JP5349806B2 - Urethane resin composition - Google Patents

Description

  The present invention relates to a urethane resin composition obtained by reacting a crystalline polyoxyalkylene polyol and a polyisocyanate.

The urethane resin is manufactured by reacting an isocyanate component and a polyol component. As the polyol component, various polyols are used because they greatly affect the properties of the urethane resin.
For example, as a polyol component, there are a urethane resin using a polyester polyol as a raw material and a urethane resin using a polyether polyol as a raw material (for example, Non-Patent Document 1).
Polyurethane resin handbook (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987)

However, for example, a urethane resin using the former polyester polyol as a raw material has good friction resistance (sliding property), tensile strength, tear strength, etc., but has low water resistance and is in contact with water, Since it is also hydrolyzed by the moisture in it, there is a problem in terms of the service life. On the other hand, the urethane resin in which the latter polyether polyol is used as a raw material has a long service life because of its good water resistance, but has a disadvantage that its mechanical strength is inferior.
Then, this invention makes it a subject to give mechanical strength, such as favorable friction resistance (sliding property) and tensile strength, to urethane resin, and to improve the durable performance of urethane resin.

（式中、Ｒ ¹ 〜Ｒ ⁴ は、水素原子、脂肪族、脂環族、芳香族もしくは芳香脂肪族炭化水素基、またはハロゲン原子を表し、そのうちの任意の２つが結合して環を形成していてもよく、その炭素原子に結合する水素原子が反応に関与しない置換基で置換されていてもよい。Ｒ ⁵ 〜Ｒ ¹² は、水素原子、ハロゲン原子、脂肪族、脂環族、芳香族もしくは芳香脂肪族炭化水素基、またはハロゲン原子を表し、そのうちの隣接した２つが結合して環を形成していてもよい。Ｍは第３〜１１族元素を表し、Ｌは配位子を表し、ｎは１または２の整数を表す。ｎが２のとき、２つの配位子Ｌは同一の配位子でも異なった配位子でもよい。）

（式中、Ｒ ¹³ 〜Ｒ ¹⁶ は、水素原子、脂肪族、脂環族、芳香族もしくは芳香脂肪族炭化水素基、またはハロゲン原子を表し、そのうちの任意の２つが結合して環を形成していてもよく、その炭素原子に結合する水素原子が反応に関与しない置換基で置換されていてもよい。Ｒ ⁵ 〜Ｒ ¹² 、Ｍ、Ｌ、ｎは、それぞれ式（１）の記号と同じものを表す。）

The present invention relates to a urethane resin composition that obtained by a crystalline polyoxyalkylene polyol isotacticity is 95% or more (A) reacting a polyisocyanate (B) as the polyol component, is (A) in the presence of a catalyst of the following general formulas (1) or salen complexes represented by (2) (C), urethane resin, characterized in Oh Rukoto polyol obtained alkylene oxide with (a) by ring-opening polymerization Related to things.

(Wherein R ^{1 to} R ⁴ represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic or araliphatic hydrocarbon group, or a halogen atom, and any two of them combine to form a ring. The hydrogen atom bonded to the carbon atom may be substituted with a substituent that does not participate in the reaction, and R ^{5 to} R ¹² are a hydrogen atom, a halogen atom, an aliphatic group, an alicyclic group, an aromatic group. Or it represents an araliphatic hydrocarbon group or a halogen atom, and two of them may be bonded to form a ring, M represents a Group 3 to 11 element, and L represents a ligand. , N represents an integer of 1 or 2. When n is 2, the two ligands L may be the same or different.

(Wherein R ^{13 to} R ¹⁶ represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic or araliphatic hydrocarbon group, or a halogen atom, and any two of them combine to form a ring. And a hydrogen atom bonded to the carbon atom may be substituted with a substituent that does not participate in the reaction, and R ^{5 to} R ¹² , M, L, and n are the same as the symbols in formula (1), respectively. Represents things.)

  The urethane resin composition of the present invention has the friction resistance (sliding property) and low mechanical strength, which are disadvantages of a urethane resin using a polyether polyol as a raw material, and the disadvantages of a urethane resin using a polyester polyol as a raw material. It exhibits good mechanical properties such as good friction resistance (slidability) and tensile strength, and water resistance, with improved hydrolyzability.

  The urethane resin composition in the present invention is obtained by reacting a crystalline polyoxyalkylene polyol (A) and a polyisocyanate (B), and uses a polyoxyalkylene polyol (A) having high isotacticity as a polyol component. Features.

  As polyoxyalkylene polyol (A) having high isotacticity used in the present invention, (1) ring-opening polymerization of a special chiral alkylene oxide (a-1) with a catalyst usually used in the polymerization of alkylene oxide (2) A polyol obtained by ring-opening polymerization of a usual racemic alkylene oxide (a-2) with a special complex described later can be used.

