JP4475003B2 - Long chain alkyl group-containing diol, process for producing the same and polyurethane resin - Google Patents

Description

  The present invention relates to a long-chain alkyl chain-containing diol having a long-chain alkyl chain in a pendant shape and having two primary hydroxyl groups, a method for producing the same, and a polyurethane resin using the same.

The urethane resin is a resin in which a polyol and a polyisocyanate are linked by a urethane bond to increase the molecular weight, and various performances can be imparted to the urethane resin by variously changing the polyol and the polyisocyanate.
For the purpose of imparting non-adhesiveness (non-blocking property), slipperiness, water repellency, lipophilicity, etc. to the surface of the urethane resin, it has been studied to introduce a long chain alkyl group into the urethane resin. As this general method, it is known to use a long-chain alkyl diol as a diol component which is a raw material of a urethane resin. The long-chain alkyl diol is usually a diol having hydroxyl groups at both ends, such as 1,8 octanediol, 1,9 nonanediol, 1,10 decanediol, 1,12 dodecanediol, and the like. In urethane resins made from these diols, long-chain alkyl groups are introduced into the main chain. Therefore, it is difficult for the long-chain alkyl group to be oriented on the surface interface. In addition, when a highly crystalline diol such as 1,12 dodecanediol is used, there is a drawback that the urethane resin becomes very hard.

However, if a long-chain alkyl group can be grafted onto the side chain of the urethane resin in a pendant form, the long-chain alkyl group can be easily oriented on the surface of the urethane resin, and non-adhesiveness, slipperiness, water repellency, lipophilicity, etc. The performance is further improved.
In order to graft a long-chain alkyl group into the side chain of a urethane resin in a pendant manner, conventional 1,8 octanediol, 1,9 nonanediol, 1,10 decanediol, 1,12 having hydroxyl groups at both ends are used. Instead of an alkylene diol such as dodecanediol, a diol having a long alkyl chain in a pendant form is required. As such a diol, there is a method of using an oligomer having a diol at one end by radical polymerization of monomethacrylate such as polyethylene glycol using thioglycerin as a chain transfer agent (see, for example, Patent Documents 1 and 2).
However, in this method, 1) Ordinary diols have primary and secondary hydroxyl groups, and of these, secondary hydroxyl groups have a slow reaction with isocyanates, so that urethanization takes time. 2) An oligomer that does not react with thioglycerin, that is, has no hydroxyl group is by-produced. Oligomers that do not have a hydroxyl group cannot react with isocyanate, so they are not incorporated into the urethane resin and become a blended state with the urethane resin, causing problems such as gradual bleeding out or extraction with water or a solvent. ing.

Japanese Laid-Open Patent Publication No. 4-178417 (Example 4 on page 4) Japanese Laid-Open Patent Publication No. 4-272717 (page 5)

  An object of the present invention is to provide a high-purity long-chain alkyl group-containing diol having a long-chain alkyl group in a pendant form and having two primary hydroxyl groups, and further by a polyaddition reaction with a polyisocyanate. It is to provide a method for producing a chain alkyl group-containing diol, and to provide a novel polyurethane resin in which a long chain alkyl group is grafted onto a side chain in a pendant form.

As a result of intensive studies on the above problems, the present inventors have found that a primary diol having a long-chain alkyl group in a pendant form can be obtained by reacting a specific diol with a diisocyanate. It came to complete.
Furthermore, it has been found that a novel graft urethane resin obtained by polyaddition reaction with polyisocyanate using this diol as a raw material and having a long-chain alkyl group introduced pendant into the side chain of the polyurethane resin can be obtained.

  That is, the present invention provides a long-chain alkyl group-containing diol represented by the general formula (1).

