Amino Silicone Polymer, Silicone Emulsion Comprising Same, and Method for Manufacturing Same

Abstract

The present invention relates to: an amino silicone polymer composition comprising hydroxyl-terminated polysiloxane, amino silane, and alkyl alkoxy silane; a silicone emulsion comprising same, showing excellent conditioning effects, and having excellent environment-friendliness; and a method for manufacturing same.

Claims

1. An amino silicone polymer composition comprising hydroxyl-terminated polysiloxane, amino silane, and alkyl alkoxy silane represented by the following Chemical Formula 1:
R.sup.1.sub.4-nSi(OR.sup.2).sub.n  [Chemical Formula 1] Wherein, R.sup.1 and R.sup.2 are each independently C.sub.1-10 alkyl groups, and n is 2 to 3.

2. The amino silicone polymer composition of claim 1, wherein the composition comprises 100 parts by weight of the hydroxyl-terminated polysiloxane, 1 to 10 parts by weight of the amino silane, and 0.1 to 1 part by weight of the alkyl alkoxy silane.

3. The amino silicone polymer composition of claim 1, wherein the hydroxyl-terminated polysiloxane has the viscosity at 25° C. of 1 to 5,000 cP, the weight average molecular weight of 100 to 50,000 g/mol, and the polymerization degree of 1 to 1,000.

4. A silicone emulsion comprising an amino silicone polymer prepared from the amino silicone polymer composition of claim 1, a solvent, a non-ionic emulsifier, and a cationic emulsifier.

5. The silicone emulsion of claim 4, wherein the silicone emulsion comprises 25 to 40 parts by weight of the amino silicone polymer, 50 to 70 parts by weight of the solvent, 1 to 10 parts by weight of the non-ionic emulsifier, and 1 to 10 parts by weight of the cationic emulsifier.

6. A method for manufacturing a silicone emulsion comprising the steps: preparing a first mixture by mixing a first solvent and a non-ionic emulsifier; preparing a second mixture by mixing the first mixture and an amino silicone polymer; and preparing a third mixture by mixing the second mixture and a cationic emulsifier and adding a neutralizing agent and a second solvent, wherein the steps are performed at 15° C. to 30° C., respectively.

7. The method for manufacturing the silicone emulsion of claim 6, wherein the amino silicone polymer is prepared by reacting a composition comprising hydroxyl-terminated polysiloxane, amino silane, and alkylalkoxy silane represented by the following Chemical Formula 1 at 80° C. to 95° C.
R.sup.1.sub.4-nSi(OR.sup.2).sub.n  [Chemical Formula 1] Wherein, R.sup.1 and R.sup.2 are each independently alkyl groups having 1 to 10 carbon atoms, and n is 2 to 3.

Description

EXAMPLES

Example 1. Manufacture of Silicone Emulsion

[0117] 1-1: Preparation of Amino Silicone Polymer

[0118] In a reactor, 95.18 parts by weight of hydroxyl-terminated polysiloxane was added, raised to 95° C. and stirred for 30 minutes. Thereafter, 3 parts by weight of first amino silane and 0.32 part by weight of methyltriethoxy silane ware added and 1 part by weight of 20 wt % of a NaOH aqueous solution as a catalyst was added for 10 minutes. Thereafter, the viscosity was checked and the mixture was cooled to 40° C. for 5 hours when reaching a target viscosity (25,000 cP) and added with 0.5 part by weight of acetic acid as a neutralizing agent to be neutralized to prepare an amino silicone polymer.

[0119] The prepared amino silicone polymer had the viscosity at 25° C. of 25,000 cP and the weight average molecular weight of 80,000 g/mol.

[0120] 1-2: Manufacture of Silicone Emulsion (Room Temperature Stirring)

[0121] In a reactor, a homomixer mounted with an impeller was provided, and 1.5 parts by weight of deionized water (first solvent) as a solvent and 2.5 parts by weight of a non-ionic emulsifier were added and stirred at 25° C. for 20 minutes. Thereafter, 32 parts by weight of an amino silicone polymer of Example 1-1 was slowly added for 80 minutes. After the addition of the amino silicone polymer was completed, the particle size of the dispersed particles was measured every 30 minutes and the mixture was stirred at 25° C. for 90 minutes. When the average particle size of the dispersed particles reached less than 270 nm, 2 parts by weight of a cationic emulsifier was added and stirred. Thereafter, 0.3 parts by weight of 23 wt % of an acetic acid aqueous solution as a neutralizing agent was added and stirred at 25° C. for 30 minutes. Thereafter, 5 parts by weight of deionized water (second solvent) was added and stirred at 25° C. for 30 minutes, and then parts by weight of deionized water (third solvent) was added and stirred at 25° C. for 30 minutes. Thereafter, 20 parts by weight of deionized water (fourth solvent) was added and stirred at 25° C. and then 16.7 parts by weight of deionized water (fifth solvent) was added and stirred at 25° C. to manufacture a silicone emulsion. At this time, the stirring rate was kept constant at 500 rpm.

