Method of producing super soft polyacrylate-urethane (PAU) core-shell copolymer dispersions by solvent free process

Abstract

Method of producing super soft PAU core-shell copolymer dispersions is a solvent free process. The products have characteristics of both polyurethane and polyacrylate including being non-sticky, having a feeling of touching a peach when touching it by the hand, and having improved adhesion, tensile strength, and toughness.

Claims

1. A method of producing dispersions from acrylate monomers by a solvent free process comprising: (a) synthesizing a solvent free polyurethane dispersion (PUD) in the amount of 40.0 wt % of the acrylate monomers as a seed emulsion; (b) taking an initiator in the amount of 0.20 wt. %-0.60 wt. % of the acrylate monomers to dissolve in deionized water to obtain an initiator solution which is equally distributed into first, second and third parts; (c) taking an emulsifier in the amount of 0.20 wt %-0.30 wt % of the acrylate monomers, polyoxyethylene alkyl ether ammonium sulfate in the amount of 0.20-0.30 wt. % of the acrylate monomer, and n-butyl acrylate (n-BA) as a soft monomer in the amount of 3.0-8.0 wt. % of the acrylate monomers to emulsify in the deionized water to obtain a first pre-emulsion acrylate; (d) taking the emulsifier in the amount of 0.20 wt %-0.30 wt % of the acrylate monomers, the polyoxyethylene alkyl ether ammonium sulfate in the amount of 0.13 wt %-0.30 wt % of the acrylate monomers, the n-BA in the amount of 43.3 wt %-86.7 wt % of the acrylate monomers, and methyl methacrylate (MMA) as a hard monomer in the amount of 8.0 wt %-52.0 wt % of the acrylate monomers to emulsify in the deionized water to obtain a second pre-emulsion acrylate; (e) pouring the solvent free PUD into a reaction vessel having a reaction temperature set at 70-90 C. and a rotational speed set at 300-500 rpm for reaction; (f) adding the first pre-emulsion acrylate and the first part of the initiator solution to the reaction vessel for one to two hours; (g) adding the second pre-emulsion acrylate and the second part of the initiator solution into the reaction vessel; (h) after adding more than half of the second pre-emulsion acrylate, adding the third part of the initiator solution into the reaction vessel; (i) increasing the reaction temperature up to 90-95 C.; (j) maintaining the reaction temperature for one to two hours and turning off heating; and (k) cooling the reaction vessel for one hour to produce a solid content of 40.0 wt % of solvent free super soft polyacrylate-urethane (PAU) core-shell copolymer dispersions, wherein a weight percentage ratio of polyacrylate (PA) and polyurethane (PU) is 25 wt %:100 wt % -100 wt %:100 wt %.

2. The method of claim 1, wherein synthesizing the seed emulsion comprises: (1) drying polyol at a temperature in vacuum for a period of time; (2) placing both the dried polyol and 2,2-dimethylol butanoic acid (DMBA) in another reaction vessel to mix at 90 C. and rotate at a rotational speed 100 rpm until a mixture becomes transparent; (3) adding diisocyanate having an isocyanate functional group (NCO) to the mixture to react at 70-90 C. and a rotational speed of 50-100 rpm for 5-10 minutes until a NCO terminated first prepolymer is formed; (4) decreasing temperature of the NCO terminated first prepolymer to 65 C.; (5) adding a neutralizing agent to the NCO terminated first prepolymer for neutralization and catalysis until a NCO terminated second prepolymer is formed; (6) adding the remaining diisocyanate having the isocyanate functional group to the NCO terminated second prepolymer to form a NCO terminated third prepolymer; (7) adding deionized water to the third prepolymer to form a prepolymer dispersion; and (8) adding a chain extension agent to the prepolymer dispersion to rotate at a range of 1,000 to 2,000 rpm for a chain extension for 1-3 hours until the solvent free PUD is produced; wherein a mole ratio of the polyol to the DMBA is 0.57 to 9.11, and a molar percentage of the polyol to DMBA is 36.3%:63.7% to 90.1%:9.9%; wherein a mole ratio of the diisocyanate having the isocyanate functional group to the mixture of the NCO terminated first prepolymer is 1.08 to 1.12 and a molar percentage of the diisocyanate having the isocyanate functional group to the mixture of the NCO terminated first prepolymer is 51.9%:48.1% to 52.9%:47.1%; wherein a mole ratio of the NCO terminated first prepolymer to the neutralizing agent is 0.38 to 1.56, and a molar percentage of the NCO terminated first prepolymer to the neutralizing agent is 27.7%:72.3% to 61.0%:39.0%; and wherein a mole ratio of the NCO terminated second prepolymer to the diisocyanate having the isocyanate functional group is 0.14 to 0.63, and a molar percentage of the NCO terminated second prepolymer to the diisocyanate having the isocyanate functional group is 12.2%:87.8% to 38.6%:61.4%.

3. The method of claim 2, further comprising adding hydroxyethyl acrylate (HEA) to the NCO terminated third prepolymer and agitating for two to four hours to form a NCO terminated fourth prepolymer having a CC-functional group; and wherein a mole ratio of the NCO terminated third prepolymer to the HEA is 0 to 2.0, and a molar percentage of the NCO terminated third prepolymer to the HEA is 66.7% :33.3% to 100.0%:0%.