（式中、Ｒ１は、炭素原子数が２〜９のアルキレン基又はジアルキレンエーテル基であり、Ｒ２は、炭素原子数が８〜３６のアルキル基であり、Ｒ３は、−ＣＯ−ＮＨ−Ｒ４−ＮＨ−ＣＯ−であり、Ｒ４は、炭素原子数が２〜１８の炭素原子を含む有機基で、アルキレン基、フェニレン基、シクロヘキシレン基、ビフェニレン基の何れかの官能基を含むジイソシアネート残基である。）

(In the formula, R 1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, R 2 is an alkyl group having 8 to 36 carbon atoms, and R 3 is —CO—NH—R 4. -NH-CO-, wherein R4 is an organic group containing a carbon atom having 2 to 18 carbon atoms, and a diisocyanate residue containing any functional group of an alkylene group, a phenylene group, a cyclohexylene group, or a biphenylene group .)

The present invention provides compounds represented by the general formula _{(2) HO-R1-NHCH} 2 CH 2 COO-R2 (2)
(In the formula, R 1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, and R 2 is an alkyl group having 8 to 36 carbon atoms.)
The present invention provides a process for producing a long-chain alkyl group-containing diol represented by the general formula (1) , wherein the diisocyanate is reacted with diisocyanate.

  The high-purity long-chain alkyl group-containing diol having a long-chain alkyl group in a pendant form and having two primary hydroxyl groups is excellent in reactivity with polyisocyanate and has a long-chain alkyl group as a side chain. A new polyurethane resin grafted in a pendant form has excellent water repellency, blocking resistance and non-aqueous dispersibility.

Next, the present invention will be described in detail.
First, the long-chain alkyl group-containing diol represented by the general formula (1) of the present invention will be described.

一般式（１）中、Ｒ１は、炭素原子数が２〜９のアルキレン基又はジアルキレンエーテル基である。炭素原子数が２〜９のアルキレン基又はジアルキレンエーテル基としては、例えばエチレン基、プロピレン基、ブチレン基、ジエチレンエーテル基、ジプロピレンエーテル基、ジブチレンエーテル基等が挙げられる。これらのうち、エチレン基、ジエチレンエーテル基等が特に好ましい。

In general formula (1), R1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms. Examples of the alkylene group or dialkylene ether group having 2 to 9 carbon atoms include an ethylene group, a propylene group, a butylene group, a diethylene ether group, a dipropylene ether group, and a dibutylene ether group. Of these, an ethylene group, a diethylene ether group, and the like are particularly preferable.

  R2 is an alkyl group having 8 to 36 carbon atoms, and examples thereof include an octyl group, a decyl group, a lauryl group, a cetyl group, and a stearyl group.

Furthermore, R3 is -CO-NH-R4-NH-CO-, in which R4 is an organic group containing 2 to 18 carbon atoms. Examples of the organic group include diisocyanate residues containing any functional group of alkylene group, phenylene group, cyclohexylene group, and biphenylene group . For example, hexamethylene group derived from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) An isophorone group derived from the above and a norbornene group derived from norbornene diisocyanate (NBDI) are preferred.

  The long-chain alkyl group-containing diol of the present invention has two primary hydroxyl groups in the molecule, and the molecular weight is preferably 500 to 2,000.

  Next, a method for producing the long-chain alkyl group-containing diol represented by the general formula (1) will be described. As such a production method, first, the following compound (I) and compound (II) are subjected to a Michael addition reaction to produce a compound (III) having a primary hydroxyl group at the end of the molecule. This is expressed as follows.

  Compound (I) represents a primary amine having a hydroxyl group in which R1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, and Compound (II) is an alkyl group in which R2 is 8 to 36 carbon atoms. Represents a monoacrylate.

  Next, 2 mol of the secondary amine (III) is reacted with 1 mol of the diisocyanate represented by (IV), the NH group and the NCO group of the diisocyanate are reacted leaving the hydroxyl group, and the long-chain alkyl group of the present invention. Containing diols can be produced. This is expressed as follows.

  Examples of the primary amine having a hydroxyl group of the compound (I) include primary hydroxyl groups and primary amino groups such as 2-aminoethanol (monoethanolamine), 2- (2-aminoethoxy) ethanol, 3-aminopropanol 4-aminobutanol and the like. The compound which has is mentioned.

