilizers and benzophenone-based light stabilizers. In addition, radical scavenging light stabilizers such as hindered amine compounds can be used. These light stabilizers may be used individually by 1 type, and may use 2 or more types together.

-Antiaging agent As said antiaging agent (secondary antiaging agent), a phosphorus compound, a sulfur compound, etc. can be used, for example. Examples of the phosphorus compound include “PEP-36”, “PEP-24G”, “HP-10” (all trade names: manufactured by Asahi Denka Co., Ltd.), “Irgafos168” (trade names: manufactured by Ciba Geigy) ) Etc. can be used. Examples of the sulfur compound include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP). These anti-aging agents may be used individually by 1 type, and may use 2 or more types together.

・ Plasticizer Examples of the plasticizer include phthalate esters such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate; tricresyl Phosphate esters such as phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate; trimellitic acid such as trimellitic acid octyl ester, trimellitic acid isodecyl ester Esters; pyromellitic esters such as octyl ester of pyromellitic acid; dipentaerythritol ester, geo Fatty acid esters such as octyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methyl acetyl ricinoate; epoxidized soybean oil, epoxidized linseed Oil, epoxy plasticizers such as epoxidized fatty acid alkyl esters; polyether plasticizers such as adipic acid ether esters and polyethers; liquid rubbers such as liquid NBR, liquid acrylic rubber, and liquid polybutadiene; non-aromatic paraffin oils, etc. Is mentioned. These plasticizers may be used alone or in combination of two or more. The content of the plasticizer in the composition of the present invention can be appropriately selected according to required hardness, physical properties and the like, and is preferably 50 parts by mass or less with respect to 100 parts by mass of polyurethane.

Inorganic filler Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, and carbon black. These inorganic fillers may be used alone or in combination of two or more.

<Application>
The use of the polyurethane of the present invention or the composition containing the same is not particularly limited, but the polyurethane of the present invention is excellent in flexibility and can be easily produced. Polyurethane), spandex (elastic fiber), synthetic or artificial leather, ink binder, rigid foam, flexible foam, etc., can be widely used from soft use to hard use. Moreover, as a form of the polyurethane in these uses, a solvent system and an aqueous system may be used besides a solventless system.

  Hereinafter, the case where the polyurethane of the present invention or a composition containing the same is used for a synthetic or artificial leather and a photocurable composition will be described in more detail.

Synthetic or artificial leather The polyurethane of the present invention or a composition containing the same can be preferably used for synthetic or artificial leather. Such synthetic or artificial leather is generally a laminate having a fibrous base material layer and a polyurethane-containing layer (preferably a skin layer) laminated on at least one surface of the fibrous base material layer. Including the body. The polyurethane of the present invention can be used as a polyurethane in the polyurethane-containing layer, thereby making it possible to more restrain the fibers, and synthetic or artificial leather excellent in tear strength, tensile strength, heat distortion resistance, etc. Can be obtained.

  As the fibrous base material constituting the fibrous base material layer in the laminate, various fibrous base materials conventionally used in the production of synthetic or artificial leather can be used, for example, various nonwoven fabrics, various woven fabrics. Knitted fabrics can be used. These fibrous base materials may form a fibrous base material layer alone, but the fibrous base material layer may be formed in a state in which at least a part of the voids is filled with a resin. . In the latter case, the polyurethane of the present invention can be used as at least part of the resin.

  When using a nonwoven fabric as a fibrous base material, there is no particular limitation on the material of the nonwoven fabric, but when using a nonwoven fabric in which leather fibers and chemical fibers are entangled, sensory characteristics peculiar to natural leather such as appearance, touch, and texture. Can be more easily applied.

  The leather fibers constituting the nonwoven fabric can be obtained by processing the leather into fibers. The raw material includes, for example, leather scraps generated in the manufacturing process of leather products, particularly in the process from tanned leather to products. Examples of the leather waste include shaving waste and cutting waste as well as buff waste generated when the surface of the dense layer is polished with sandpaper. After removing moisture by heat treatment, these can be used as they are, or, for relatively large sizes such as cutting waste, processed into fibers of an appropriate size using a pulverizer or a spreader. . Moreover, as leather, the thing derived from mammals, such as a cow, a horse, a pig, a goat, a sheep, a deer, a kangaroo, can be used, for example.

