[0089] Example
[0090] Hereinafter, the present invention will be described more specifically based on synthesis examples and evaluation examples, but the present invention is not limited to these examples. The physical property analysis of the obtained polyurethane oligomer can be performed by the following method.
[0091] (1) Molecular weight determination
[0092] The weight average molecular weight and the content of low molecular weight components of the obtained polyurethane oligomer were determined by high-speed liquid chromatography ("LC-10A" manufactured by Shimadzu Corporation, column: Shodex GPC KF-806L (excluded) Limit molecular weight: 2×10 7 , Separation range: 100~2×10 7 , Theoretical plate number: 10,000 plates/column, filler material: styrene-divinylbenzene copolymer, filler particle size: 10μm), eluent: tetrahydrofuran) determination, and standard polystyrene molecular weight Calculated by conversion.
[0093] (2) Viscosity measurement
[0094] Using a cone-plate viscometer ("RE550 type viscometer" manufactured by Toki Sangyo Co., Ltd.), the polyurethane oligomers obtained in each synthesis example and comparative synthesis example were measured at a given temperature in accordance with JIS K5600-2-3. Viscosity.
[0095] (3) Measurement of glass phase transition temperature (Tg)
[0096] 1 part by weight of the synthesized polyurethane oligomer, 1 part by weight of methyl ethyl ketone (MEK) and 0.03 part by weight of Darocur 1173 product as a photopolymerization initiator are uniformly mixed to prepare an ultraviolet curable resin composition. The obtained curable composition was coated on a fluororesin sheet, dried (80°C, 2 minutes), and then irradiated with ultraviolet rays (cumulative light quantity 2000mJ/cm) 2 ) Make it solidify. From the obtained cured film, 10 mg of a homopolymer of a polyurethane oligomer was taken out, put in an aluminum pan and sealed, and measured using a differential scanning calorimeter (manufactured by SII Nanotechnology Co., Ltd., EXSTAR 6000) at a temperature increase rate of 10°C/min.
[0097] Synthesis Example 1 Synthesis of polyurethane oligomer UTB-1
[0098] After adding 13.9g (62.5mmol) of isophorone diisocyanate (IPDI) and 0.04g of dibutyltin dilaurate (dibutyltin dilaurate) to a 300mL 4-necked flask equipped with a stirrer, thermometer, cooler, and gas introduction tube, While blowing in dry nitrogen gas, 70.0 g (50.0 mmol) of G-1000 (polybutadiene with hydroxyl groups on both ends, number average molecular weight = 1400) was dropped and the dropping rate was adjusted to maintain the temperature at 80°C. Let it react for 2 hours. Next, after cooling the reaction liquid to 40°C, 0.1 g of methylhydroquinone (MHQ) was added, and dry air was blown in for 10 minutes. Then, 2.4 g (20.7 mmol) of hydroxyethyl acrylamide (manufactured by Kejie Chemical Products Co., Ltd., registered trademark "HEAA") was added, and stirring was continued for 6 hours while maintaining the internal temperature of the system at 80°C under a stream of dry air. Obtain 84.1 g of light yellow viscous liquid UTB-1 with a yield of 98.5%. Analyzed by infrared absorption spectroscopy (IR), the characteristic absorption of the isocyanate group of the raw material IPDI (2250cm -1 ) Completely disappeared, and the characteristic absorption of the amide group derived from "HEAA" (1650cm -1 ) And the characteristic absorption of the resulting urethane bond (1740cm -1 ), based on this, it is confirmed that the target polyurethane oligomer UTB-1 has been produced. The weight average molecular weight of UTB-1 is 8,300, and the viscosity at 60°C is 88,000 mPa·s. The Tg is 1.3°C, and the low molecular weight components contained are 2.5%.
[0099] Synthesis Example 2 Synthesis of polyurethane oligomer UTB-2
[0100] As in Synthesis Example 1, GI-1000 (hydrogenated polybutadiene with hydroxyl groups at both ends) was dropped into a mixed solution of 13.5 g (80.0 mmol) of hexamethylene diisocyanate (HDI) and 0.04 g of dibutyltin dilaurate. Number average molecular weight: 1500) 75.0 g (50.0 mmol), and reacted at 70°C for 2 hours. Then, as in Synthesis Example 1, 0.1 g of MHQ and 4.4 g (34.2 mmol) of N-methylhydroxyethyl acrylamide (MHEAA) were added, and the reaction was carried out at 80°C for 2 hours. Obtain 88.2 g of light yellow viscous liquid UTB-2, with a yield of 97.8%. Through IR analysis, it is confirmed that UTB-2 has been generated. UTB-2 has a weight average molecular weight of 5300, a viscosity at 60°C of 65000 mPa·s, a Tg of 5.4°C, and a low molecular weight component of 2.1%.