4. The method of claim 1, wherein: adding the first pre-emulsion acrylate to the reaction vessel is at the speed of 0.40-0.70 mL/min, and adding of the KPS initiator solution to the reaction vessel is at a speed of 0.30-0.45 mL/min; adding the second pre-acrylate emulsion is at a speed of 1.00-1.20 mL/min and the second part of the initiator solution is at the speed of 0.10-0.30 mL/min; and adding the third part of the initiator solution is at a speed of 0.10-0.30 mL/min.

5. The method of claim 1, wherein the acrylate monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, dodecyl 2-methylacylate, acrylic acid, methacrylic acid, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, glycidyl acrylate or glycidyl methacrylate.

6. The method of claim 1, wherein the initiator solution is potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, organic peroxide, diacyl peroxide, peroxy acid, perester or azo compounds.

7. The method of claim 1, wherein the emulsifier is sodium dodecyl benzene sulfonate, dioctyl sodium sulfosuccinate, sodium dodecyl diphenyl disalfonate, succinate polyoxyethylene alkyl phenol ether sulfonate half ester, succinate polyoxyethylene alkyl phenol ether sulfonate half ester, poly ehthylene oxide-b-propylene oxide or polyoxyethylene alxylphenol ether.

8. The method of claim 1, wherein the super soft PAU core-shell copolymer dispersions have a shell of PUD and a core of polyacrylate dispersions.

9. The method of claim 8, wherein the super soft PAU core-shell copolymer dispersions have a 500% modulus less than 6.0 MPa, and a tensile strength greater than 15.0 MPa.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flowchart of a method of producing super soft polyacrylate-urethane (PAU) core-shell copolymer dispersions by a solvent free process according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

(2) Referring to FIG. 1, a flowchart of a method of producing super soft PAU core-shell copolymer dispersions by a solvent free process according to the invention is illustrated by 12 preferred embodiments.

(3) Embodiments 1-3discuss the effect of a coupling agent hydroxyethyl acrylate (HEA) content in solvent free PAU dispersions in which a chain extension agent in PUD has a composition ratio of HEA: ethylene diamine (EDA) being one of 2:8, 0:10, and 4:6 for producing solvent free super soft PAU dispersion products.

(4) Embodiment 1

(5) A composition ratio of HEA:EDA as PUD chain extension agents is 2:8, and the synthesized PAU copolymer is called AUH2M2.

(6) 1. Synthesizing PUD Seed Emulsion:

(7) (a) 210 -230 g (0.105 -0.115 mol) of polytetramethylene ethrer glycol (PTMEG) 2000 with a molar mass of 2000 g/mol is dried at 120 C. in vacuum for about two hours.

(8) (b) the dried PTMEG 2000 is mixed with 15.0 -17.0 g (0.101 -0.115 mol) of DMBA at a reaction vessel at 70 -90 C. at a rotational speed of 100 rpm for about one hour until both DMBA and PTMEG 2000 become transparent.

(9) (c) 16.0 -17.0 g (0.095 -0.101 mol) of hexamethylene diisocyanate (HDI and 33.0-35.0 g (0.148 -0.157 mol) of isophorone diisocynate (IPDI) are added in step 2 together and are reacted to form isocyanate terminated polyurethane at 90 C. and 50 -100 rpm for a polymerization reaction for 5 -10 minutes until a NCO terminated first prepolymer is formed.

(10) (d) the temperature is decreased to 65 C. and then 11.0 -12.0 g (0.109 -0.119 mol) of triethylamine (TEA) is added for neutralization and catalysis until a NCO terminated second prepolymer is formed.

(11) (e) the di-n-butylamine back titration method is used to measure the equivalent of the NCO terminated prepolymer until the equivalent of the prepolymer is controlled at 4,500 g/eq. mol5% (free NCO % =0.935%). Then, 17.0 -18.0 g (0.076 -0.081 mol) of the remaining IPDI at step (c) is added and mixed at 50 rpm for 10 -15 minutes until a NCO terminated third prepolymer is formed.

(12) (f) 2.5 -3.0 g (0.022 -0.026 mol) of the coupling agent HEA added at 70 C. and 50 rpm is reacted for 2 -4 hours until NCO terminated and containing a CC functional fourth prepolymer is formed.

(13) (g)470-490 g of the deionized water is added to decrease temperature to 40 C., and the rotational speed is increased to 200-300 rpm to be in a PU prepolymer dispersion stage for one hour.

(14) (h) the prepolymer dispersion is conveyed to an emulsifier machine, and 2.5-3.0 g (0.042-0.050 mol) of EDA chain extension agent is added. The emulsifier machine is rotated at 2,000 rpm for a chain extension for 1-2 hours until the solid content of 40.0 wt % of the solvent free PUD seed emulsion is produced.

(15) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(16) (i) 0.50-0.80 g (0.33 wt %-0.53 wt % of acrylate monomers) of KPS is dissolved in 60-75 g of the deionized water to obtain an initiator solution which is equally distributed into three parts.

(17) (j) 0.30-0.40 g (0.20 wt %-0.27 wt % of the acrylate monomers) of SDS and 0.30-0.40 g (0.20 wt %-0.27 wt % of the acrylate monomers) of LRS 10, and 5.0-8.0 g (3.33 wt %-5.33 wt % of the acrylate monomers) of the soft monomer n-BA are emulsified in 15-30 g of the deionized water to obtain a first pre- emulsion acrylate.