  As said chemical fiber which comprises a nonwoven fabric, a synthetic fiber, a semisynthetic fiber, a regenerated fiber etc. are mentioned, for example. These may be used individually by 1 type and may use 2 or more types together. Specific examples of the chemical fiber include polyester fiber, nylon fiber, acrylic fiber, and rayon fiber.

  There is no restriction | limiting in particular in the manufacturing method of a nonwoven fabric, It can manufacture by a well-known method. As a typical method for producing a nonwoven fabric, there is one including two steps of a fleece forming step and an interfiber bonding step. In this manufacturing method, first, a fiber accumulation layer called a fleece (sometimes called a web) is formed in a fleece forming step, and then fibers are bonded in an interfiber bonding step. As a fleece formation method, for example, a dry method, a wet method, a spunbond method, etc. can be adopted. As a fiber bonding method, for example, a chemical bond method, a needle punch method, a spunlace method, a stitch bond method, etc. The steam jet method can be employed, and any of them can be appropriately selected according to the specific use of the resulting synthetic or artificial leather. Above all, it is possible to fix fibers while maintaining the feeling of swelling, tactile sensation, and texture, and to obtain a nonwoven fabric suitable for synthetic or artificial leather, and consequently a fibrous base material. It is preferable.

  As described above, the resin may be filled in at least a part of the voids of the fibrous base material. The polyurethane of the present invention may be used as the resin, or other resins may be used. When the polyurethane of the present invention is used as the resin, the polyurethane of the present invention may be used alone, but for the purpose of imparting heat resistance, flex resistance, stagnation resistance, wear resistance, etc., the polyurethane of the present invention. In addition, other resins such as an acrylic resin may be blended. There is no particular limitation on the usage form of the polyurethane of the present invention to be filled in the voids of the fibrous base material, and any of solvent-based and water-based may be used, but water-based is preferable from the viewpoint of environmental load, and one-pack type is preferable. preferable.

  For the above resin to be filled in the voids of the fibrous base material, a catalyst, a crosslinking agent, a smoothing agent, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, and a light resistance are added as necessary. Stabilizer, fluorescent brightener, foaming agent, thermoplastic resin, thermosetting resin, dye, pigment, flame retardant, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam Body, crystal water-containing compound, water-absorbing agent, moisture-absorbing agent, deodorant, foam stabilizer, antifoaming agent, antifungal agent, antiseptic, algae-proofing agent, pigment dispersant, inert gas, anti-blocking agent, hydrolysis Various additives such as an inhibitor, a matting agent, a tactile sensation improver, a slip improver, and a thickener can be contained.

  There is no particular limitation on the method for filling the voids in the fibrous base material with a resin, and a known method can be adopted. For example, the fibrous base material is immersed in a liquid (resin liquid) containing the resin and then squeezed with a mangle. A liquid method (mangle-pad method); a method of applying a resin liquid to a fibrous base material using a spray coater, a gravure coater, a reverse coater, a doctor knife coater, or the like can be employed. Among these, the mangle-pad method is preferable because the resin liquid can be uniformly filled in the voids of the fibrous base material.

  After filling the resin liquid, the target fibrous base material layer can be obtained by evaporating the solvent in the resin liquid by heat treatment. There is no restriction | limiting in particular in the heat processing temperature at the time of performing the said heat processing, Although it can set suitably according to the additive used arbitrarily, a filling amount, etc., it is preferable to exist in the range of 80-140 degreeC. When the heat treatment temperature is 80 ° C. or higher, the resin liquid is sufficiently dried, and the flex resistance, the sag resistance, and the wear resistance are further improved. In addition, when the heat treatment temperature is 140 ° C. or lower, when leather fibers are used, they shrink and harden, resulting in problems such as the feel or texture of the resulting synthetic or artificial leather becomes coarse. Can be suppressed. Although there is no restriction | limiting in particular in the heat processing time at the time of performing the said heat processing, It is preferable to exist in the range of 50 to 400 second. When the heat treatment time is 50 seconds or longer, the resin liquid is sufficiently dried, and the flex resistance, the sag resistance, and the wear resistance are further improved. In addition, the heat treatment time of 400 seconds or less suppresses the occurrence of problems such as shrinkage and curing of leather fibers when used, and the resulting synthetic or leather texture and texture becoming coarse. can do. For the heat treatment, for example, a known apparatus such as a loop dryer, a net dryer, an oven, or a heat setter can be used.