[0101] Synthesis Example 3 Synthesis of polyurethane oligomer UTB-3
[0102] Use the same as Synthesis Example 1, add 11.9g (53.5mmol) IPDI, 125g (50.0mmol) Poly ip (polyisoprene with hydroxyl at both ends, number average molecular weight: 2500) and 0.07g dibutyltin dilaurate, The reaction was carried out at 90°C for 5 hours while blowing dry nitrogen gas. Next, 0.1 g MHQ and 1.7 g (14.8 mmol) "HEAA" were added, and the reaction was continued at 80°C for 5 hours. 136.5 g of light yellow viscous liquid UTB-3 was obtained, and the yield was 98.2%. Through IR analysis, it is confirmed that UTB-3 has been generated. UTB-3 has a weight average molecular weight of 18,000, a viscosity of 91,000 mPa·s at 60°C, a Tg of -9.3°C, and 1.5% of low-molecular-weight components.
[0103] Synthesis Example 4 Synthesis of polyurethane oligomer UTB-4
[0104] Using the same device as in Synthesis Example 1, after adding 70.0g (50.0mmol) of G-1000 and 0.04g of dibutyltin dilaurate, while blowing in dry nitrogen, 18.5g (110.0mmol) of HDI was dropped while maintaining at 80°C , And then react at 80°C for 7 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 3.9 g (30.0 mmol) of hydroxyethylmethacrylamide (HEMAA) were added, and stirring was continued at 80°C for 7 hours. 90.4 g of light yellow viscous liquid UTB-4 was obtained, and the yield was 97.6%. Through IR analysis, it is confirmed that UTB-4 has been generated. UTB-4 has a weight average molecular weight of 12,000, a viscosity of 85,000 mPa·s at 60°C, a Tg of -2.3°C, and a low molecular weight component of 1.8%.
[0105] Synthesis Example 5 Synthesis of polyurethane oligomer UTB-5
[0106] Using the same device (500mL in capacity) as in Synthesis Example 1, add 70.0g (50.0mmol) of G-1000, 22.2g (100.0mmol) of IPDI and 110g of dimethylacetamide (DMAc), and add dry nitrogen to 100 It was allowed to react at °C for 10 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ, 8.0 g (69.3 mmol) of "HEAA", and 30 g of DMAc were added, and the reaction was continued at 80°C for 8 hours. The solvent was distilled off under reduced pressure to obtain 91.5 g of light yellow viscous liquid UTB-5 with a yield of 96.4%. Through IR analysis, it is confirmed that UTB-5 has been generated. The weight average molecular weight of UTB-5 is 2700, the viscosity at 60°C is 13000 mPa·s, the Tg is 13.3°C, and the low-molecular-weight components contained are 1.1%.
[0107] Synthesis Example 6 Synthesis of polyurethane oligomer UTB-6
[0108] As in Synthesis Example 1, into a mixture of 16.1 g (95.8 mmol) of HDI and 0.04 g of dibutyltin dilaurate, a mixture of 42.0 g (30.0 mmol) of G-1000 and 75.0 g (30.0 mmol) of Poly ip was dropped at 80°C After that, it was allowed to react for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 5.1 g (39.8 mmol) of MHEAA were added, and stirring was continued at 80°C for 6 hours. 136.4 g of light yellow viscous liquid UTB-6 was obtained with a yield of 98.5%. By IR analysis, it was confirmed that the target polyurethane oligomer UTB-6 had been produced. UTB-6 has a weight average molecular weight of 6000, a viscosity at 60°C of 70,000 mPa·s, a Tg of 4.2°C, and contains 4.1% of low molecular weight components.