(18) (k) 0.30-0.40 g (0.20 wt %-0.27 wt % of the acrylate monomers) of emulsifier SDS, 0.30-0.40 g (0.20 wt %-0.27 wt % of the acrylate monomers) of emulsifier LRS 10, 110-115 g (73.3 wt %-76.7 wt % of the acrylate monomers) of n-BA, and 27-33 g (18.0 wt % -22.0 wt % of the acrylate monomers) of MMA are emulsified in 120-140 g of the deionized water to obtain a second pre-emulsion acrylate.

(19) 3. Synthesizing PAU Copolymer:

(20) (1) Synthesized 500 g of PUD seed emulsion is added to a reaction vessel, the temperature is set at 70-90 C., the rotational speed is set at 300-500 rpm, the first pre-emulsion acrylate is added to the reaction vessel at the speed of 0.40-0.70 mL/min, and the first KPS initiator solution is added to the reaction vessel at the speed of 0.30-0.45 mL/min.

(21) (m) After reacting for 1-2 hours, the second pre-emulsion acrylate is added to the reaction vessel at the speed of 1.00-1.20 mL/min, and a second KPS initiator solution is added to the reaction vessel at the speed of 0.10-0.30 mL/min.

(22) (n) After adding half of the amount of the second pre-emulsion acrylate, the remaining third KPS initiator solution is added to the reaction vessel at the speed of 0.10-0.30 mL/min.

(23) (o) After adding, the reaction temperature is increased to 90-95 C. and maintained for 1-2 hours prior to turning off the heating. The reaction vessel is cooled for one hour, and the solid content of 40.0 wt % of the solvent free super soft PAU, called AUH2M2, is produced.

(24) Embodiment 2: Composition ratio of HEA:EDA as PUD chain extension agents is 0:10, and the synthesized PAU copolymer is called AUH0M2.

(25) 1. Synthesizing PUD Seed Emulsion:

(26) Steps (a)-(g) are the same as embodiment 1, step (f) is omitted herein, and HEA is not added to the process. Thus, a detailed description thereof is omitted herein for the sake of brevity.

(27) (h) the prepolymer dispersion is conveyed to an emulsifier machine, and 3.0 -3.4 g (0.050-0.057 mo1) of the EDA chain extension agent is added. The emulsifier machine is rotated at 2,000 rpm for a chain extension for 1-2 hours until a solid content of 40.0 wt % of the solvent free PUD seed emulsion is produced.

(28) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(29) Steps (i) to (k) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(30) 3. Synthesizing PAU Copolymer:

(31) Steps (l) to (o) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called AUH0M2.

(32) Embodiment 3: Composition ratio of HEA:EDA as PUD chain extension agents is 4:6, and the synthesized PAU product is called AUH4M2.

(33) 1. Synthesizing PAD Seed Copolymer:

(34) Steps (a) to (e) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(35) (f) 5.0-6.0 g (0.043-0.052 mol) of HEA is added. Reaction is taken at 70 C., and the rotational speed is 50 rpm. The reaction takes 2-4 hours.

(36) (g) 470-490 g of deionized water is added to the reaction vessel. Temperature is decreased to 40 C., and the rotational speed is increased to 200-300 rpm at PU prepolymer dispersion stage for one hour.

(37) (h) the prepolymer dispersion is conveyed to an emulsifier machine, and 2.3-2.5 g (0.038-0.042 mol) of EDA chain extension agent is added. The emulsifier machine is rotated at 2,000 rpm for the chain extension for 1-2 hours until the solid content of 40.0 wt % of the solvent free PUD seed emulsion is produced.

(38) 2. Preparation of Initiator Solution and Pre-Acrylate Emulsion:

(39) Steps (i) to (k) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(40) 3. Synthesizing PAU Copolymer:

(41) Steps (l) to (o) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity. The PAU copolymer is called AUH4M2.

(42) Composition and mechanical properties of the solvent free super soft PAU with different amounts of HEA of embodiments 1 to 3 are tabulated in tables 1 and 2 respectively.

(43) As shown with the mechanical properties of PAU in table 2, and with the addition of the amount of HEA, a chemical bonding degree of HEA and PAD is increased, and the modulus of each extension rate is increased. From the PUD formula, HEA:EDA is 2.0:8.0, the synthesized AUH2M2has 500% modulus of 4.0 MPa complying with a super soft PAU specification, but the tensile strength is 13.7 MPa, which is less than the required 15.0 MPa.

(44) TABLE-US-00001 TABLE 1 (embodiment) prescription table AUH2M2 AUH0M2 AUH4M2 PUD composition HDI-IPDI (g) 66-70 66-70 66-70 polyol (g) 210-230 210-230 210-230 carboxylic diol (g) 15-17 15-17 15-17 TEA (g) 11-12 10-11 11-12 HEA (g) 2.5-3.0 0 5.0-6.0 EDA (g) 2.5-3.0 3.0-3.4 2.3-2.5 free NCO (g) 0.93 5.0% 0.93 5.0% 0.93 5.0% D.I. water (g) 470-490 470-490 470-490 HEA:EDA (molar 2:8 0:10 4:6 ratio) PAU composition PUD (g) 500 500 500 KPS (g) 0.5-0.8 0.5-0.8 0.5-0.8 SDS (g) 0.6-0.8 0.6-0.8 0.6-0.8 LRS 10 (g) 0.6-0.8 0.6-0.8 0.6-0.8 MMA (g) 27.0-35.0 27.0-35.0 27.0-35.0 n-BA (g) 110-115 110-115 110-115 D.I. water (g) 200-230 200-230 200-230