  Moreover, as monoacrylate (II) which has a long-chain alkyl chain, for example, n-octyl group, 2-ethylhexyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group (lauryl group) cetyl group, stearyl Examples thereof include esters of monoalcohol having a group and acrylic acid.

  A diisocyanate is used for the purpose of reacting the secondary amino group of the secondary amine (III) with an isocyanate group to dimerize the secondary amino compound (III) with a urea bond. Aromatic diisocyanates such as isocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, Aliphatic or alicyclic diisocyanates such as norbornene diisocyanate In particular, aliphatic and alicyclic diisocyanates are preferable to highly reactive aromatic diisocyanates. Specifically, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated). MDI) is more preferably used.

  Next, a long-chain alkyl group-containing diol obtained by graft-adding a long-chain alkyl group to a side chain in a pendant form obtained by polyaddition reaction of a long-chain alkyl group-containing diol of the general formula (1) with a polyisocyanate A polyurethane resin having a component unit and a polyisocyanate component unit and having a number average molecular weight of 5,000 to 500,000 will be described.

  The number average molecular weight of the polyurethane resin of the present invention is 5,000 to 500,000, preferably 30,000 to 150,000.

  Examples of the raw material include the long-chain alkyl group-containing diol represented by the general formula (1) of the present invention, and polyols and polyisocyanates used as raw materials for ordinary polyurethane resins.

  As the polyol that reacts with the polyisocyanate, in addition to the long-chain alkyl group-containing diol represented by the general formula (1) of the present invention, a polyol, a low-molecular polyol, or the like that is usually used as a raw material for a polyurethane resin may be used in combination. Can do.

  Examples of such polyols include polyesters, polycarbonates, polyester carbonates, polyethers, polyether carbonates and polyester amides having a hydroxyl group at the end. Of these, polyester, polycarbonate and polyether are preferred.

  Examples of the polyester having a hydroxyl group at the terminal include a reaction product of a divalent alcohol and a dibasic carboxylic acid. Instead of the free dicarboxylic acids, the corresponding anhydrides or diesters of lower alcohols or mixtures thereof can also be used for the production of the polyester.

  The dihydric alcohol is not particularly limited, but ethylene glycol, 1,3- and 1,2-propylene glycol, 1,4- and 1,3- and 2,3-butanediol, 1,6-hexane glycol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-methyl-1,3- Propanediol, 2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, etc. Can be mentioned.

  The dibasic carboxylic acid can be aliphatic, alicyclic, aromatic and / or heterocyclic, and can be unsaturated or substituted with, for example, a halogen atom. Examples of these carboxylic acids include, but are not limited to, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimethic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahexan anhydride Hydrophthalic acid, tetrahydroisophthalic anhydride, hexahydroisophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, maleic acid, fumaric acid, dimer fatty acids such as oleic acid, dimethyl terephthalate and A mixed terephthalate is mentioned.

  These polyesters having hydroxyl groups at the ends can also have some of the carboxy end groups. For example, a lactone such as ε-caprolactone or a polyester of a hydroxycarboxylic acid such as ε-hydroxycaproic acid can be used.

  On the other hand, examples of the polycarbonate having a hydroxyl group at the terminal include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polyethylene glycol. Diols such as polyol, polypropylene glycol and / or polytetramethylene glycol and phosgene, diallyl carbonate (eg diphenyl carbonate) or cyclic carbonate (eg propylene carbonate) -Bonate).

  On the other hand, as the polyether having a hydroxyl group at the terminal, a starting compound having a reactive hydrogen atom, an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, or these alkylene oxides are used. A reaction product with a mixture is mentioned.

  Starting compounds having such reactive hydrogen atoms include water, bisphenol A and the divalent alcohols described above to produce polyester polyols.

  Examples of the low molecular weight polyol include the divalent alcohol described above.