[0109] Synthesis Example 7 Synthesis of polyurethane oligomer UTB-7
[0110] As in Synthesis Example 1, 28.0 g (20.0 mmol) of GI-1000 and 75.0 g of GI-1000 were dropped into a mixture of 12.1 g (57.5 mmol) of trimethylhexamethylene diisocyanate (TMDI) and 0.04 g of dibutyltin dilaurate ( 30.0 mmol) A mixture of EPOL (hydrogenated polyisoprene having hydroxyl groups at both ends, number average molecular weight = 2500) was reacted at 80°C for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.3 g (20.0 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. 114.8 g of light yellow viscous liquid UTB-7 was obtained, with a yield of 97.6%. Through IR analysis, it is confirmed that UTB-7 has been generated. UTB-7 has a weight average molecular weight of 12,000, a viscosity of 100,000 mPa·s at 60°C, a Tg of -5.1°C, and a low molecular weight component of 1.7%.
[0111] Synthesis Example 8 Synthesis of polyurethane oligomer UTB-8
[0112] Using the same device as in Synthesis Example 1, 56.0 g (40.0 mmol) G-1000, 25.0 g (10.0 mmol) Poly ip, and 0.04 g of dibutyltin dilaurate were added, and the temperature was maintained at 80°C while blowing in dry nitrogen. 10.1 g (60.0 mmol) of HDI was dropped down, and then reacted at 80°C for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.3 g (20.0 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. 92.3 g of light yellow viscous liquid UTB-8 was obtained, with a yield of 96.9%. Through IR analysis, it is confirmed that UTB-8 has been generated. UTB-8 has a weight average molecular weight of 9,300, a viscosity at 60°C of 95,000 mPa·s, a Tg of 0.5°C, and a low molecular weight component of 1.8%.
[0113] Synthesis Example 9 Synthesis of polyurethane oligomer UTB-9
[0114] As in Synthesis Example 8, 9.7 g (57.5 mmol) HDI was dropped at 80°C into a mixed solution of 3.8 g (2.5 mmol) GI-1000, 118.8 g (47.5 mmol) EPOL and 0.04 g dibutyltin dilaurate, and then It reacted for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.9 g (25.0 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. 133.6g of light yellow viscous liquid UTB-9 was obtained, and the yield was 98.9%. Through IR analysis, it is confirmed that UTB-9 has been generated. UTB-9 has a weight average molecular weight of 10,600, a viscosity at 60°C of 150,000 mPa·s, a Tg of -1.1°C, and a low molecular weight component of 2.3%.
[0115] Synthesis Example 10 Synthesis of polyurethane oligomer UTB-10
[0116] Using the same device as in Synthesis Example 1, 150.0g (50.0mmol) of G-3000 (polybutadiene with hydroxy at both ends, number average molecular weight: 3000) and 22.2g (100.0mol) of IPDI were added, and dry nitrogen was added while The reaction was carried out at 130°C for 1 hour. Next, as in Synthesis Example 1, 0.2 g of MHQ and 45.0 g (391.3 mmol) of "HEAA" were added, and stirring was continued at 70°C for 8 hours. Obtained 205.3 g of pale yellow viscous liquid with a yield of 97.7%. IR analysis confirmed that polyurethane oligomers had been produced. The low-molecular-weight component contained was measured to be 6.5%, so the purification step was further carried out.
[0117] The obtained polyurethane oligomer is re-precipitated using a mixed liquid of methyl ethyl ketone and water to remove low molecular weight bodies. Under reduced pressure, methyl ethyl ketone and water were completely removed to obtain a light yellow viscous liquid target polyurethane oligomer UTB-10. Evaluation by the above-mentioned method revealed that the weight average molecular weight of UTB-10 was 4200, the viscosity at 60°C was 22000 mPa·s, the Tg was 8.4°C, and the low molecular weight component contained was 0.4%.
[0118] Synthesis Example 11 Synthesis of polyurethane oligomer UTC-1
[0119] In the same manner as in Synthesis Example 1, 12.7 g (57.0 mmol) of IPDI and 0.03 g of dibutyltin dilaurate were added, and C-1090 (a polycarbonate polyol with hydroxyl groups at both ends manufactured by Kuraray Co., Ltd.) was dropped at 80°C. 3-methyl-1,5-pentanediol/1,6-hexanediol = 9/1, weight average molecular weight = 1000) 50.0 g (50.0 mmol), and the reaction was allowed to proceed for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 1.6 g (14.1 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. Obtained 63.0 g of pale yellow viscous liquid UTC-1 with a yield of 97.8%. Through IR analysis, it is confirmed that UTC-1 has been generated. The weight average molecular weight of the obtained UTC-1 was 8,900, the viscosity at 60°C was 65000 mPa·s, the Tg was 5.8°C, and the low molecular weight component contained was 1.8%.