(45) TABLE-US-00002 TABLE 2 (embodiment) mechanical properties of PAU AUH2M2 AUH0M2 AUH4M2 100% modulus (MPa) 1.2 0.6 2.0 300% modulus (MPa) 2.2 1.2 3.9 500% modulus (MPa) 4.0 1.9 8.2 Tensile strength (MPa) 13.7 9.5 20.2 Elongation (%) 934 1,246 748

(46) Embodiments 4 to 8 discuss the effect of the ratios of the added hard monomer MMA and the soft monomer n-BA in PAU for solvent free super soft PAU core-shell copolymer dispersions in which weight percentage ratios of added MMA and n-BA are 1.0:9.0, 2.0:8.0, 3.0:7.0, 4.0:6.0 and 5.0:5.0 for synthesizing a solvent free super soft PAU, in which the composition ratio of HEA:EDA is 2.0:8.0, and in which the PA:PU is 75:100 (wt %:wt %).

(47) Embodiment 4: added weight percentage ratio of hard monomer MMA and soft monomer n-BA in PUD is 1.0:9.0, and the synthesized PAU is called A75H2M1.

(48) 1. Synthesizing PUD Seed Emulsion:

(49) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(50) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(51) (i) 0.50-0.80 g (0.33 wt %-0.53 wt % of acrylate monomers) of KPS is dissolved in 70-75 g of deionized water to obtain an initiator solution which is equally distributed into three parts.

(52) (j) 0.30-0.40 g (0.20 wt %-0.27 wt % of acrylate monomers) of SDS and 0.30-0.40 g (0.20 wt %-0.27 wt % of acrylate monomers) of LRS10 and 5.0-8.0 g (3.33 wt %-5.33 wt % of acrylate monomers) of n-BA are emulsified in 25-30 g of deionized water to obtain a first pre-emulsion acrylate.

(53) (k) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of LRS 10 and 125-130 g (83.3 wt %-86.7 wt % of acrylate monomers) of n-BA, and 12-18 g (8.0 wt %-12.0 wt % of acrylate monomers) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-emulsion acrylate.

(54) 3. Synthesizing PAU Copolymer:

(55) (l) synthesized 500 g of the seed emulsion PUD is added to a reaction vessel, temperature is set at 70-90 C., rotational speed is set at 300-500 rpm, the first pre-emulsion acrylate is added to the reaction vessel at the speed of 0.50-0.65 mL/min, and the first KPS initiator solution is added to the reaction vessel at the speed of 0.35-0.45 mL/min.

(56) (m) After reacting for 1-2 hours, the second pre-emulsion acrylate is added to the reaction vessel at the speed of 1.00-1.50 mL/min, and a second KPS initiator solution is added to the reaction vessel at the speed of 0.20-0.25 mL/min.

(57) (n) after adding half of the amount of the second pre-emulsion acrylate, the remaining third KPS initiator solution is added to the reaction vessel at the speed of 0.20-0.25 mL/min.

(58) (o) after the adding, the reaction temperature is increased to 90-95 C. and maintained for 1-2 hours prior to turning off the heating. The reaction vessel is cooled for one hour, and the solid content of 40.0 wt % of the solvent free super soft PAU, called A75H2M1, is produced.

(59) Embodiment 5: added weight percentage ratio of hard monomer MMA and soft monomer n-BA in PUD is 2.0:8.0, and the synthesized PAU copolymer is called A75H2M2.

(60) 1. Synthesizing PUD Seed Emulsion:

(61) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(62) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(63) Steps (i) to (j) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity.

(64) (k) 0.30-0.40 g (0.20 wt %-0.27 wt % of acrylate monomers) of SDS, 0.30-0.40 g (0.20 wt %-0.27 wt % of acrylate monomers) of LRS 10, 110-115 g (73.3 wt % -76.7 wt % of acrylate monomers) of n-BA, and 27-33 g (18.0 wt %-22.0 wt % of acrylate monomer) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-emulsion acrylate.

(65) 3. Synthesizing PAU Copolymer:

(66) Steps (l) to (o) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A75H2M2.

(67) Embodiment 6: added weight percentage ratio of hard monomer MMA and soft monomer n-BA in PUD is 3.0:7.0, and the synthesized PAU is called A75H2M3.

(68) 1. Synthesizing PUD Seed Emulsion:

(69) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(70) 2. Preparation of Initiator Solution and Pre-acrylate Emulsion:

(71) Steps (i) to (j) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity.

(72) (k) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of LRS 10, 95-99 g (63.3 wt %-66.0 wt % of acrylate monomers) of n-BA, and 43-48 g (28.7 wt %-32.0 wt % of acrylate monomers) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-emulsion acrylate.

(73) 3. Synthesizing PAU Copolymer:

(74) Steps (l) to (o) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity. The synthesized PAU is called A75H2M3.

(75) Embodiment 7: added weight percentage ratio of hard monomer MMA and soft monomer n-BA in PUD is 4.0:6.0, and the synthesized PAU copolymer is called A75H2M4.

(76) 1. Synthesizing PUD Seed Emulsion:

(77) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(78) 2. Preparation of Initiator Solution and Pre-acrylate Emulsion:

(79) Steps (i) to (j) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity.

(80) (k) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of LRS 10, 80-84 g (53.3 wt %-56.0 wt % of acrylate monomers) of n-BA, and 58-63 g (38.7 wt %-42.0 wt % of acrylate monomers) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-emulsion acrylate.