Next, as the polyisocyanate used in the present invention, the following formula R (NCO) ₂
(Wherein R is any divalent organic group)
The diisocyanate shown by these is mentioned.

  Examples of such polyisocyanates include, but are not limited to, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3- and 1 , 4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (= isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (= dicyclohexylmethane diisocyanate ), 2- and 4-isocyanatocyclohexyl-2'-isocyanatocyclohexylmethane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) Methane, 1,3- and 1,4-tetramethylxylide Diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate -To, p- and m-phenylene diisocyanate, xylylene diisocyanate, diphenyl-4,4'-diisocyanate and the like. Among these, 4,4'-diphenylmethane diisocyanate (hereinafter, 4,4′-MDI).

  The production conditions of the above polyurethane resin are not particularly limited, but usually 0 to 120 ° C., preferably 40 to 100 ° C., in the presence of a suitable organic solvent or water, these urethanized raw materials are prepared without a catalyst. Alternatively, a known urethanization catalyst is used, or a reaction retarder is added and mixed by stirring. Further, in the case of polymerization, a compound having monofunctional active hydrogen can be added at or near the end point of the reaction to substantially eliminate unreacted isocyanate groups. Among them, a relatively low molecular weight resin having isocyanate groups at both ends, that is, a urethane prepolymer can also be produced. The number average molecular weight of the urethane prepolymer is preferably 1000 to 10,000.

  Examples of such organic solvents include, for example, aromatic hydrocarbons such as toluene and xylene, nonpolar solvents such as n-hexane, n-heptane, n-octane and terpenes, esters such as ethyl acetate and butyl acetate, acetone , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate And ether esters such as dimethylformamide, diethylformamide, dimethylacetamide, and dimethylsulfoxide. These organic solvents may be used in the total amount at the beginning of the urethanization reaction, or may be partially divided and used during the reaction.

  As the urethanization catalyst, dibutyltin diisocyanate, tin compounds such as stannous octylate, tertiary amines such as diazabicycloundecene, or carboxylates thereof can be used. 10 ppm to 1000 ppm is appropriate for the minute.

  As the reaction retarder, an acid such as phosphoric acid is usually used. The amount used is suitably 10 ppm to 1000 ppm relative to the solid content of the urethane resin.

  As the compound having monofunctional active hydrogen, a monoalcohol such as methanol and butanol or a monoamine such as dibutylamine is used.

  The NCO / OH equivalent ratio in the polyurethane resin using the long-chain alkyl group-containing diol of the present invention is usually 0.95 to 1.05, preferably 0.98 to 1.03 in the case of polymerization. In the case of prepolymerization, usually 1.05-2.5, preferably 1.5-2.0 is used.

  On the other hand, in the present invention, an organic diamine is optionally used as a chain extender for the urethane prepolymer.

  These organic diamines are not particularly limited, for example, diaminoethane, 1,2- or 1,3-diaminopropane, 1,2- or 1,3- or 1,4-diaminobutane, 1,5-diaminopentane. 1,6-diaminohexane, piperazine, N, N′-bis- (2-aminoethyl) piperazine, 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (= isophoronediamine), bis -(4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, 1,3-diaminopropane, norbornene diisocyanate, etc. Hydrazine, amino acid hydrazide, hydrazide of semi-carbazide carboxylic acid, bis (hydrazide) and bis Semicarbazide), and the like can also be used. The chain extension reaction conditions using the organic diamine are not particularly limited, but are usually 80 ° C. or lower, preferably 0 to 70 ° C. under good stirring conditions.

  In the method for producing the polyurethane resin of the present invention, a stabilizer such as an antioxidant, a lubricant, a non-solvent, a pigment, a filler, an antistatic agent and other additives are added at any time of the reaction as necessary. Can do.

