Modified amino silicone oil emulsion as well as preparation method and application thereof

Abstract

The invention provides a modified amino silicon oil emulsion which comprises the following components in parts by weight: 10-40 parts of modified amino silicon oil, 5-15 parts of an emulsifier, 0.1-0.8 part of a pH regulator and water, the modified amino silicon oil comprises a reaction product of amino silicon oil and carboxyl silicon oil, and the molar ratio of carboxyl in the carboxyl silicon oil to amino groups in the amino silicon oil is 1: 2-3: 1. The modified amino silicon oil emulsion has improved hand feeling, alkali resistance and yellowing resistance, and the amino silicon oil is easy to package and emulsify.

Description

Technical Field

[0001] The invention belongs to the technical field of amino silicone oil emulsions, and particularly relates to modified amino silicone oil emulsions, a preparation method and applications thereof. Background Art

[0002] Amino silicone oil (amino-modified polysiloxane) emulsion has a large adsorption capacity on fibers and strong permeability, which can improve the effect of amino silicone oil. It is widely used in textile, leather and other fields, especially as a softener in the finishing process of textiles, thereby improving the feel of textiles.

[0003] However, amino silicone oil-treated textiles have a good feel, but amino silicone oil is prone to yellowing and difficult to emulsify. If you want to achieve an ultra-smooth and elastic feel, you usually need silicone oil with a large molecular weight, but a large molecular weight will bring problems such as packaging and difficulty in emulsification.

[0004] Chinese patent application CN110615898A discloses a method for preparing a high-temperature alkali-resistant aminosilicone oil emulsion. The raw materials are aminosilicone oil, a specific emulsifier, a glycerol additive, trifluoromethyl maleic anhydride and water, and the emulsifier is composed of ethylene vinyl acetate copolymer, ethylene glycol ether, sodium disodium hexadecyl diphenyl ether disulfonate, calcium carbonate, carbon nanotubes and water. The synergistic effect between the ethylene vinyl acetate copolymer, ethylene glycol ether and carbon nanotubes enhances the stability of the emulsion, and the trifluoromethyl maleic anhydride can undergo amidation with the aminosilicone oil, reducing the active hydrogen of the amino group and increasing the carboxyl group in the aminosilicone oil structure, thereby reducing the yellowing of the emulsion and increasing the high-temperature resistance and alkali resistance of the aminosilicone oil emulsion, but at the same time increasing the viscosity of the aminosilicone oil.

[0005] Chinese patent application CN108752935A discloses an aminosilicone oil emulsion and its preparation method. The aminosilicone oil emulsion is prepared using glass beads, has an internal oil viscosity of 2,000-15,000, and is dispersed using a dual-center mixing disperser. Chinese patent application CN108752935A suggests that high-viscosity aminosilicone oils are difficult to emulsify. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to address the technical problems existing in the prior art and provide a modified aminosilicone oil emulsion, a preparation method and an application thereof. The modified aminosilicone oil emulsion of the present invention has improved fabric feel and yellowing resistance. In addition, the modified aminosilicone oil emulsion of the present invention utilizes two low-viscosity silicone oils to react to generate a high-viscosity (high molecular weight) modified aminosilicone oil, effectively solving the problems of difficult packaging and high loss of high-viscosity silicone oil.

[0007] The objectives of the present invention are achieved through the following technical solutions.

[0008] In a first aspect, the present invention provides a modified aminosilicone oil emulsion, wherein the modified aminosilicone oil emulsion comprises: 10-40 parts by weight of modified aminosilicone oil, 5-15 parts by weight of emulsifier, 0.1-0.8 parts by weight of pH adjuster and water; the modified aminosilicone oil comprises the reaction product of aminosilicone oil and carboxyl silicone oil, wherein the molar ratio of the carboxyl group in the carboxyl silicone oil to the amino group in the aminosilicone oil is 1:2-3:1.

[0009] The inventors of this application have discovered that by mixing and reacting aminosilicone oil with carboxyl silicone oil in a specific ratio, a high-viscosity modified aminosilicone oil can be obtained. This improves the feel of the aminosilicone oil, stabilizes the aminosilicone oil during processing, prevents oil spots, and avoids the packaging difficulties and high waste associated with directly using high-viscosity aminosilicone oil. Furthermore, emulsions formulated with this modified aminosilicone oil exhibit improved alkali resistance and yellowing resistance (whiteness) of fabrics.

[0010] According to the modified amino silicone oil emulsion provided by the present invention, the amino silicone oil has an ammonia value of 0.1-0.8, for example, 0.1, 0.12, 0.15, 0.18, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8 or a range consisting of these, preferably 0.15-0.8, more preferably 0.4-0.8.

[0011] In the present invention, the term "ammonia value" refers to the mass (g) of nitrogen in 100g of silicone oil.

[0012] According to the modified amino silicone oil emulsion provided by the present invention, the viscosity of the amino silicone oil may be 300-150000 mPa·s, for example, 300 mPa·s, 800 mPa·s, 1000 mPa·s, 1500 mPa·s, 2000 mPa·s, 3000 mPa·s, 4000 mPa·s, 4500 mPa·s, 4800 mPa·s, 5000 mPa·s, 10000 mPa·s, 20000 mPa·s, 30000 mPa·s, 50000 mPa·s, 80000 mPa·s, 100000 mPa·s, 150000 mPa·s or a range consisting of these, preferably 300-5000 mPa·s.