Examples of the chiral alkylene oxide (a-1) include those having 3 to 9 carbon atoms, and examples thereof include the following compounds.
(1) C3 alkylene oxide [(R) -propylene oxide, (S) -propylene oxide, (R) -1-chlorooxetane, (S) -1-chlorooxetane, (R) -2-chlorooxetane (S) -2-chlorooxetane, (1R, 2R) -1,2-dichlorooxetane, (1R, 2S) -1,2-dichlorooxetane, (1S, 2R) -1,2-dichlorooxetane, ( 1S, 2S) -1,2-dichlorooxetane, (R) -epichlorohydrin, (S) -epichlorohydrin, (S) -epibromohydrin, (R) -epibromohydrin];
(2) C4 alkylene oxide [(R) -1,2-butylene oxide, (S) -1,2-butylene oxide, (2R, 3R) -2,3-butylene oxide, (2R, 3S) -2,3-butylene oxide, (2S, 3R) -2,3-butylene oxide, (2S, 3S) -2,3-butylene oxide, (R) -methyl glycidyl ether, (S) -methyl glycidyl ether] ;
(3) C 5 alkylene oxide [(R) -1,2-pentylene oxide, (S) -1,2-pentylene oxide, (2R, 3R) -2,3-pentylene oxide, (2R 3S) -2,3-pentylene oxide, (2S, 3R) -2,3-pentylene oxide, (2S, 3S) -2,3-pentylene oxide, (R) -3-methyl-1, 2-butylene oxide, (S) -3-methyl-1,2-butylene oxide];
(4) C6 alkylene oxide [(R) -1,2-hexylene oxide, (S) -1,2-hexylene oxide, (2R, 3R) -3-methyl-1,2-pentylene Oxide, (2R, 3S) -3-methyl-1,2-pentylene oxide, (2S, 3R) -3-methyl-1,2-pentylene oxide, (2S, 3S) -3-methyl-1, 2-pentylene oxide, (R) -4-methyl-1,2-pentylene oxide, (S) -4-methyl-1,2-pentylene oxide, (2R, 3R) -2,3-hexylene Oxide, (2R, 3S) -2,3-hexylene oxide, (2S, 3R) -2,3-hexylene oxide, (2S, 3S) -2,3-hexylene oxide, (2R, 3R)- 4-methyl-2,3- Nitylene oxide, (2R, 3S) -4-methyl-2,3-pentylene oxide, (2S, 3R) -4-methyl-2,3-pentylene oxide, (2S, 3S) -4-methyl- 2,3-pentylene oxide, allyl glycidyl ether];
(5) C7 alkylene oxide [(R) -1,2-heptylene oxide, (S) -1,2-heptylene oxide];
(6) C8 alkylene oxide [(R) -styrene oxide, (S) -styrene oxide];
(7) C9 alkylene oxide [(R) -phenylglycidyl ether, (S) -phenylglycidyl ether]
Etc.

Among these alkylene oxides, (R) -propylene oxide, (S) -propylene oxide, (R) -1,2-butylene oxide, (S) -1,2-butylene oxide, (2R, 3R) ) -2,3-butylene oxide, (2R, 3S) -2,3-butylene oxide, (2S, 3R) -2,3-butylene oxide, (2S, 3S) -2,3-butylene oxide, (R ) -Styrene oxide and (S) -styrene oxide are preferred.
More preferably (R) -propylene oxide, (S) -propylene oxide, (R) -1,2-butylene oxide, (S) -1,2-butylene oxide, (R) -styrene oxide and (S)- Styrene oxide. Most preferred are (R) -propylene oxide and (S) -propylene oxide.

  The polyoxyalkylene polyol (A) having a high isotacticity according to the present invention is obtained by polymerizing these chiral alkylene oxides (a-1) on the following active hydrogen-containing compound (b).

Examples of the active hydrogen-containing compound (b) include water, 2 to 8 carbon alcohols having 2 to 15 carbon atoms, ammonia, 2 to 4 carbon atoms having 2 to 15 carbon atoms, alkanolamines, and polyhydric phenols. Specific examples include the following compounds.
Water, 2- to 8-valent alcohol [ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc.]; ammonia, 2- to 4-valent amine [monoamine (butylamine, etc.) ), Aliphatic polyamines (ethylenediamine, triethylenediamine, diethylenetriamine, etc.), alicyclic polyamines (piperazine, N-aminoethylpiperazine, etc.), aromatic polyamines (phenylenediamine, tolylenediamine, xylylenediamine, diphenylmethanediamine, etc.)] Alkanolamine [monoethanolamine, diethanolamine, triethanolamine, etc.]]; polyhydric phenol [polyhydric phenol (pyrogallol, hydroquinone, etc.), bisphenol (bisphenol Lumpur A, etc.), etc.]; and mixtures of two or more thereof.
Of these, water and divalent alcohol are preferable, and water, ethylene glycol, propylene glycol, and glycerin are more preferable.