(81) 3. Synthesizing PAU Copolymer:

(82) Steps (l) to (o) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A75H2M4.

(83) Embodiment 8: added weight percentage ratio of hard monomer MMA and soft monomer n-BA in PUD is 5.0:5.0, and the synthesized PAU copolymer is called A75H2M5.

(84) 1. Synthesizing PUD Seed Emulsion:

(85) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(86) 2. Preparation of Initiator Solution and Pre-acrylate Emulsion:

(87) (i) to (j) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity.

(88) (k) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of LRS 10, 65-70 g (43.3 wt %-46.7 wt % of acrylate monomers) of n-BA, and 72-78 g (48.0 wt %-52.0 wt % of acrylate monomers) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-acrylate emulsion.

(89) 3. Synthesizing PAU Copolymer:

(90) Steps (l) to (o) are the same as embodiment 4 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A75H2M5.

(91) In embodiments 4 to 8, different added weight percentage ratios of MMA and n-BA in PUD are used to prepare solvent free super soft PAU. Composition and mechanical properties of the PAU products are tabulated in tables 3 and 4 respectively.

(92) As shown in the mechanical properties of PAU of table 4, with the addition of the amount of MMA, 100% modulus is increased. A75H2M1is synthesized by added weight percentage ratio of MMA and n-BA being 1.0:9.0; A75H2M2is synthesized by added weight percentage ratio of MMA and n-BA being 2.0:8.0; A75H2M3is synthesized by added weight percentage ratio of MMA and n-BA being 3.0:7.0; and A75H2M4is synthesized by added weight percentage ratio of MMA and n-BA being 4.0:6.0. 500% modulus of each of 3.4 MPa, 4.0 MPa, 4.3 MPa and 3.4 MPa is complied with a super soft PAU specification. The tensile strength of A75UH2M2is 13.7 MPa is increased to that of A75H2M4being 15.6 MPa and is complied with the specifications of the super soft PAU. When A75H2M5is synthesized by the added weight percentage ratio of MMA and n-BA being 5.0:5.0, 500% modulus is 6.7 MPa which does not comply with the specifications of the super soft PAU.

(93) TABLE-US-00003 TABLE 3 (embodiment) prescription A75H2M1 A75H2M2 A75H2M3 A75H2M4 A75H2M5 PUD composition HDI-IPDI (g) 66-70 66-70 66-70 66-70 66-70 polyol (g) 210-230 210-230 210-230 210-230 210-230 carboxylic diol (g) 15-17 15-17 15-17 15-17 15-17 TEA (g) 11-12 11-12 11-12 11-12 11-12 HEA (g) 2.5-3.0 2.5-3.0 2.5-3.0 2.5-3.0 2.5-3.0 EDA (g) 2.5-3.0 2.5-3.0 2.5-3.0 2.5-3.0 2.5-3.0 free NCO (g) 0.93 5.0% 0.93 5.0% 0.93 5.0% 0.93 5.0% 0.93 5.0% D.I. water (g) 470-490 470-490 470-490 470-490 470-490 PAU composition PUD (g) 500 500 500 500 500 KPS (g) 0.50-0.80 0.50-0.80 0.50-0.80 0.50-0.80 0.50-0.80 SDS (g) 0.40-0.80 0.40-0.80 0.40-0.80 0.40-0.80 0.40-0.80 LRS 10 (g) 0.40-0.80 0.40-0.80 0.40-0.80 0.40-0.80 0.40-0.80 MMA (g) 12-18 27-33 43-48 58-63 72-78 n-BA (g) 132-138 117-123 102-107 87-92 72-78 D.I. water (g) 205-235 205-235 205-235 205-235 205-235 MMA:n-BA 1.0:9.0 2.0:8.0 3.0:7.0 4.0:6.0 5.0:5.0 (wt. %:wt. %)

(94) TABLE-US-00004 TABLE 4 (embodiment) Mechanical properties A75H2M1 A75H2M2 A75H2M3 A75H2M4 A75H2M5 100% 1.0 1.2 1.3 1.3 1.4 modulus (MPa) 300% 1.8 2.2 2.3 2.1 2.7 modulus (MPa) 500% 3.4 4.0 4.3 3.4 6.7 modulus (MPa) Tensile 10.8 13.7 14.7 15.6 18.0 strength (MPa) Elongation 757 934 779 897 731 (%)

(95) Embodiments 9 to 12 discuss the effect of the weight ratios of PAD and PUD in PAU products of solvent free super soft PAU core-shell copolymer dispersions in which the added weight percentage ratios of PAD and PUD in the PAU products are 25:100, 50:100, 75:100 and 100:100. The composition ratio of HEA:EDA is 2.0:.8.0, and the ratio of MMA and n-BA is 4.0:6.0.

(96) Embodiment 9: The added weight percentage ratio of PAD and PUD is 25 wt %:100 wt %, and the synthesized PAU copolymer is called A25H2M4.

(97) 1. Synthesizing PUD Seed Emulsion:

(98) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(99) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(100) (i) 0.10-0.30 g (0.20 wt %-0.60 wt % of acrylate monomers) of KPS is dissolved in 24-27 g of deionized water to obtain an initiator solution which is equally distributed into three parts.