Examples 2 to 13 and Comparative Examples 1 to 4. Manufacture of Silicone Emulsions

[0122] The silicone emulsions were manufactured in the same manner as in Example 1, except for using components in compositions as described in Tables 1 to 3 and adjusting a temperature and a cooling time when preparing an amino silicone polymer.

TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple (Parts by weight) 1 2 3 4 5 6 Amino Hydroxyl- 30.46 30.46 30.46 30.46 30.46 30.46 silicone terminated polymer polysiloxane Cyclosiloxane — — — — — — First amino 0.96 0.96 0.96 2 2 0.96 silane Methyltriethoxy 0.1 0.1 0.1 0.1 0.2 0.1 silane Catalyst 0.32 0.32 0.32 0.32 0.32 0.32 Neutralizing 0.16 0.16 0.16 0.22 0.22 0.16 agent Deionized water 63.2 63.2 63.2 62.1 62.0 57.5 Non-ionic emulsifier 2.5 2.5 2.5 2.5 2.5 4 Cationic emulsifier 2 2 2 2 2 6 Neutralizing agent 0.3 0.3 0.3 0.3 0.3 0.5 Total 100 100 100 100 100 100 Viscosity (cP) 25,000 10,000 80,000 40,000 80,000 25,000 at 25° C. of amino silicone polymer Temperature (° C.) when 95 95 95 95 95 95 preparing amino silicone polymer Cooling time (hr) when 5 3 9 3 5 5 preparing amino silicone polymer

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example (Parts by weight) 7 8 9 10 11 12 13 Amino Hydroxyl- 30.46 30.46 30.46 30.46 30.46 30.46 30.46 silicone terminated polymer polysiloxane First amino 0.96 0.96 0.96 0.96 0.96 0.28 3.09 silane Methyltriethoxy 0.2 0.1 — 0.02 0.35 0.1 0.1 silane Dimethyldiethoxy — — 0.1 — — — — silane Catalyst 0.32 0.32 0.32 0.32 0.32 0.32 0.32 Neutralizing 0.16 0.16 0.16 0.16 0.16 0.16 0.16 agent Deionized water 57.4 55 63.2 63.2 63.2 63.2 61.2 Non-ionic emulsifier 4 2.7 2.5 2.5 2.25 2.28 2.37 Cationic emulsifier 6 10 2 2.08 2 2 2 Neutralizing agent 0.5 0.3 0.3 0.3 0.3 1.2 0.3 Total 100 100 100 100 100 100 100 Viscosity (cP) at 25° C. 35,000 15,000 10,000 5,000 150,000 7,000 120,000 of amino silicone polymer Temperature (° C.) when 95 90 95 95 95 95 95 preparing amino silicone polymer Cooling time (hr) when 5 5 5 5 5 5 5 preparing amino silicone polymer

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative (Parts by weight) Example 1 Example 2 Example 3 Example 4 Amino Hydroxyl-terminated — — — 30.46 silicone polysiloxane polymer Cyclosiloxane 35 32 32 — First amino silane — — — 0.96 Second amino silane 2 1 0.92 — Trimethylethoxy — — — 0.1 silane Catalyst 0.4 0.5 0.1 0.32 Neutralizing agent — — — 0.16 Deionized water 54.67 60 52.83 63.2 Non-ionic emulsifier 2.8 3 2.76 2.5 Cationic emulsifier 1.83 2.5 10.39 2 Neutralizing agent 3.3 1 1 0.3 Total 100 100 100 100 Viscosity (cP) at 25° C. of amino 5,000 5,000 5,000 4,000 silicone polymer Temperature (° C.) when preparing 95 95 90 95 amino silicone polymer Cooling time (hr) when preparing 4 5 9 5 amino silicone polymer

[0123] The manufacturers and product names of respective components used in Comparative Examples and Examples were shown in Table 4.

TABLE-US-00004 TABLE 4 Manufacturer and Component Product name Note Hydroxyl- Manufacturer: Viscosity at 25° C.: 60 cP, terminated KCC, Product Polymerization degree: 25, Mw: polysiloxane name: HEO-60 2,000 g/mol, OH content: 1.8 to 2 wt % Cyclosiloxane Manufacturer: Mw: 296 g/mol KCC, Product name: Octamethyl cyclotetrasiloxane First amino Manufacturer: Aminopropylmethyldiethoxy silane SHINETSU, Product silane name: KBE-903 Second amino Manufacturer: Aminoethylaminopro- silane SHINETSU, Product pyltrimethoxy name: KBM-603 silane Non-ionic Manufacturer: Tridecyl polyoxyethylene ether emulsifier HANNONG (HLB value: 14, CHEMICALS, Mw: 720 g/mol, Product name: Viscosity at TDE12 25° C.: 200 cP) Cationic Manufacturer: Cetrimonium chloride (Amine emulsifier Miwon Chemicals, content: 0.2 wt %, Solid Product name: content: 29 wt %, Mw: CTAC29 320 g/mol) Cationic Manufacturer: — surfactant Akzonobel, Product name: ARQUAD16-29 Non-ionic Manufacturer: — surfactant Croda, Product name: RENEX 30

Test Examples: Characteristic Evaluation of Silicone Emulsion

[0124] The physical properties of the silicone emulsions of Examples 1 to 13 and Comparative Examples 1 to 4 were measured by the following methods and the results were shown in Tables 5 and 6.