The polymerization method of the chiral alkylene oxide (a-1) may be a conventional method, and commonly used KOH, CsOH, tris (pentafluorophenyl) borane, etc. can be used as the polymerization catalyst.
The reaction is usually −50 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably 0 ° C. to 110 ° C.

Even if it is a racemic alkylene oxide, a polyoxyalkylene polyol (A) with high isotacticity can be obtained by using a special catalyst.
Examples of the racemic alkylene oxide (a-2) include the racemic alkylene oxide (a-1).
Preferred are propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and styrene oxide, more preferred are propylene oxide, 1,2-butylene oxide and styrene oxide, and most preferred is propylene oxide.

  As a method of polymerizing racemic alkylene oxide (a-2) to obtain a polyoxyalkylene polyol (A) having high isotacticity, a salen complex (C), a lanthanoid complex (D), a bimetal μ can be used as a catalyst. Examples include a method of polymerizing with an active hydrogen-containing compound (b) using oxoalkoxide (E) or the like.

  As the salen complex (C), a complex represented by the following general formula (1) or (2) can be used.

In the formula, R ^{1 to} R ^{4 each} represent a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic or araliphatic hydrocarbon group, or a halogen atom, and any two of them are bonded. May form a ring, and the hydrogen atom bonded to the carbon atom is substituted with a substituent that does not participate in the reaction (halogen atom, organic silyl group, alkoxy group, aryloxy group, ester group, amide group, etc.) May be.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonacyl group, a dodecyl group, an iso-propyl group, an iso-butyl group, Examples include sec-butyl group, tert-butyl group, iso-pentyl group, sec-pentyl group, neopentyl group, 2-ethylhexyl group, sec-octyl group and the like.
Of these, preferred are an ethyl group, a propyl group, a butyl group, an iso-propyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group, and particularly preferred are an ethyl group and an iso-propyl group. Most preferred is an ethyl group.

  Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the aromatic or araliphatic hydrocarbon group include a monocyclic aromatic hydrocarbon group and a polycyclic aromatic hydrocarbon group.
Examples of the monocyclic aromatic hydrocarbon group include phenyl group, tolyl group, mesityl group, cumenyl group, benzyl group, phenethyl group, methylbenzyl group, xylyl group, 2,4-dimethoxyphenyl group, 2,5- And a diethoxytolyl group.

  Examples of the polycyclic aromatic hydrocarbon group include a pentalyl group, a naphthyl group, an anthracyl group, a heptaryl group, a phenaryl group, a phenanthryl group, and the like.

Any ^one of R ^{1 to} R ⁴ in the general formula (1) may be bonded to form a ring, and (i) R ^{1 to} R ⁴ are bonded to adjacent carbon atoms. Arbitrary two combine to form a 3-membered to 7-membered skeleton as a divalent hydrocarbon group, or (ii) any two of R ^{1 to} R ⁴ bonded to the same carbon atom Are bonded to form a spiro ring skeleton as a divalent hydrocarbon group. Furthermore, the case where this bivalent hydrocarbon group itself is partially substituted with an alicyclic ring is mentioned. Of (i) and (ii), (i) is preferred from the viewpoint of ring stability.
Specific examples of the divalent hydrocarbon group to which any two of R ^{1 to} R ⁴ are bonded include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group.

Moreover, the hydrogen atom couple | bonded with the carbon atom of a hydrocarbon group may be substituted by the substituent which does not participate in reaction with an isocyanate group etc. Examples of the substituent not involved in the reaction include a halogen atom, an organic silyl group, an alkoxy group, an aryloxy group, an ester group, and an amide group.
Accordingly, specific examples of the case where a part of the linear alkyl group is substituted with these functional groups include, for example, a trichloromethyl group, a perfluoroethyl group, a 2,3-dichloropropyl group, and 1,2-difluorohexyl. Group, perfluoropentyl group, perchlorooctyl group, trimethylsilylmethyl group, trimethylsilylbutyl group, triethylsilylbutyl group, trimethylmethoxyethyl group, phenoxyethyl group, phenoxydecyl group, naphthoxyethyl group, benzoxypentyl group, acetyl group, acetyl group Amide group etc. are mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

From the viewpoint of the strength of the obtained urethane resin, among these R ^{1 to} R ⁴ , a preferable combination is alkylene in which R ² and R ³ bonded to adjacent carbon atoms are bonded to each other among R ^{1 to} R ^4. An alicyclic ring is formed with two carbon atoms as a group, and the remaining two R ¹ and R ⁴ are a combination of hydrogen atoms.
A more preferable combination is one in which R ² and R ³ are bonded to form a cyclohexane ring as a whole as a butylene group [see (C-2) of Production Example 2)].