  Moreover, as above-mentioned, the polyurethane of this invention can be used as a polyurethane in the layer (preferably skin layer) containing the polyurethane which comprises the said laminated body contained in synthetic | combination thru | or artificial leather. The form of use of the polyurethane of the present invention in forming a layer containing polyurethane is not particularly limited, and may be any of hot-melt, solvent-based, and water-based, one-component, two-component curable, moisture Any of curable types may be used. Among these, a hot-melt two-component curable type is preferable because it has a low environmental load and a porous layer is obtained by foaming.

  The layer containing polyurethane may be formed by using the polyurethane of the present invention alone, but may be formed by a composition containing the polyurethane of the present invention. In the composition, in addition to the polyurethane of the present invention, various components as described above in the description of the composition of the present invention, various additives that can be contained in the resin filled in the voids of the fibrous base material, etc. One or more of them can be contained.

  In the production of the laminate, there is no particular limitation on the method of laminating a layer containing polyurethane (preferably a skin layer) on at least one surface of the fibrous base material layer, and a known method can be adopted. A method of applying a polyurethane-containing liquid (polyurethane liquid) to the base material layer and then forming a film; applying a polyurethane liquid to the releasable base material, and then bonding the fibrous base material layer to form a film Or the like can be adopted. The polyurethane liquid is a liquid containing at least polyurethane and further containing additives and a solvent as necessary. When using a hot-melt polyurethane, the coating operation can be performed by heating and melting. It may be liquefied.

  In order to apply the polyurethane liquid to the fibrous base material layer or the releasable base material, for example, a known device such as a spray coater, a roll coater, a knife coater, a comma coater, a T-die coater, or a reverse coater may be used. it can. Among these, a comma coater is preferable because it is easy to control the processing speed and the coating amount.

  An appropriate method may be adopted for forming the polyurethane liquid after the coating depending on the form of polyurethane to be selected. For example, when solvent-based or water-based polyurethane is used, a film can be formed by evaporating the solvent in the polyurethane liquid by heat treatment. Further, solvent-based or water-based polyurethane is often one-pack type, and it is preferable to add a crosslinking agent in order to further improve the film strength. In this case, it is preferable to perform a heat treatment in order to promote the reaction.

  There is no restriction | limiting in particular in the heat processing temperature at the time of performing the said heat processing, Although it can set suitably according to the additive used arbitrarily, an application quantity, etc., it is preferable to exist in the range of 80-140 degreeC. When the heat treatment temperature is 80 ° C. or higher, the polyurethane liquid is sufficiently dried and crosslinked, and the wear resistance is further improved. Moreover, when the heat treatment temperature is 140 ° C. or lower, it is possible to suppress the occurrence of problems such as pinholes due to excessive heating of polyurethane and the appearance being impaired. Although there is no restriction | limiting in particular in the heat processing time at the time of performing the said heat processing, It is preferable to exist in the range of 50 to 400 second. When the heat treatment time is 50 seconds or longer, the polyurethane liquid is sufficiently dried and crosslinked, and the wear resistance is further improved. In addition, when the heat treatment time is 400 seconds or less, it is possible to suppress the occurrence of problems such as deterioration of the polyurethane and poor wear resistance. For the heat treatment, for example, a known apparatus such as a loop dryer, a net dryer, an oven, or a heat setter can be used. When hot-melt polyurethane is used, it can be solidified (formed into a film) by cooling.