The polyurethane resin of the present invention is a so-called comb-type urethane in which a long-chain alkyl group is grafted into a side chain of a urethane resin in a pendant manner, that is, a urethane in which a long-chain alkyl group is introduced into a side chain of a urethane resin in a comb-like shape. Resin (FIG. 1).
By introducing a long-chain alkyl group into the side chain in a pendant manner, the function of the surface or interface of the polyurethane resin can be improved. For example, a urethane resin having a long-chain alkyl group in the side chain facilitates orientation of the long-chain alkyl group on the surface of the urethane resin particles in a non-polar solvent, and can improve dispersibility in the non-polar solvent (FIG. 2). . Further, non-adhesive (non-blocking) slipperiness, water repellency, lipophilicity, etc. can be imparted to the surface of the urethane resin.

  Next, as a use of the polyurethane resin of the present invention, for example, it can be used for non-aqueous dispersion urethane (urethane dispersed in a nonpolar solvent), and the conventional polar solvent type urethane (urethane resin solution dissolved in a strong solvent) It can be used as an environmentally friendly product. Further, those having a surface imparted with non-adhesive (non-blocking) slipperiness, water repellency, lipophilicity and the like can be used for applications such as synthetic leather, artificial leather, industrial parts, and films.

  Next, with respect to the long-chain alkyl group-containing diol of the present invention and the polyurethane resin using the diol, synthesis examples and application examples thereof will be shown to describe the present invention more specifically. The present invention is not limited to these synthesis examples and application examples. In the synthesis examples and application examples, parts and% relate to the weight unless otherwise specified. The molecular weight refers to the number average molecular weight calculated from the hydroxyl value.

[Example 1] Diol having an octyl group (2-ethylhexyl group) in a pendant form A 1-liter four-necked round bottom flask equipped with a nitrogen introduction tube, a condenser for cooling, a thermometer, and a stirrer was charged with 61 g of monoethanolamine ( 1.0 mol) was added and stirred. Subsequently, 184 g (1.0 mol) of 2-ethylhexyl acrylate was added dropwise over about 2 hours while maintaining the internal temperature at 30 to 40 ° C. Then, it stirred for 5 hours, keeping internal temperature at 40-50 degreeC. Next, 84 g (0.5 mol) of hexamethylene diisocyanate (HDI) was added over about 60 minutes while maintaining the internal temperature at 30 to 40 ° C. It stirred for 1 hour, keeping internal temperature at 40-50 degreeC after throwing in. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The obtained diol was an almost colorless and transparent viscous liquid at room temperature. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. The actually measured value of the hydroxyl value was 172.1 with respect to the calculated value of the hydroxyl value of 170.5, and it was confirmed that the hydroxyl group and HDI did not react during the dimerization with HDI.
Measurement result of H-NMR using DMSO as a solvent 0.8 ppm: —CH ₃
1.2ppm :-( CH ₂₎ n-
6.2 ppm: urea bond (-NH-CO-N)
In addition, acrylic double bond and urethane bond were not detected by H-NMR.

[Example 2] Diol having an n-dodecyl group (lauryl group) in a pendant form In a 1-liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer, 2- (2-amino 105 g (1.0 mol) of ethoxy) ethanol was added and stirred. Next, 240 g (1.0 mol) of lauryl acrylate was added dropwise in about 2 hours while maintaining the internal temperature at 30 to 40 ° C. Thereafter, the mixture was stirred for about 5 hours while maintaining the internal temperature at 30 to 40 ° C. Next, 84 g (0.5 mol) of hexamethylene diisocyanate (HDI) was added over about 60 minutes while maintaining the internal temperature at 30 to 40 ° C. It stirred for 1 hour, keeping internal temperature at 30-40 degreeC after throwing in. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The obtained diol was a colorless and transparent viscous liquid that solidified in the form of a wax at room temperature. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. When the hydroxyl value was measured, the actually measured value was 131.0 with respect to the calculated value of 130.7, which almost coincided, and it was confirmed that the hydroxyl group and HDI did not react during the dimerization with HDI.
Measurement result of H-NMR using DMSO as solvent 0.9 ppm: —CH ₃
1.2ppm :-( CH ₂₎ n-
6.3 ppm: urea bond (-NH-CO-N)
In addition, the acrylic double bond and the urethane bond were not detected by H-NMR.