R ^{5 to} R ¹² in the general formula (1) and the general formula (2) are a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic or araliphatic hydrocarbon group, or a halogen atom. And two adjacent ones of them may be bonded to form a ring.

Examples of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic or araliphatic hydrocarbon group, and halogen atom are the same as those exemplified for R ^{1 to} R ⁴ .

R ^{5 to} R ¹² in the general formula (1) and the general formula (2) may be bonded to each other to form a ring, and among R ^{5 to} R ¹² , adjacent carbons Arbitrary two bonded to an atom combine to form a 3-membered ring to 7-membered ring skeleton as a divalent hydrocarbon group, and furthermore, the divalent hydrocarbon group itself is an aromatic ring or alicyclic ring The case where it is partially substituted with is mentioned.
Specific examples of the divalent hydrocarbon group to which any two of R ^{5 to} R ¹² are bonded include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a phenylene group.

From the viewpoint of the strength of the obtained urethane resin, a preferable combination among these R ^{5 to} R ¹² is that all of R ⁶ , R ⁸ , R ¹⁰ and R ¹² are tert-butyl group, iso-propyl group, iso-butyl. A group, a sec-butyl group, an iso-pentyl group, a sec-pentyl group or a neopentyl group, and the remainder is a combination of hydrogen atoms. A particularly preferred combination is a combination in which all of R ⁶ , R ⁸ , R ¹⁰ and R ¹² are tert-butyl groups or neopentyl groups, and the rest are all hydrogen atoms. The most preferred combination is a combination in which R ⁶ , R ⁸ , R ¹⁰ and R ¹² are all tert-butyl groups and the rest are all hydrogen atoms.

R ^{13 to} R ¹⁶ in the general formula (2) each represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic or araliphatic hydrocarbon group, or a halogen atom. May be bonded to form a ring.
These are the same as those described for R ^{1 to} R ⁴ .

Among these, a preferable combination is a combination in which all of R ^{13 to} R ¹⁶ are hydrogen atoms, or only one of R ^{13 to} R ¹⁶ is a methyl group and the rest are hydrogen atoms. Most preferably, any of R ^{13 to} R ¹⁶ is a combination of hydrogen atoms.

M in the formula represents a Group 3-11 element in the periodic table, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, and Au are mentioned. From the viewpoint of reactivity, Co, Cr, V and Mn are preferable.

  L in the formula represents a ligand, and n represents an integer of 1 or 2. When n is 2, the two ligands L may be the same or different types of ligands.

Examples of the ligand of the catalyst of the salen complex (C) of the present invention include an anionic or neutral ligand.
As preferred ligands for the catalyst of the salen complex (C) of the present invention, organic carboxylate anions such as acetate ion, hexanoate ion, trifluoroacetate ion, benzoate ion; nitrate ion, phosphate ion, PF6 ^- , BF4- ^{and the} like, and water, propylene glycol, ethylene glycol and the like.
Preferred among these are an acetate ion, trifluoroacetate ion, propylene ^glycolate, PF6 @ -, BF4 @ ^- it is.

  The salen complex (C) of the present invention can be obtained by a known synthesis method. For example, Journal of the American Chemical Society Vol 127 No. 33, 11567 (published in 2005), Science Vol 277, 936 (issued in 1997) It can be synthesized by the method of

The method for carrying out the ring-opening addition reaction of the alkylene oxide (a) using the salen complex (C) can be carried out by the same method as the usual ring-opening addition reaction. For example, the following methods can be mentioned.
(1) A racemic alkylene oxide (a-2) is added little by little to a mixture of active hydrogen-containing compound (b), salen complex (C), and a solvent to be used if necessary (prepared to the reaction temperature in advance). A method of ring-opening addition reaction,
(2) A method of adjusting a reaction temperature by mixing a racemic alkylene oxide (a-2), a salen complex (C) and a solvent to be used if necessary,
(3) The product obtained by ring-opening addition reaction of the racemic alkylene oxide (a-2) with the salen complex (C) is left in the reaction vessel as it is, and the racemic alkylene oxide (a-2) Examples thereof include a method of changing the type and causing a ring-opening addition reaction.

  Further, after the ring-opening addition reaction, the catalyst can be removed by treating with a mineral acid, hydrochloric acid, or organic acid and separating the solution.

  In addition, the crystalline polyoxyalkylene polyol (A) can be obtained by hydrolyzing the ring-opening addition reaction product after the catalyst removal treatment with an amine or an alkali metal hydroxide.