  When using a two-component curable polyurethane or a moisture curable polyurethane, it is preferable to perform an aging treatment after solidification (film formation). The curing reaction rate in the aging treatment varies depending on the type and amount of the main agent (prepolymer), the curing agent, and optionally used additive (especially catalyst). Although it is preferable, it is usually performed at room temperature for about 1 day to 1 week. In this process, the curing reaction between the main agent and the curing agent can be completed. Finally, if the curing reaction is incomplete, the wear resistance may be reduced.

  The thickness of the layer containing polyurethane (preferably the skin layer) in the laminate is preferably in the range of 100 to 400 μm. Abrasion resistance improves because the said thickness is 100 micrometers or more. In addition, when the thickness is 400 μm or less, it is possible to suppress the occurrence of problems such as the feeling of touch and texture of the synthetic or artificial leather to be obtained.

  The layer containing polyurethane may be either a nonporous layer or a porous layer, but is preferably a porous layer from the viewpoint of touch and texture. In order to form a layer containing polyurethane as a porous layer, a known method, for example, a method using carbon dioxide gas generated by the reaction between a main agent (prepolymer) and a curing agent in a two-component curing type polyurethane is adopted. can do.

  The layer containing polyurethane may be laminated on at least one surface of the fibrous base material layer via an adhesive layer. As a result, excessive penetration of the polyurethane (prepolymer composition, etc.) constituting the polyurethane-containing layer into the fibrous base material layer, which may occur when the polyurethane-containing layer is directly laminated on the fibrous base material layer In addition, the formation of non-uniform pores in the layer containing polyurethane is suppressed, and a natural leather-like feel and texture can be provided more easily.

  The adhesive layer can be formed of polyurethane formed by a moisture curing reaction of a urethane polyisocyanate prepolymer. Here, the urethane polyisocyanate prepolymer is a urethane prepolymer having an isocyanate group at the molecular end. Polyurethane is formed by the reaction of the isocyanate groups present at the molecular ends of the urethane polyisocyanate prepolymer with moisture in the atmosphere.

  Polyols and polyisocyanates that can be used in producing the urethane polyisocyanate prepolymer are not particularly limited, and the polycarbonate polyol of the present invention may be used, or other polyols (polymer polyols, etc.) other than that. Can also be used. The said polyol may be used individually by 1 type, and may use 2 or more types together. Among these, as the polyol, polyether polyol or polycarbonate polyol is preferable from the viewpoint of hydrolysis resistance, and polycarbonate polyol is more preferable from the viewpoint of light resistance and heat resistance. The polyisocyanate is preferably 4,4'-diphenylmethane diisocyanate (MDI) from the viewpoint of easy control of the curing reaction.

  The polyurethane forming the adhesive layer may be a two-component curable hot melt polyurethane. In this case, the heating and melting temperature of the corresponding urethane polyisocyanate prepolymer is usually set in the range of 30 to 150 ° C., whereby the viscosity of the urethane polyisocyanate prepolymer at the time of heating and melting is 1,000 to 15,000 cps. It can be.

  The thickness of the adhesive layer is preferably 10 to 70 μm. Abrasion resistance improves because thickness is 10 micrometers or more. In addition, when the thickness is 70 μm or less, it is possible to suppress the occurrence of problems such as tactile sensation and texture becoming hard.

  Synthetic or artificial leather may be composed only of the laminate, but may have other layers as necessary, for example, polyurethane on the surface of the laminate containing polyurethane. You may further have a protective layer which consists of. The polyurethane used for forming the protective layer is not particularly limited, and the same polyurethane as used for forming the layer containing polyurethane of the laminate can be used. The additive that can be blended in the protective layer can be the same as the layer containing polyurethane, and the lamination method of the protective layer can be the same as the layer containing polyurethane.

-Photocurable composition The polyurethane of this invention, especially the urethane (meth) acrylate which has a (meth) acryloyl group in a molecule | numerator as mentioned above can be used preferably as a structural component of a photocurable composition. The photocurable composition typically contains the urethane (meth) acrylate and a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzophenone, acetophenone, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, 4,4′-bisdimethylaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropane. Examples include -1-one, benzyldimethyl ketal, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone. A photoinitiator may be used individually by 1 type and may use 2 or more types together. The content of the photopolymerization initiator in the photocurable composition is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of urethane (meth) acrylate. Is more preferable.