(101) (j) 0.10-0.13 g (0.20 wt %-0.26 wt % of acrylate monomers) of SDS, 0.10-0.13 g (having 0.20 wt %-0.26 wt % of acrylate monomers) of LRS10, and 2.0-4.0 g (4.00 wt %-8.00 wt % of acrylate monomers) of n-BA are emulsified in 5-10 g of deionized water to obtain a first pre-acrylate emulsion.

(102) (k) 0.10-0.13 g (0.20 wt %-0.26 wt % of acrylate monomers) of SDS, 0.10-0.13 g (0.20 wt %-0.26 wt % of acrylate monomers) of LRS 10, 25-30 g (50.0 wt %-60.0 wt % of acrylate monomers) of n-BA, and 16-23 g (32.0 wt %-46.0 wt % of acrylate monomers) of MMA are emulsified in 35-45 g of deionized water to obtain a second pre-emulsion acrylate.

(103) 3. Synthesizing PAU Copolymer:

(104) (l) The synthesized 500 g of the seed emulsion PUD is poured into a reaction vessel, temperature is set at 70-90 C., a rotational speed 300-500 rpm is set, a first pre-emulsion acrylate is added to the reaction vessel at the speed of 0.20-0.25 mL/min, and the first KPS initiator solution is added to the reaction vessel at the speed of 0.10 mL-0.20 mL/min.

(105) (m) After reacting for 1-2 hours, the second pre-emulsion acrylate is added to the reaction vessel at the speed of 0.25-0.30 mL/min, and a second KPS initiator is added to the reaction vessel at the speed of 0.05-0.10 mL/min.

(106) (n) After adding a half amount of the second pre-emulsion acrylate, the remaining third KPS initiator solution is added to the reaction vessel at the speed of 0.05-0.10 mL/min.

(107) (o) After the adding, the reaction temperature is increased to 90-95 C. and maintained for 1-2 hours prior to turning off the heating. The reaction vessel is cooled for one hour, and the solid content of 40.0 wt % of the solvent free super soft PAU, called A25H2M4, is produced.

(108) Embodiment 10: added weight percentage ratio of PAD and PUD in PAU is 50 wt %:100 wt %, and the synthesized PAU copolymer is called A50H2M4.

(109) 1. Synthesizing PUD Seed Emulsion:

(110) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(111) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(112) (i) 0.30-0.51 g (0.30 wt %-0.51 wt % of acrylate monomers) of KPS is dissolved in 48-60 g of deionized water to obtain an initiator solution which is equally distributed into three parts.

(113) (j) 0.20-0.30 g (0.20 wt %-0.30 wt % of acrylate monomers) of SDS, 0.20-0.30 g (0.20 wt %-0.30 wt % of acrylate monomers) of LRS10, and 3.0-6.0 g (3.0 wt %-6.0 wt % of acrylate monomers) of n-BA are emulsified in 10-20 g of deionized water to obtain a first pre-emulsion acrylate.

(114) (k) 0.20-0.30 g (0.20 wt %-0.30 wt % of acrylate monomers) of SDS, 0.20-0.30 g (0.20 wt %-0.30 wt % of acrylate monomers) of LRS 10, 52-57 g (52.0 wt %-57.0 wt % of acrylate monomers) of n-BA, and 37-45 g (37.0 wt %-45.0 wt % of acrylate monomers) of MMA are emulsified in 85-95 g of deionized water to obtain a second pre-emulsion acrylate.

(115) 3. Synthesizing PAU Copolymer:

(116) Steps (l) to (o) are the same as embodiment 9 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A50H2M4.

(117) Embodiment 11: added weight percentage ratio of PAD and PUD in PAU is 75 wt %:100 wt %, and the synthesized PAU copolymer is called A75H2M4.

(118) 1. Synthesizing PUD Seed Emulsion:

(119) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(120) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(121) (i) 0.50-0.80 g (0.33 wt %-0.53 wt % of acrylate monomers) of KPS is dissolved in 60-75 g of deionized water to obtain an initiator solution which is equally distributed into three parts.

(122) (j) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.30-0.40 g (0.20 wt %-0.27 wt % of acrylate monomers) of LRS10, and 5.0-8.0 g 3.3 wt %-5.3 wt % of acrylate monomers) of n-BA are emulsified in 15-30 g of deionized water to obtain a first pre-acrylate emulsion.

(123) (k) 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of SDS, 0.20-0.40 g (0.13 wt %-0.27 wt % of acrylate monomers) of LRS 10, 80-85 g (53.3 wt %-56.7 wt % of acrylate monomers) of n-BA, and 57.0-63.0 g (38.0 wt %-42.0 wt % of acrylate monomers) of MMA are emulsified in 120-130 g of deionized water to obtain a second pre-emulsion acrylate.

(124) 3. Synthesizing PAU Copolymer:

(125) Steps (l) to (o) are the same as embodiment 9 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A75H2M4.

(126) Embodiment 12: added weight percentage ratio of PAD and PUD in PAU is 100 wt %:100 wt %, and the synthesized PAU copolymer is called A100H2M4.

(127) 1. Synthesizing PUD Seed Emulsion:

(128) Steps (a) to (h) are the same as embodiment 1 and, thus, are omitted herein for the sake of brevity.

(129) 2. Preparation of Initiator Solution and Pre-emulsion Acrylate:

(130) (i) 0.90-1.20 g (0.45 wt %-0.60 wt % of acrylate monomers) of KPS is dissolved in 90-100 g of deionized water to obtain an initiator solution which is equally distributed three parts.