The reaction can be usually carried out at -50 ° C to 200 ° C, and preferably -50 ° C to 150 ° C, more preferably -50 ° C to 120 ° C, from the viewpoint of the strength of the obtained urethane resin.
The amount of the salen complex (C) used is 0.001 to 30% by weight based on the weight of the alkylene oxide (a).

When the amount of the catalyst used is small, the molecular weight of the resulting polyoxyalkylene polyol (A) is too high, and the production rate of the polyoxyalkylene polyol (A) is not preferable. On the other hand, since the price of the catalyst itself is high, increasing the amount of the catalyst used is not preferable in terms of increasing the cost when producing the polyoxyalkylene polyol (A).
Accordingly, an appropriate amount of catalyst used is appropriately selected according to the molecular weight of the target polyoxyalkylene polyol (A).

  When the ring-opening polymerization of the racemic alkylene oxide (a-2) using the salen complex (C), trialkylaluminum (for example, triethylaluminum and trimethylaluminum) and trialkylamine (for example, A cocatalyst such as triethylamine may also be used.

  When using the cocatalyst, the amount of the cocatalyst used is preferably 0.001 to 1.0% by weight, more preferably 0.001 to 0.5% by weight, based on the weight of the metal catalyst of the present invention. Most preferably, it is 0.005-0.1 weight%.

Examples of the lanthanoid complex (D) include samarium trifluoroacetylacetonate and neodymium trifluoroacetylacetonate described in JP-A-11-12353.
The amount of the lanthanoid complex (D) used is usually 0.001 to 30% by weight based on the weight of the alkylene oxide (a).

Examples of the bimetal μ-oxoalkoxide (E) include di-oxo- [bis (1-methylethyloxy) -aluminum] -zinc described in JP-T-2001-521957.
The amount of bimetal μ-oxoalkoxide (E) used is usually 0.05 to 60 mol% based on the weight of the alkylene oxide (a).

  Of these catalysts, the salen complex (C) is preferred from the viewpoint of isotacticity of the obtained crystalline polyoxyalkylene polyol (A).

Among the ring-opening polymerization methods of these crystalline polyoxyalkylene polyols (A), from the viewpoint of isotacticity of the obtained crystalline polyoxyalkylene polyol (A), preferably (R) -propylene oxide or (S)- These are a method of ring-opening polymerization of propylene oxide with a catalyst used in usual polymerization of alkylene oxide, and a method of ring-opening polymerization of racemic propylene oxide with a salen complex (C).
When (R) -propylene oxide or (S) -propylene oxide is polymerized with commonly used KOH, the configuration of about 5% of the whole is reversed [for example, “ring-opening polymerization (I)” (sampling See the description on page 146 of Takeo, 1971). ]. In this respect, a method of ring-opening polymerization of racemic propylene oxide with a salen complex (C) is more preferable.

  The isotacticity of the crystalline polyoxyalkylene polyol (A) is 50% or more, preferably 70% or more, more preferably 80% or more, and most preferably 95%, from the viewpoint of mechanical strength of the resulting urethane resin. That's it.

Isotacticity is described in Macromolecules, vol. 35, p2389, 2002, and can be calculated as follows.
About 30 mg of a measurement sample was weighed into a ¹³ C-NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent was added and dissolved to obtain an analysis sample. Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

Signals derived from three types of ¹³ C-NMR methine groups are syndiotactic (S) around 75.1 ppm, heterotactic (H) around 75.3 ppm, and isotactic (I) 75.5 ppm, respectively. Observed nearby. Isotacticity is calculated by the following calculation formula (1).
Isotacticity = [I / (I + S + H)] × 100 (1)
Where I is the integrated value of the isotactic signal; S is the integrated value of the syndiotactic signal; and H is the integrated value of the heterotactic signal.

  The number average molecular weight (hereinafter referred to as Mn) of the crystalline polyoxyalkylene polyol (A) is usually Mn 1000 to 50,000. From the viewpoint of mechanical strength of the obtained urethane resin, Mn is preferably 1500 to 50000, more preferably Mn 2000 to 50000, and most preferably 2000 to 10,000.

This Mn is calculated by the hydroxyl value.
The hydroxyl value (mgKOH / g) is determined by a method based on JISK-1557 (1970 edition). Mn can be calculated by the following calculation formula (2).
Mn = (F × 56,100) / hydroxyl value (2)
However, F represents the number of hydroxyl groups contained in one molecule of the crystalline polyoxyalkylene polyol (A).

  The polyisocyanate (B) is a compound having at least two isocyanate groups, and includes aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products of these polyisocyanates (urethanes). Groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups or oxazolidone group-containing modified products); and mixtures of two or more of these.