[Example 3] Diol having an n-octadecyl group (stearyl group) in a pendant form A 2-liter 4-neck round bottom flask equipped with a nitrogen introduction tube, a condenser for cooling, a thermometer, and a stirrer was charged with 2- (2-amino Ethoxy) ethanol, 52.5 g (0.5 mol) toluene 30 g (final NV = 90%) was added and stirred. Next, 162 g (0.5 mol) of pulverized stearyl acrylate was added little by little in about 60 minutes while maintaining the internal temperature at 45 to 50 ° C. Thereafter, the mixture was stirred for about 5 hours while maintaining the internal temperature at 30 to 40 ° C. Next, 52.5 g (0.25 mol) of trimethylhexamethylene diisocyanate (TMDI) was added over about 60 minutes while maintaining the internal temperature at 30 to 40 ° C. It stirred for 1 hour, keeping internal temperature at 30-40 degreeC after throwing in. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The resulting diol was a pale yellow viscous liquid that solidified at room temperature. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. When the hydroxyl value was measured, the measured value was 94.1, which was almost the same as the calculated value 94.6, and it was confirmed that the hydroxyl group and TMDI did not react during the dimerization with TMDI.
Measurement result of H-NMR using DMSO as a solvent 0.8 ppm: —CH ₃
1.3pm :-( CH ₂₎ n-
6.1 ppm: urea bond (-NH-CO-N)
In addition, acrylic double bond and urethane bond were not detected by H-NMR.

[Example 4] Diol having an isostearyl group in a pendant form In a 1-liter four-necked round bottom flask equipped with a nitrogen introduction tube, a condenser for cooling, a thermometer, and a stirrer, 2- (2-aminoethoxy) ethanol, 52 0.5 g (0.5 mol) was added and stirred. Next, 162 g (0.5 mol) of isostearyl acrylate was added in about 60 minutes while maintaining the internal temperature at 45 to 50 ° C. Then, it stirred for 5 hours, keeping internal temperature at 30-40 degreeC. Next, 42 g (0.25 mol) of hexamethylene diisocyanate (HDI) was added over about 30 minutes while maintaining the internal temperature at 30 to 40 ° C. It stirred for 1 hour, keeping internal temperature at 30-40 degreeC after throwing in. An infrared spectrophotometer was used to confirm that there was no isocyanate group peak, and the sample was taken out. The obtained diol was almost colorless and transparent at room temperature and was a viscous liquid. It was confirmed by high performance liquid chromatography (Tosoh 8020) that it had a single peak and was a high purity product. The measured value of the hydroxyl value was almost equal to 110.3 with respect to the calculated value of the hydroxyl value of 109.4, and it was confirmed that the hydroxyl group and HDI did not react during the dimerization with HDI.
Measurement result of H-NMR using DMSO as a solvent 0.8 ppm: —CH ₃
1.2ppm :-( CH ₂₎ n-
6.2 ppm: urea bond (-NH-CO-N)
In addition, acrylic double bond and urethane bond were not detected by H-NMR.

[Example 5] Synthesis of polyurethane resin having lauryl group in pendant form Polytetramethylene ether glycol (molecular weight 2,000) was placed in a 1 liter four-necked round bottom flask equipped with a nitrogen inlet tube, a condenser for cooling, a thermometer, and a stirrer. PTMG) 100 parts, 25 parts of the diol obtained in Example 2, 10 parts of 1,4-butanediol, 121 parts of methyl ethyl ketone (MEK) as a solvent and 47 parts of 4,4′-MDI were mixed at 70 ° C. After reacting for 2 hours, 101 parts of MEK and 0.02 part of stannous octylate as a urethanization catalyst were added and reacted for another 5 hours to obtain a resin concentration of 45% and a viscosity of 300 dP. s, a polyurethane resin solution having a number average molecular weight of 50,000 was obtained. The reaction time was 7 hours.
In H-NMR, urethane bonds were detected, and no isocyanate group peak was detected with an infrared spectrophotometer.