[0120] Synthesis Example 12 Synthesis of polyurethane oligomer UTC-2
[0121] Using the same device as in Synthesis Example 1, after adding 13.5 g (80.0 mmol) of HDI, 50.0 g (50.0 mmol) of C-1090 was dropped while maintaining the temperature at 60°C while blowing dry nitrogen, and reacted at 60°C 5 hour. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.5 g (21.6 mmol) of "HEAA" were added, and stirring was continued at 80°C for 2 hours. Obtained 61.4 g pale yellow viscous liquid UTC-2, with a yield of 97.2%. As in Synthesis Example 1, it was confirmed by IR analysis that UTC-2 was generated. The weight average molecular weight of UTC-2 is 5600, the viscosity at 60°C is 32000 mPa·s, the Tg is 8.6°C, and the low-molecular-weight components contained are 1.2%.
[0122] Synthesis Example 13 Synthesis of polyurethane oligomer UTC-3
[0123] Using the same device as in Synthesis Example 1, 9.5 g (56.5 mmol) of HDI, 50.0 g (50.0 mmol) of C-1090, and 0.03 g of dibutyltin dilaurate were added, mixed and heated at 80°C for 4 hours while blowing in dry nitrogen. Next, as in Synthesis Example 1, 0.1 g of MHQ and 1.4 g (10.8 mmol) of MHEAA were added, and stirring was continued at 60°C for 3 hours. Obtained 59.9g pale yellow viscous liquid UTC-3 with a yield of 98.2%. Through IR analysis, it is confirmed that UTC-3 has been generated. The weight average molecular weight of the obtained polyurethane oligomer UTC-3 was 11,000, the viscosity at 60°C was 85000 mPa·s, the Tg was 3.2°C, and the low-molecular-weight components contained were 2.5%.
[0124] Synthesis Example 14 Synthesis of polyurethane oligomer UTC-4
[0125] In the same manner as in Synthesis Example 5, 50.0 g (50.0 mmol) of C-1090, 16.7 g (75.0 mmol) of IPDI, 0.03 g of dibutyltin dilaurate, and 120 g of DMAc were added and reacted at 100°C for 3 hours while blowing dry nitrogen. Next, as in Synthesis Example 1, 0.1 g of MHQ, 6.6 g (51.3 mmol) of HEMAA, and 10 g of DMAc were added, and stirring was continued at 90°C for 5 hours. The solvent was distilled off under reduced pressure to obtain 70.4 g of a pale yellow viscous liquid UTC-4 with a yield of 95.9%. Through IR analysis, it is confirmed that UTC-4 has been generated. The weight average molecular weight of the obtained UTC-4 was 2600, the viscosity at 60°C was 8900 mPa·s, the Tg was 13.3°C, and the low molecular weight component contained was 0.8%.
[0126] Synthesis Example 15 Synthesis of polyurethane oligomer UTC-5
[0127] Using the same device as in Synthesis Example 1, 13.3 g (60.0 mmol) IPDI, 45.0 g (45.0 mmol) C-1090, 5.0 g (5.0 mmol) Uniol D-1000 (Uniol D-1000, manufactured by NOF Corporation After mixing propylene glycol, weight average molecular weight = 1000) and 0.03 g of dibutyltin dilaurate, they were allowed to react at 80°C for 2 hours while blowing in dry nitrogen. As in Synthesis Example 1, 0.1 g of MHQ and 2.3 g (20.1 mmol) of "HEAA" were added, and stirring was continued at 60°C for 3 hours. Obtained 64.8 g pale yellow viscous liquid UTC-5 with a yield of 98.5%. Through IR analysis, it is confirmed that UTC-5 has been generated. The weight average molecular weight of the obtained UTC-5 was 6,300, the viscosity at 60°C was 50,000 mPa·s, the Tg was 7.10°C, and the low-molecular weight component contained was 0.9%.