  The aromatic polyisocyanate includes 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following polyisocyanates are also the same). Etc. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminodiphenylmethane {condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; And the like, polyallyl polyisocyanate (PAPI) and the like], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.

  Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 15 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.

  Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.

  Of these, preferred are 6 to 16 aromatic diisocyanates, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 16 carbon atoms, particularly preferably 2,4- and / or 2, 6-tolylene diisocyanate (TDI), 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI).

  The urethane resin composition of the present invention can be polymerized in the same manner as before, and can be polymerized in the presence or absence of a catalyst for urethanization.

  The amine catalyst for urethanization used as necessary in the present invention is an amine-based catalyst usually used for polyurethane reaction. For example, triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ′, N '-Tetramethylhexamethylenediamine, triethylenediamine, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7, bis (dimethylaminoethyl) ether (carboxylate) Etc.

  Furthermore, a metal catalyst can be used if necessary. Examples of the metal catalyst include stannous octylate, dibutylstannic dilaurate, and lead octylate. The amount of the catalyst used is preferably 0.001 to 6%, more preferably 0.1 to 5%, based on the weight of the crystalline polyoxyalkylene polyol (A).

  Moreover, a urethane resin composition can also be made into a polyurethane foam using a foaming agent by the same method as before.

  As the foaming agent, water or the like can be used.

In the production of the urethane resin, other additives as described below may be used as necessary.
For example, colorants (dyes, pigments), flame retardants (phosphate esters, halogenated phosphate esters, etc.), anti-aging agents (triazoles, benzophenones, etc.), antioxidants (hindered phenols, hindered amines) Etc.) can be reacted in the presence of a commonly used additive.

  When this urethane resin is used as a coating agent, it has characteristics such as excellent adhesion to polyolefin rubber, polyolefin, etc., and various applications such as urethane foam, urethane elastomer, urethane coating material are possible. Examples of the urethane foam include cushioning materials for automobiles, back materials for automobiles, cast potting materials for urethane elastomers, and adhesives and paints for coating materials.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Production Example 1>
10.8 g (100 mmol) of 1,2-diaminobenzene, 50 g (214 mol) of 3,5-di-t-butylsalicylaldehyde and 40 mL of ethanol were placed in a 1 L eggplant flask equipped with a reflux tube. Refluxing was carried out for 4 hours with stirring. After refluxing, the mixture was allowed to stand at room temperature for 44 hours, followed by filtration and washing with 1 L of ethanol.
The obtained solid was vacuum-dried for 24 hours to obtain 41 g (75 mmol, yield 75%) of an intermediate (X1-1) of tan crystals. Identification was performed by H-NMR and C-NMR.

  Under a nitrogen atmosphere, 40 g (73 mmol) of the intermediate (X1-1), 13.1 g (52 mmol) of cobalt acetate tetrahydrate and 2 L of ethanol were placed in a 4 L Nathlasco equipped with a reflux tube. Refluxing was carried out for 2 hours with stirring. After cooling to room temperature, the precipitated solid was filtered under reduced pressure and washed with 2000 mL of methanol. The solid was dissolved in 400 mL of dichloromethane and placed in 10 L of hexane. Cool to 0 ° C. and let stand for 24 hours. The precipitated solid was filtered under reduced pressure and washed with 1 L of hexane to obtain 29 g (48.4 mmol, yield: 93%) of an intermediate (X1-2) of orange colored crystals. Identification was performed by mass spectrometry (hereinafter abbreviated as MS).

Intermediate (X1-1) 27.2 g (45.1 mmol), acetic acid 100 mL (1750 mmol) and dichloromethane 200 mL were placed in a 1 L eggplant flask and stirred for 1 hour. After removing the solvent at 60 ° C. with a rotary evaporator, the solution was filtered under reduced pressure using 200 mL of pentane to obtain 29 g (45.7 mmol, yield 97%) of reddish brown salen complex (C-1) of the present invention. Identification was performed by MS. From the molecular weight of MS, the two ligands L were acetate ion and water, respectively.
The estimated chemical structural formula of the salen complex (C-1) is shown as chemical formula (3).

<Production Example 2>
The reaction was performed in the same manner except that 11.4 g (100 mmol) of 1,2-diaminocyclohexane was used instead of 1,2-diaminobenzene, and 39 g (72 mmol, Yield 72%). Identification was performed by MS.

The reaction was carried out in the same manner except that 39.8 g (73 mmol) of intermediate (X2-1) was used instead of intermediate (X1-1), and 28 g 4.6 mmol, yield 63%). Identification was performed by MS.
Further, acetic acid was reacted, and the reaction was carried out in the same manner except that 27.2 g (45.1 mmol) of intermediate (x2-2) was used instead of intermediate (X1-2). 27 g (41 mmol, yield 91%) of complex (C-2) was obtained. Identification was performed by MS. From the molecular weight of MS, the two ligands L were acetate ion and water, respectively.
The estimated chemical structural formula of the salen complex (C-2) is shown as chemical formula (4).