[Comparative Example 1] Synthesis of a polyurethane resin having a dodecyl group in the main chain In place of the diol obtained in Example 2 in Example 5, a dodecane diol having hydroxyl groups at both ends was used to introduce a dodecyl group into the main chain. Resin concentration 45%, viscosity 300 dP. A polyurethane resin solution of s was obtained. The reaction time was 7 hours as in Example 5.

[Comparative Example 2] Synthesis of polyurethane resin in which lauryl group was introduced into pendant by macromonomer method In Example 5, lauryl methacrylate was radically polymerized with thioglycerin as a chain transfer agent instead of the diol obtained in Example 1, and molecular weight was obtained. Using a dihydroxy-terminated macromonomer of about 2000, resin concentration 45%, viscosity 300 dP. A polyurethane resin solution of s was obtained. The reaction time required about twice that of Example 5 and Comparative Example 1.

Contact angle of water: The polyurethane resin solutions obtained in Example 5 and Comparative Examples 1 and 2 were cast on a release paper and dried at 120 ° C. for 5 minutes to form a film of about 50 microns, and this was used as a sample. FACE automatic contact angle meter The contact angle of water was measured with a CA-Z type. The measurement results are shown in Table-1.
Blocking resistance; cast the polyurethane resin solutions obtained in Example 5 and Comparative Examples 1 and 2 onto a release paper, and dry at 120 ° C. for 5 minutes to form a film of about 50 microns. Two sheets were stacked, a load of 500 g was applied, and after placing in a dryer at 50 ° C. for 12 hours, the peel strength of the two films was measured using an autograph AG-100KNG from Shimadzu Corporation. The measurement results are shown in Table-1.

［応用例１］ドデシル基をペンダント状に導入したポリウレタン樹脂とドデシル基を主鎖に導入したポリウレタン樹脂の転相乳化品
実施例５、及び比較例１，２で得られたポリウレタン樹脂溶液を、攪拌しながらｎ−ヘプタンに少しずつ滴下して非水分散化した。実施例５は安定な非水分散液が得られたが、比較例１，２は、すぐに分離沈降し、安定な非水分散ポリウレタンは得られなかった。

[Application Example 1] Phase change emulsion of polyurethane resin in which dodecyl group is introduced in a pendant manner and polyurethane resin in which dodecyl group is introduced in the main chain Example 5 and the polyurethane resin solutions obtained in Comparative Examples 1 and 2 While stirring, the solution was added dropwise to n-heptane little by little to disperse in water. In Example 5, a stable non-aqueous dispersion was obtained, but Comparative Examples 1 and 2 were immediately separated and settled, and a stable non-aqueous dispersion polyurethane was not obtained.

The conceptual diagram of the polyurethane resin of this invention is shown. Urethane in water of polyurethane resin having polyethylene glycol chain in the side chain

The conceptual diagram of particle | grains is shown.

Claims (3)

A long-chain alkyl group-containing diol represented by the general formula (1).

(In the formula, R 1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, R 2 is an alkyl group having 8 to 36 carbon atoms, and R 3 is —CO—NH—R 4. -NH-CO-, wherein R4 is an organic group containing a carbon atom having 2 to 18 carbon atoms, and a diisocyanate residue containing any functional group of an alkylene group, a phenylene group, a cyclohexylene group, or a biphenylene group .) General formula (2)
_{HO-R1-NHCH 2 CH 2} COO-R2 (2)
In the formula, R1 is an alkylene group or dialkylene ether group having 2 to 9 carbon atoms, and R2 is an alkyl group having 8 to 36 carbon atoms. The method for producing a long-chain alkyl group-containing diol represented by the general formula (1) according to claim 1, wherein: A polyurethane resin having a component unit of the long-chain alkyl group-containing diol according to claim 1 and a polyisocyanate component unit and having a number average molecular weight of 5,000 to 500,000.

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