(131) (j) 0.40-0.60 g (0.20 wt %-0.30 wt % of acrylate monomers) of SDS, 0.40-0.6 g (0.20 wt %-0.30 wt % of acrylate monomers) of LRS10, and 8.0-12.0 g (4.0 wt %-6.0 wt % of acrylate monomers) of n-BA are emulsified in 30-40 g of deionized water to obtain a first pre-emulsion acrylate.

(132) (k) 0.40-0.60 g (0.20 wt %-0.30 wt % of acrylate monomers) of SDS, 0.40-0.60 g (0.20 wt %-0.30 wt % of acrylate monomers) of LRS 10, 148-152 g (74.0 wt %-76.0 wt % of acrylate monomers) of n-BA, and 38-44 g (19.0 wt %-22.0 wt % of acrylate monomers) of MMA are emulsified in 160-190 g of deionized water to obtain a second pre-emulsion acrylate.

(133) 3. Synthesizing PAU Copolymer:

(134) Steps (l) to (o) are the same as embodiment 9 and, thus, are omitted herein for the sake of brevity. The synthesized PAU copolymer is called A100H2M4.

(135) In embodiments 9 to 12, different weight ratios of PAD and PUD are used to prepare the solvent free super soft PAU. The composition and mechanical properties of the PAU products are tabulated in tables 5 and 6 respectively.

(136) As shown with the mechanical properties of PAU in table 6, with increasing the amount of PAD, the tensile strength is decreased due to plasticization of n-BA. As obtained by experiments, 500% modulus is less than 6.0 MPa, and the tensile strength is greater than 15.0 MPa for solvent free super soft PAU products such as A50H2M4, A75H2M4 and A100H2M4 synthesized by added weight percentage ratios of PAD and PUD being 50 wt %:100 wt %, 75 wt %:100 wt % and 100 wt %:100 wt % respectively. The solvent free super soft PAU products display smoothness.

(137) TABLE-US-00005 TABLE 5 (embodiment) PUD prescription table A25H2M4 A50H2M4 A75H2M4 A100H2M4 PUD composition HDI-IPDI (g) 66-70 66-70 66-70 66-70 polyol (g) 210-230 210-230 210-230 210-230 carboxylic 15-17 15-17 15-17 15-17 diol (g) TEA (g) 11-12 11-12 11-12 11-12 HEA (g) 2.5-3.0 2.5-3.0 2.5-3.0 2.5-3.0 EDA (g) 2.3-2.5 2.3-2.5 2.3-2.5 2.3-2.5 free NCO (g) 0.93 5.0% 0.93 5.0% 0.93 5.0% 0.93 5.0% D.I. water (g) 470-490 470-490 470-490 470-490 PAU composition PUD (g) 500 500 500 500 KPS (g) 0.10-0.30 0.30-0.51 0.60-0.80 0.90-1.20 SDS 0.20-0.26 0.40-0.60 0.40-0.80 0.80-1.20 LRS 10 0.20-0.26 0.40-0.60 0.40-0.80 0.80-1.20 MMA 16.0-23.0 37.0-45.0 57.0-63.0 38.0-44.0 n-BA 25-30 52-57 80-85 148-152 D.I. water (g) 60-90 145-170 205-235 300-340 PAD:PUD 25:100 50:100 75:100 100:100 (wt. %:wt. %)

(138) TABLE-US-00006 TABLE 6 (embodiment) mechanical properties A25H2M4 A50H2M4 A75H2M4 A100H2M4 100% modulus (MPa) 1.7 1.2 1.3 1.3 300% modulus (MPa) 3.2 2.0 2.1 2.4 500% modulus (MPa) 7.7 3.8 3.4 5.4 Tensile strength (MPa) 31.0 21.4 15.6 15.1 Elongation (%) 871 1,267 897 712

(139) In embodiments 1 to 12, they discuss products such as A50H2M4, A75H2M4 and A100H2M4 of solvent free super soft PAU core-shell copolymer dispersions for the composition ratio of HEA:EDA being 2.0:8.0, with the weight percentage ratio of MMA and n-BA being 4.0:6.0, and with the weight ratios of PAD:PUD being 50:100, 75:100 and 100:100. These PAU products are smooth. Further, PAU has good adhesion with nylon and polyester.

(140) A mole ratio of the polyol to the DMBA is 0.57 to 9.11, and a molar percentage of the polyol to DMBA is 36.3%:63.7% to 90.1%:9.9%; a mole ratio of the diisocyanate having isocyanate functional group to the first mixture is 1.08 to 1.12, and a molar percentage of the diisocyanate having the isocyanate functional group to the first mixture is 51.9%:48.1% to 52.9%:47.1%; a mole ratio of the NCO terminated first prepolymer to the neutralizing agent is 0.38 to 1.56, and a molar percentage of the NCO terminated first prepolymer to the neutralizing agent is 27.7%:72.3% to 61.0%:39.0%; a mole ratio of the NCO terminated second prepolymer to the remaining diisocyanate having isocyanate functional group is 0.14 to 0.63, and a molar percentage of the NCO terminated second prepolymer to the remaining diisocyanate having isocyanate functional group is 12.2%:87.8% to 38.6%:61.4%; and a mole ratio of the NCO terminated third prepolymer to the HEA is 0 to 2, and a molar percentage of the NCO terminated third prepolymer to the HEA is 66.7%:33.3% to 100.0%:0%.