<Production Example 3>
Under a nitrogen atmosphere, 18 g (27 mmol) of the salen complex (C-1) obtained in Production Example 1, 114 g (1.97 mol) of racemic propylene oxide, and 1 L of toluene were placed in a 2 L eggplant flask and heated at 0 ° C. for 2 hours. Stir. When 1 L of 0.1 mol / L hydrochloric acid was added, a precipitate was formed, and 5 L of dichloromethane was added and dissolved. After liquid separation, the solvent was distilled off from the organic layer with an evaporator. The precipitated solid was dissolved in 4 L of acetone at 40 ° C. and cooled at 0 ° C. for 24 hours. The solid was filtered, 1 L of a 0.1 mol / L KOH-methanol solution was added to the obtained solid, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, the mixture was neutralized with 0.1 mol / L hydrochloric acid, and 1 L of toluene was added. 1 L of water was added and liquid separation was performed 3 times. 100 g of crystalline polyalkylene oxide polyol (A-1) was obtained by removing the solvent from the toluene layer with an evaporator.
The isocity was 99%, Mn was 4200, the hydroxyl value was 26.7 mgKOH / g, and the melting point was 56 ° C.

<Production Example 4>
Under a nitrogen atmosphere, 36 g (54 mmol) of the salen complex (C-2) obtained in Production Example 2, 228 g (3.94 mol) of racemic propylene oxide, and 2 L of toluene were placed in a 5 L eggplant flask, and at 0 ° C. for 2 hours. Stir. When 2 L of 0.1 mol / L hydrochloric acid was added, a precipitate was formed, and 7 L of dichloromethane was added and dissolved. Liquid separation was performed, and the solvent was distilled off from the organic layer with an evaporator. The precipitated solid was dissolved in 6 L of acetone at 40 ° C. and cooled at 0 ° C. for 24 hours. The solid was filtered, 1 L of a 0.1 mol / L KOH-methanol solution was added to the obtained solid, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, the mixture was neutralized with 0.1 mol / L hydrochloric acid, and 1 L of toluene was added. 1 L of water was added and liquid separation was performed 3 times. 100 g of crystalline polyalkylene oxide polyol (A-2) was obtained by removing the solvent from the toluene layer with an evaporator.
The isocity was 99%, Mn was 8000, the hydroxyl value was 14.0 mgKOH / g, and the melting point was 55 ° C.

<Production Example 5>
120 g of (S) -propylene oxide (manufactured by ALDRICH) and 28 g of KOH were placed in a 1 L autoclave and allowed to stir at room temperature for 48 hours. Thereafter, the temperature was raised to 50 ° C., 100 g of toluene and 100 g of water were added to separate the solution three times. Thereafter, the mixture was neutralized with 0.1 mol / L hydrochloric acid, and 100 g of water was added, followed by liquid separation three times. The solvent was distilled off from the filtrate with an evaporator to obtain 100 g of a white crystalline polyalkylene oxide polyol (A-3).
The isotacticity was 93%, Mn was 3900, the hydroxyl value was 28.8 mgKOH / g, and the melting point was 53 ° C.

<Example 1>
Under a nitrogen atmosphere, 91.92 g (0.024 mol) of crystalline polyalkylene oxide polyol (A-3), 8.08 g (0.130 mol) of ethylene glycol, and 39.23 g (0.157 mol) of 4,4′-diphenylmethane diisocyanate. Then, 0.0069 g of dibutyl stannic dilaurate and 325 g of DMF were placed in a 1 liter eggplant flask. Stir at 60 ° C. for 16 hours. A urethane resin solution having a weight average molecular weight of 97,000 (according to the gel permeation method using polystyrene as a standard substance) was obtained.

<Example 2>
Instead of the crystalline polyalkylene oxide polyol (A-3), 91.82 g (0.022 mol) of the crystalline polyalkylene oxide polyol (A-1) and the amount of ethylene glycol charged were 8.18 g (0.132 mol). Except for the above, polymerization was carried out in the same manner as in Example 1 to obtain a urethane resin solution having a weight average molecular weight of 10,000.

<Example 3>
In place of the crystalline polyalkylene oxide polyol (A-3), 91.17 g (0.011 mol) of the crystalline polyalkylene oxide polyol (A-2) and the amount of ethylene glycol charged were 8.83 g (0.142 mol). Was polymerized in the same manner as in Example 1 to obtain a urethane resin solution having a weight average molecular weight of 12,000.