  The photocurable composition may further contain a diluent for the purpose of reducing the viscosity. As the diluent, a liquid ethylenically unsaturated compound can be preferably used. Examples of the diluent include 2-hydroxyethyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, styrene, vinyl pyrrolidone, and tetrahydrofurfuryl acrylate. A diluent may be used individually by 1 type and may use 2 or more types together. It is preferable that it is 10-60 mass parts with respect to 100 mass parts of urethane (meth) acrylates, and, as for content of the diluent in a photocurable composition, it is more preferable that it is 20-40 mass parts.

  The photocurable composition of the present invention improves the flexibility of a cured product such as a coating film or coating film, and is excellent in adhesion, so that it includes paints, adhesives, printing ink vehicles, solder resist inks. It can be preferably used for various applications such as letterpress materials, mortar floor lining materials, PVC tile coating materials, optical fiber coating materials, and plastic coating materials. In addition, as an active energy ray at the time of hardening a photocurable composition, an electron beam, a gamma ray, light etc. are mentioned, for example, As a light, an ultraviolet-ray is preferable.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In addition, each evaluation method employ | adopted in the following examples and comparative examples is shown below.

<Number average molecular weight>
Acetic anhydride (12.5 g) was diluted with 50 mL of pyridine to prepare an acetylating reagent. In a 100 mL eggplant flask, 2.5 to 5.0 g of the sample is accurately weighed (this mass is defined as e (g)), 5 mL of an acetylating reagent and 10 mL of toluene are added with a whole pipette, and a condenser tube is attached. Stir and heat at 1 ° C. for 1 hour. Thereafter, 2.5 mL of distilled water was added with a whole pipette, and the mixture was further heated and stirred for 10 minutes. After cooling for 2 to 3 minutes, 12.5 mL of ethanol was added, and 2 to 3 drops of phenolphthalein was added as an indicator, followed by titration with 0.5 mol / L ethanolic potassium hydroxide (this titration amount was determined as a (mL )). On the other hand, as a blank test, 5 mL of an acetylating reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL eggplant flask and stirred for 10 minutes, and then titrated in the same manner (this titration was defined as b (mL). To do). Based on these results, the hydroxyl value was calculated by the following formula (i). In the formula (i), f is a factor of the titrant (0.5 mol / L ethanolic potassium hydroxide). Next, based on the obtained hydroxyl value, the number average molecular weight was determined by the following formula (ii).
Hydroxyl value (mg-KOH / g) = {(ba) × 28.05 × f} / e (i)
Number average molecular weight = 2 / (hydroxyl value × 10 ⁻³ /56.11) (ii)

<Copolymerization composition ratio>
^It calculated | required using < ¹ > H-NMR. The analysis used “AV400” manufactured by Bruker, and deuterated chloroform as a measurement solvent. ^The copolymer composition ratio (molar ratio) of each diol component in the polycarbonate polyol was calculated from the integral ratio of peaks corresponding to each structural unit in the spectrum obtained by ¹ H-NMR.

[Example 1]
・ Production of polycarbonate polyol containing structural units derived from 2-methyl-1,3-propanediol and structural units derived from MPD Stirrer, thermometer, Oldershaw type distillation column with vacuum jacket having reflux head at the top Into a 2 L separable flask equipped with a 2-methyl-1,3-propanediol 300 g (3.33 mol), 3-methyl-1,5-pentanediol 393 g (3.33 mol), and ethylene carbonate 581 g (6 .6 mol) was added and dissolved by stirring at 70 ° C., and then 0.015 g of lead acetate trihydrate was added. Subsequently, the reaction was carried out for 12 hours at 140 ° C. and a pressure of 1.5 kPa while removing a portion of the fraction from the reflux head at a reflux ratio of 4. Thereafter, the Oldershaw type distillation column was replaced with a simple distillation apparatus, and concentrated at an internal temperature of 140 to 150 ° C. and a pressure of 0.5 kPa. Thereafter, the mixture was further reacted at an internal temperature of 160 to 165 ° C. for 4 hours to obtain a polycarbonate polyol containing a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from MPD. The polycarbonate polyol was liquid at room temperature and excellent in handleability. The number average molecular weight of the obtained polycarbonate polyol was 2020, and the copolymer composition ratio (molar ratio) determined by ¹ H-NMR analysis was [structural unit derived from 2-methyl-1,3-propanediol] / [MPD Structural unit derived from] = 50/50.