(141) Preferably, a hydrophilic percentage is defined as the weight of hydrophilic molecules divided by the weight of polyurethane (PU) molecules times 100%; a weight percentage (w/w) of hydrophilic molecules is 2.0 to 7.0%, and the weight percentage is 2.0 wt %:98.0 wt % to 6.5 wt %:93.5 wt %. The weight of hydrophilic molecules is the weight of DMBA molecules; and the weight of PU molecules is defined as a summation of weights of molecules of diisocyanates, polyol, DMBA, the neutralizing agent, the coupling agent, and the chain extension agent.

(142) Preferably, a molar mass of the polyol is 500 to 2,000 g/mol, and the polyol is implemented as a polycarbonate diols (PCD) having a functional group of carbonate, a polyether diols having a functional group of ether, a polyester diols having a functional group of ester, or a combination of any of polycarbonate diols (PCD) having a functional group of carbonate, a polyether diols having a functional group of ether, and a polyester diols having a functional group of ester.

(143) Preferably, diisocyanates is implemented as m-tetramethylxylene diisocynate, m-TMXDI, isophorone diisocyanate (IPDI), 4,4-Methylene dicyclohexyl diisocyanate (H.sub.12MDI), hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate (CHDI), xylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H.sub.6XDI), 2,2,4/2,4, 4-trimethyl-1, 6-diisocyanatohexane, 50%/50%, 2,2,4/2,4,4-trimethyl-1, 6-diisocyanatohexane; 50%/50% (TMHDI), 5/2,6-bis (isocyanatomethyl) bicycle[2.2.1] heptane, isocyanatomethyl bicycle[2.2.1] heptane, (NBDI), methyl cyclohexamethylene diisocyanate (HTDI), L-lysine diisocyanate, (LDI), 1,8-octamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2-methylpentane-1,5-diyl diisocyanate (MPDI), or a combination of any of m-TMXDI, IPDI, H12MDI, HDI, CHDI, XDI, H6XDI, 2,2,4/2,4,4-trimethyl-1,6-diisocyanatohexane, 50%/50%, TMHDI, 2,6-bis (isocyanatomethyl) bicycle[2.2.1] heptane, NBDI, HTDI, LDI, 1,8-octamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, and MPDI.

(144) Preferably, the amines neutralizing agent is implemented as triethylamine (TEA), tripropylamine (TPA), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), or a combination of any of TEA, TPA, LiOH, NaOH, and KOH.

(145) Preferably, a molar mass of the chain extension agent is less than 400 g/mol, and the chain extension agent are implemented as diamines or diols. The diamines is implemented as ethylene diamine (EDA), butane diamine (BDA), pentane diamine (PDA), hexamethylene diamine (HDA), hydrazine (HH), carbonic dihydrazide (CDH), adipic dihydrazide (ADH); and the diols are implemented as ethylene glycol (EG), propylene glycol (PG), butylene glycol(BG), pentylene glycol, hexylene glycol(HG), or a combination of any of EG, PG, BG, pentylene glycol, and HG.

(146) In the above steps of preparing the initiator solution and pre-emulsion acrylate, the initiator solution is peroxymonosulfuric acid, potassium persulfate, KPS, sodium persulfate, ammonium persulfate, hydrogen peroxide, organic peroxide, diacyl peroxide, peroxy acid, perester or azo compounds.

(147) In the above steps of preparing the initiator solution and pre-emulsion acrylate, the emulsifier is polyoxyethylene alkyl ether ammonium sulfate, sodium dodecyl sulfate, SDS, sodium dodecyl benzene sulfonate, dioctyl sodium sulfosuccinate, sodium dodecyl diphenyl disalfonate, succinate polyoxyethylene alkyl phenol ether sulfonate half ester, hexadecyltrimethylammonium bromide, poly ehthylene oxide-b-propylene oxide or polyoxyethylene alxylphenol ether.

(148) In the above steps of preparing the initiator solution and pre-emulsion acrylate, the acrylate involves using methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, dodecyl 2-methylacylate, acrylic acid, methacrylic acid, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, glycidyl acrylate, or glycidyl methacrylate.

(149) The above polyurethane is a polymer containing a urethane group on the molecular bond and includes a polymer having both an urethane group and an urea group.

(150) The polyacrylate of the invention is defined as a copolymer of acrylic acid, and acrylic acid and ester.

(151) The dispersion solution of the invention is defined as a dispersed emulsion having water as a solvent.

(152) In the method of producing the polyurethane dispersion (PUD) and polyacrylate-urethane (PAU) dispersions by a solvent free process of the invention, no organic solvent is added thereto.

(153) The core-shell of the invention is defined as PAU products having a shell structure of PUD and a core structure of PAD as observed by transmission electron microscope (TEM).

(154) The super soft PAU core-shell copolymers of the invention are defined as having a 500% modulus less than 6.0 MPa, and the tensile strength greater than 15.0 MPa. The hand touching a fabric having the super soft characteristic of the invention feels like touching a peach.

(155) A soft monomer of the invention is called an adhesive monomer. It is defined as the major monomer for preparing a poly acrylate emulsion. Its main function is to provide adhesiveness and to increase elasticity and softness of a plastic layer. A hard monomer of the invention is called a cohesive monomer. It is defined as one for providing increased cohesive strength and higher operating temperatures for the poly acrylate emulsion. It also can improve water resistance, adhesive strength and transparency of a plastic layer.

(156) While the invention has been described in terms of preferred embodiments, those skilled in the art will recognize that the invention can be practiced with modifications within the spirit and scope of the appended claims.