<Comparative Example 1>
Instead of the crystalline polyalkylene oxide polyol (A-3), 91.89 g of ordinary polypropylene glycol (Newpol PP4000, Mn: 4000, hydroxyl value: 28.1, manufactured by Sanyo Chemical Industries, 25% isotacticity) 0.023 mol) and polymerization was carried out in the same manner as in Example 1 except that the amount of ethylene glycol charged was 8.11 g (0.131 mol) to obtain a urethane resin solution having a weight average molecular weight of 10,000.

<Comparative example 2>
In place of the crystalline polyalkylene oxide polyol (A-3), polybutanediol adipate ester polyol (San Ester 4640, Mn: 4000, hydroxyl value: 28.1, manufactured by Sanyo Chemical Industries, Ltd.) 91.89 g (0. 023 mol) and polymerization was carried out in the same manner as in Example 1 except that the amount of ethylene glycol charged was 8.11 g (0.131 mol) to obtain a urethane resin solution having a weight average molecular weight of 10,000.

  DMF was further added to the urethane resin solutions of Examples 1 to 3 and Comparative Examples 1 and 2 to dilute to a 20 wt% urethane resin solution, and then poured into a 200 mm × 200 mm mold to a depth of 1 mm, and a 60 ° C. circulation It put into the dryer for 6 hours and volatilized DMF. Thereafter, the DMF was completely volatilized by placing in a vacuum dryer at 60 ° C. and a reduced pressure of 10 mmHg to obtain a 200 mm × 200 mm × 0.2 mm urethane resin sheet.

<Measurement of dynamic friction coefficient>
As the friction resistance of the obtained sheet, the dynamic friction coefficient was measured by the following method.
Using a surface tester KES-FB-4S (manufactured by Kato Tech Co., Ltd.), according to the KES (Kawabata-Evaluation-System) method, using a 20 mm × 20 mm × 0.2 mm sheet, 1 mm / s, load 50 gf Measured with The results are shown in Table 1.

<Measurement of 100% modulus, tensile strength, elongation at break>
As physical properties of the obtained sheet, 100% modulus, tensile strength, and elongation at break were all measured at 200 mm / min using a test piece type 5 test piece according to the method described in JIS K-7127 (1999 edition). It was measured. The results are shown in Table 1.

  Comparing Examples 1 to 3 and Comparative Examples 1 and 2 in Table 1, the urethane resin using a crystalline polyoxyalkylene polyol as a raw material clearly is less than polyester polyol and normal polypropylene glycol having low isotacticity. Low dynamic friction coefficient, 100% modulus, high tensile strength. Therefore, it can be said that the urethane resin composition of the present invention has excellent mechanical strength such as good friction resistance (sliding property) and tensile strength.

  The urethane resin composition of the present invention has good friction resistance (sliding property), mechanical strength such as tensile strength, and has no hydrolysable ester group in the molecule because of its chemical structure. And can be used for adhesives, paints, automotive cushioning materials, automotive back materials, cast potting materials, electronic copying machine cleaning blades, and the like.

Claims (3)

A urethane resin composition that is obtained by reacting the isotacticity is 95% or more crystalline polyoxyalkylene polyol (A) and the polyisocyanate (B), (A) is the following general formula (1) or (2) in the presence of a catalyst salen complex (C) represented by the urethane resin composition, wherein the Oh Rukoto polyol obtained alkylene oxide with (a) by ring-opening polymerization.

(Wherein R ^{1 to} R ⁴ represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic or araliphatic hydrocarbon group, or a halogen atom, and any two of them combine to form a ring. The hydrogen atom bonded to the carbon atom may be substituted with a substituent that does not participate in the reaction, and R ^{5 to} R ¹² are a hydrogen atom, a halogen atom, an aliphatic group, an alicyclic group, an aromatic group. Or it represents an araliphatic hydrocarbon group or a halogen atom, and two of them may be bonded to form a ring, M represents a Group 3 to 11 element, and L represents a ligand. , N represents an integer of 1 or 2. When n is 2, the two ligands L may be the same or different.

(Wherein R ^{13 to} R ¹⁶ represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic or araliphatic hydrocarbon group, or a halogen atom, and any two of them combine to form a ring. And a hydrogen atom bonded to the carbon atom may be substituted with a substituent that does not participate in the reaction, and R ^{5 to} R ¹² , M, L, and n are the same as the symbols in formula (1), respectively. Represents things.)   The urethane resin composition according to claim 1, wherein the crystalline polyoxyalkylene polyol (A) has a number average molecular weight of 2,000 to 50,000. The urethane resin composition according to claim 1 or 2, wherein the crystalline polyoxyalkylene polyol (A) is a crystalline polyoxypropylene polyol.