[0128] Synthesis Example 16 Synthesis of polyurethane oligomer UTC-6
[0129] Using the same device as in Synthesis Example 1, 35.0 g (35.0 mmol) of C-1090, 45.0 g (15.0 mmol) of polyester diol (Adeka New Ace Y6-30 manufactured by Asahi Denka Kogyo Co., Ltd., number average molecular weight 3000) and After 0.04 g of dibutyltin dilaurate, 13.3 g (60.0 mmol) of IPDI was dropped while maintaining the temperature at 80°C while blowing dry nitrogen gas, and then reacted at 80°C for 2 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.1 g (18.3 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. Obtained 93.0 g of pale yellow viscous liquid UTC-6 with a yield of 97.3%. Through IR analysis, it is confirmed that UTC-6 has been generated. The weight average molecular weight of the obtained UTC-6 was 10200, the viscosity at 60°C was 78500 mPa·s, and the Tg was 3.1°C.
[0130] Synthesis Example 17 Synthesis of polyurethane oligomer UTC-7
[0131] Using the same device as in Synthesis Example 1, 150.0 g (50.0 mmol) of C-3090 (carbonate polyol with hydroxyl groups at both ends, 3-methyl-1,5-pentanediol/1,6-hexanedi Alcohol = 9/1, number average molecular weight = 3000) and 27.8 g (125.2 mmol) of IPDI were allowed to react at 110°C for 5 hours while blowing dry nitrogen. Next, as in Synthesis Example 1, 0.2 g of MHQ and 5.0 g (43.5 mmol) of "HEAA" were added, and stirring was continued at 80°C for 2 hours. 180.4 g of pale yellow viscous liquid was obtained, with a yield of 98.5%. IR analysis confirmed that polyurethane oligomers had been produced. When the low molecular weight component contained was measured, it was 6.8%, so a further purification step was carried out.
[0132] The obtained polyurethane oligomer was purified in the same manner as in Synthesis Example 10, and the target polyurethane oligomer UTC-7 was obtained as a light yellow viscous liquid. Evaluation was carried out by the above method. The weight average molecular weight of UTC-7 was 16000, the viscosity at 60°C was 135000 mPa·s, the Tg was -1.2°C, and the low molecular weight component contained was 0.6%.
[0133] Comparative synthesis example 1 Synthesis of polyurethane oligomer (UAB-1)
[0134] The unrefined polyurethane oligomer (the product containing 6.5% of low molecular weight components) obtained in Synthesis Example 10 is UAB-1. Furthermore, evaluation was carried out by the above method, and the weight average molecular weight of UAB-1 was 3800, the viscosity at 60°C was 35000 mPa·s, and the Tg was 5.2°C.
[0135] Comparative Synthesis Example 2 Synthesis of Polyurethane Oligomer (UAB-2)
[0136] Using the same equipment as in Synthesis Example 1, 70.0g (50.0mmol) G-1000, 33.3g (150.0mmol) IPDI, 0.04g dibutyltin dilaurate were added, and the reaction was carried out at 50°C for 5 hours while blowing in dry nitrogen. . Next, as in Synthesis Example 1, 0.1 g of MHQ and 6.3 g (50.0 mmol) of "HEAA" were added, and stirring was continued at 80°C for 6 hours. 106.3 g of light yellow viscous liquid was obtained, and the yield was 96.8%. IR analysis confirmed that polyurethane oligomers had been produced. The weight average molecular weight of the obtained polyurethane oligomer UAB-2 was 7,900, the viscosity at 60°C was 95000 mPa·s, the Tg was -3.4°C, and the low molecular weight component contained was 5.2%.
[0137] Comparative Example Synthesis 3 Synthesis of polyurethane oligomer UAB-3
[0138] Using the same equipment as in Synthesis Example 1, after adding 13.3g (59.9mmol) of IPDI and 0.04g of dibutyltin dilaurate, 75.0g (50.0mmol) of GI-1000 was dropped while maintaining at 80°C while blowing in dry nitrogen. The reaction was carried out at 80°C for 6 hours. Next, as in Synthesis Example 1, 0.1 g of MHQ and 2.3 g (20.0 mmol) of hydroxyethyl acrylate (HEA) were added, and stirring was continued at 60° C. for 8 hours under a stream of dry air. Obtained 89.0 g of pale yellow viscous liquid with a yield of 97.9%. Through IR analysis, the characteristic absorption of the isocyanate group of the raw material IPDI (2250cm -1 ) Disappeared completely, and the characteristic absorption (1730cm -1 ) And the characteristic absorption of the urethane bond (1740cm -1 ), based on this, it is confirmed that the polyurethane oligomer UAB-3 has been produced. The weight average molecular weight of the obtained UAB-3 was 12,500, the viscosity at 60°C was 112,000 mPa·s, the Tg was -10.7°C, and the low molecular weight component contained was 2.1%.