[Example 2]
-Production of polyurethane A In a 1 L separable flask equipped with a nitrogen introduction tube and a thermometer, 120 g (60 mmol) of the polycarbonate polyol obtained in Example 1, 10.8 g (120 mmol) of 1,4-butanediol, 4,4 A solution containing polyurethane A was obtained by charging 45.0 g (180 mmol) of '-diphenylmethane diisocyanate and 350 g of dehydrated dimethylformamide and reacting at 80 ° C. for 6 hours.

[Comparative Example 1]
Example, except that polycarbonate polyol “C-2050” (number average molecular weight: 2000, diol component: MPD and 1,6-hexanediol only, liquid at room temperature) manufactured by Kuraray Co., Ltd. was used as the polycarbonate polyol. Reaction was performed in the same manner as in Example 2 to obtain a solution containing polyurethane B.

[Comparative Example 2]
As polycarbonate polyol, the same procedure as in Example 2 was used except that polycarbonate polyol “Nippolan 980R” (number average molecular weight: 2000, diol component: only 1,6-hexanediol, solid at room temperature) manufactured by Tosoh Corporation was used. To obtain a solution containing polyurethane C.

<Evaluation method>
Each polyurethane solution obtained in Example 2, Comparative Example 1 and Comparative Example 2 was coated on a polypropylene sheet using a bar coater and dried with hot air at 80 ° C. for 24 hours to obtain a polyurethane film having a thickness of 100 μm. It was. A JIS No. 4 dumbbell-shaped test piece was produced from this film. The test piece was subjected to various tensile tests using an Instron 5566 type tensile tester. The marked line section was set to 20 mm, the tensile speed was set to 500 mm / min, and the test was performed under the condition of 25 ° C. The results are shown in Table 1.

  From the above results, it can be seen that the polycarbonate polyol of the present invention is liquid at room temperature and excellent in handleability and can easily produce polyurethane, and the obtained polyurethane is excellent in flexibility.

Claims (9)

  A polyurethane comprising a structural unit derived from a polycarbonate polyol comprising a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from a diol having 6 carbon atoms having an alkyl side chain.   The molar ratio of the structural unit derived from 2-methyl-1,3-propanediol and the structural unit derived from a diol having 6 carbon atoms having an alkyl side chain is the former / the latter = 80/20 to 20/80. The polyurethane according to claim 1.   The polyurethane according to claim 1 or 2, wherein the polycarbonate polyol is a reaction product of 2-methyl-1,3-propanediol, a diol having 6 alkyl atoms and a diol having 6 carbon atoms and a carbonate compound.   The polyurethane according to claim 3, wherein the carbonate compound is ethylene carbonate.   The polyurethane according to any one of claims 1 to 4, wherein the diol having an alkyl side chain and having 6 carbon atoms is 3-methyl-1,5-pentanediol.   It is a manufacturing method of the polyurethane in any one of Claims 1-5, Comprising: The structural unit derived from the structural unit derived from 2-methyl- 1, 3- propanediol and the C6 diol which has an alkyl side chain A process comprising the step of reacting a polycarbonate polyol, polyisocyanate and a chain extender.   The composition containing the polyurethane in any one of Claims 1-5.   A polycarbonate polyol comprising a structural unit derived from 2-methyl-1,3-propanediol and a structural unit derived from a diol having 6 carbon atoms having an alkyl side chain. The molar ratio of the structural unit derived from 2-methyl-1,3-propanediol and the structural unit derived from a diol having 6 carbon atoms having an alkyl side chain is the former / the latter = 80/20 to 20/80. The polycarbonate polyol according to claim 8.