[0125] (1) Average Particle Size of Dispersed Particles

[0126] The average particle size (nm) of dispersed particles in the silicone emulsion was measured using Master Size 3000 of Marvern Co., Ltd.

[0127] (2) Viscosity

[0128] The viscosity at 25° C. was measured by using a Brookfiled viscometer and helipath stand #93 while stirring the silicone emulsion at 2.5 rpm.

[0129] (3) Storage Stability (Room Temperature)

[0130] While the silicone emulsion was left for 7 days in a 25° C. oven, the appearance of the silicone emulsion was observed to determine whether a water layer and an oil layer were separated and the high-temperature stability was evaluated. At this time, when the layer separation of the water layer and the oil layer did not occur, the room temperature stability was evaluated as good, and when the layer separation occurred within 7 days, the elapsed date when the layer separation of the water layer and the oil layer occurred was recorded.

[0131] (4) Storage Stability (High Temperature)

[0132] While the silicone emulsion was left for 7 days in a 50° C. oven, the appearance of the silicone emulsion was observed to determine whether a water layer and an oil layer were separated and the high-temperature stability was evaluated. At this time, when the layer separation of the water layer and the oil layer did not occur, the high-temperature stability was evaluated as good, and when the layer separation occurred within 7 days, the elapsed date when the layer separation of the water layer and the oil layer occurred was recorded.

[0133] (5) Contents of D4, D5 and Methanol

[0134] The contents of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and methanol in the silicone emulsion were measured using a gas chromatograph/mass spectrometer (GC/MS). At this time, when the content of the compound was less than a threshold of the meter, the content was represented as N.D.

[0135] (6) Feeling of Use

[0136] The silicone emulsion was diluted in water so as to be a concentration of 2.0 wt % to manufacture a sample. Thereafter, after the sample was used for 10 testers, the feeling of use was evaluated based on adhesion and a coating property and evaluated based on a five-point scale.

[0137] (7) Persistency

[0138] After the same sample as item (6) was used for the same testers, the persistency was evaluated and evaluated based on a five-point scale.

TABLE-US-00005 TABLE 5 Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 Viscosity 20 16 25 20 20 21 19 18 17 (cP) Particle 210 200 250 210 185 183 180 175 200 size (nm) Storage Good Good Good Good Good Good Good Good Good stability (room temperature) Storage Good Good Good Good Good Good Good Good Good stability (high temperature) D4 content 471 242 430 400 420 425 471 480 450 (ppm) D5 content 580 40 600 550 560 570 580 590 580 (ppm) Methanol N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. content (ppm) Feeling of 4 3.8 4.3 4.5 4.7 4.1 4 4.2 4.1 use Persistency 4 3.7 4.7 4.5 4.7 4.2 4 4.5 4

TABLE-US-00006 TABLE 6 Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example Example 10 11 12 13 1 2 3 4 Viscosity (cP) 20 35 25 30 17 16 16 19 Particle size 190 250 200 300 200 160 180 180 (nm) Storage Good Good Good Good Good Good Good Good stability (room temperature) Storage Good 7 Good 7 5 5 6 Good stability (high days days days days days temperature) D4 content 400 460 380 420 8,565 8,565 7,929 450 (ppm) D5 content 550 590 530 500 949 949 957 520 (ppm) Methanol N.D. N.D. N.D. N.D. 1,243 1,243 1,096 N.D. content (ppm) Feeling of use 3.6 3.7 3.6 3.9 3.5 3.4 3.4 3.0 Persistency 3.7 3.8 3.8 3.8 3.7 3.4 3.2 3.1

[0139] As shown in Tables 5 and 6, in the silicone emulsions of Examples 1 to 13, the storage stability at room temperature and high temperature was excellent, a small amount of D4 and D5 was contained and methanol was not contained to have environment-friendliness and low irritation in human body, and the feeling of use and persistency were excellent.

[0140] On the other hand, in the silicone emulsions of Comparative Examples 1 to 3, a large amount of D4 and D5 was contained and methanol was contained to have low environment-friendliness and high irritation in human body, and the storage stability at room temperature and high temperature was low. In addition, in the silicone emulsion of Comparative Example 4 comprising trimethylethoxy silane, the feeling of use and persistency were lack.