[0139] Comparative Example Synthesis 4 Synthesis of Polyurethane Oligomer UAC-1
[0140] The unrefined polyurethane oligomer (containing 6.8% of low-molecular-weight components) obtained in Synthesis Example 17 is assumed to be UAC-1. Furthermore, evaluation was carried out by the above method, and the weight average molecular weight of UAC-1 was 15,000, the viscosity at 60°C was 148,000 mPa·s, and the Tg was 0.5°C.
[0141] Comparative synthesis example 5 Synthesis of polyurethane oligomer UAC-2
[0142] Using the same device as in Synthesis Example 1, 50.0g (50.0mmol) C-1090, 32.8g (147.7mmol) IPDI and 0.03g dibutyltin dilaurate were added, and reacted at 40°C for 2 hours while blowing in dry nitrogen. . Next, as in Synthesis Example 1, 0.1 g of MHQ and 9.2 g (80.0 mmol) of "HEAA" were added, and stirring was continued at 80°C for 3 hours. 90.2 g of light yellow viscous liquid was obtained, and the yield was 97.9%. IR analysis confirmed that the polyurethane oligomer UAC-2 had been produced. The weight average molecular weight of the obtained UAC-2 was 7,900, the viscosity at 60°C was 82,000 mPa·s, the Tg was 5.3°C, and the low molecular weight component contained was 5.4%.
[0143] Comparative Example Synthesis Example 6 Synthesis of polyurethane oligomer UAC-3
[0144] Using the same equipment as in Synthesis Example 1, 50.0 g (50.0 mmol) C-1090, 13.3 g (60.0 mmol) IPDI, and 0.03 g of dibutyltin dilaurate were added, and reacted at 80°C for 2 hours while blowing in dry nitrogen. . Next, as in Synthesis Example 1, 0.1 g of MHQ and 1.3 g (11.2 mmol) of HEA were added, and stirring was continued at 60°C for 3 hours. 63.6 g of light yellow viscous liquid was obtained, with a yield of 98.3%. IR analysis confirmed that the polyurethane oligomer UAC-3 had been produced. The weight average molecular weight of the obtained UAC-3 was 12,500, the viscosity at 60°C was 103,000 mPa·s, the Tg was -2.5°C, and the low molecular weight component contained was 1.2%.
[0145] The properties of the polyurethane oligomers obtained in Synthesis Examples 1 to 17 and Comparative Synthesis Examples 1 to 6 were evaluated by the following methods. The results are shown in Tables 1 and 2. In addition, the solvents and monomers used in the evaluation are as follows.
[0146] IPA: isopropanol
[0147] MEK: Methyl ethyl ketone
[0148] THF: Tetrahydrofuran
[0149] "ACMO": N-acryloyl morpholine (made by Kejie Chemical Products Company)
[0150] HDDA: 1,6-hexanediol diacrylate
[0151] BA: Butyl acrylate
[0152] IBOA: isobornyl acrylate
[0153] 2EHA: 2-ethylhexyl acrylate
[0154] THFA: tetrahydrofurfuryl acrylate
[0155] (4) Compatibility
[0156] To 1 part by weight of the obtained urethane oligomer, a general solvent as a diluent and 1 part by weight of an acrylic monomer were added, and the mixture was stirred and left to stand overnight, and the degree of dissolution was visually confirmed.
[0157] ◎: High transparency, no white turbidity or separation was observed at all.
[0158] ○: High transparency, but slightly white turbidity is seen.
[0159] △: No layer separation but white turbidity.
[0160] ×: White turbidity and layer separation.
[0161] [Table 1]
[0162]
[0163] [Table 2]
[0164]
[0165] As shown in the results of Evaluation Examples A-1 to A-18 and Evaluation Comparative Examples A-19 to A-24, it can be seen that if the polyurethane oligomer contains 5% by weight or more of low molecular weight components, it will be combined with general solvents and single The inter-body compatibility is significantly deteriorated, and it is difficult to widely use it in optical devices.
[0166] The active energy ray curable resin composition was prepared using the polyurethane oligomer obtained in the synthesis example and the comparative synthesis example. Then, these resin compositions were used to produce an ultraviolet cured film and evaluate the characteristics of the cured film. The results are shown in Tables 3 and 4.