[0013] Examples of amino silicone oils suitable for use in the present invention include, but are not limited to, COMFORTSIL FLD C803, COMFORTSIL FLD C845, COMFORTSIL FLD C910, and COMFORTSIL FLDL15W15P available from Elkem Silicones.

[0014] According to the modified amino silicone oil emulsion provided by the present invention, the acid value of the carboxyl silicone oil is 1-50, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, 9, 10, 12, 15, 18, 20, 25, 30, 35, 40, 45, 50 or a range consisting of these, preferably 2-10, more preferably 2-5.

[0015] In the present invention, the term "acid value" is the mass (g) of -COOH in 100 g of silicone oil.

[0016] According to the modified amino silicone oil emulsion provided by the present invention, the viscosity of the carboxyl silicone oil can be 50-5000mPa·s, for example, 50mPa·s, 60mPa·s, 80mPa·s, 100mPa·s, 120mPa·s, 150mPa·s, 180mPa·s, 200mPa·s, 250mPa·s, 300mPa·s, 350mPa·s, 400mPa·s , 450mPa·s, 500mPa·s, 800mPa·s, 1000mPa·s, 1200mPa·s, 1500mPa·s, 2000mPa·s, 2500mPa·s, 3000mPa·s, 3500mPa·s, 4000mPa·s, 4500mPa·s, 5000mPa·s or a range consisting of 250-500mPa·s, preferably 250-500mPa·s.

[0017] According to the modified amino silicone oil emulsion of the present invention, the carboxyl silicone oil is a carboxyl-terminated silicone oil.

[0018] Examples of carboxylic silicone oils suitable for use in the present invention include, but are not limited to, BLUESIL FLD 1669 available from Elkem Silicones.

[0019] According to the modified amino silicone oil emulsion provided by the present invention, the molar ratio of the carboxyl groups in the carboxyl silicone oil to the amino groups in the amino silicone oil is 1:2-3:1. Within this range, the viscosity of the modified amino silicone oil can be increased by 1-120 times, particularly 3-115 times, based on the viscosity of the amino silicone oil.

[0020] The molar ratio of the carboxyl groups in the carboxyl silicone oil to the amino groups in the amino silicone oil may be 1:2, 1:1.5, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or a range consisting of these.

[0021] The inventors of the present application have found that the molar ratio of the carboxyl groups in the carboxyl silicone oil to the amino groups in the amino silicone oil is 1:1-3:1, particularly 1:2, and the modified amino silicone oil has a relatively high viscosity growth multiple.

[0022] In some embodiments, the molar ratio of the carboxyl groups in the carboxyl silicone oil to the amino groups in the amino silicone oil is 1:1-3:1, preferably 1.5:1-2.5:1.

[0023] According to the modified amino silicone oil emulsion provided by the present invention, the modified amino silicone oil is prepared by a method comprising the following steps: mixing amino silicone oil and carboxyl silicone oil, and stirring to react.

[0024] The reaction process of amino silicone oil and carboxyl silicone oil is exothermic, and usually such a reaction can be carried out at room temperature.

[0025] In some embodiments, the stirring reaction conditions include: a temperature of 15-30° C.; and / or a stirring speed of 100-500 rpm, preferably 200-400 rpm.

[0026] The present invention has no special requirements for the stirring reaction time. Generally, the stirring reaction is carried out until the viscosity stabilizes.

[0027] According to the modified amino silicone oil emulsion provided by the present invention, the content of the modified amino silicone oil in the modified amino silicone oil emulsion can be 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or a range thereof, preferably 15-25 parts by weight.

[0028] According to the modified amino silicone oil emulsion provided by the present invention, the emulsifier may be isomeric tridecanol polyoxyethylene ether.

[0029] The present invention has no special restrictions on isomeric tridecanol polyoxyethylene ethers, and the isomeric tridecanol polyoxyethylene ethers known in the art can be used, preferably the isomeric tridecanol polyoxyethylene ethers having 4-20 repeating units, especially the isomeric tridecanol polyoxyethylene ethers having 4-8 repeating units, such as emulsifier 1360 purchased from Sasol Chemical Company.

[0030] According to the modified amino silicone oil emulsion provided by the present invention, the amount of the emulsifier can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, or a range consisting thereof. In some embodiments, the amount of the emulsifier is 8-12 parts by weight.

[0031] According to the modified amino silicone oil emulsion provided by the present invention, the pH regulator is acetic acid.

[0032] According to the modified amino silicone oil emulsion provided by the present invention, the amount of the pH regulator can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight or a range thereof. In some embodiments, the amount of the pH regulator is 0.3-0.5 parts by weight.

[0033] According to the modified amino silicone oil emulsion provided by the present invention, wherein, the present invention has no special requirements for the amount of water used, as long as an emulsion can be formed. For example, the amount of water used can be 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 82 parts by weight, 85 parts by weight or a range thereof. In some specific embodiments, the amount of water is 60-85 parts by weight.

[0034] In a second aspect, the present invention provides a method for preparing a modified amino silicone oil emulsion, wherein the preparation method comprises the following steps:

[0035] (1) adding an emulsifier and a pH adjuster to the modified amino silicone oil and stirring;

[0036] (2) Add water and stir to obtain modified amino silicone oil emulsion.

[0037] According to the preparation method provided by the present invention, there is no special requirement for the stirring in steps (1) and (2), and any stirring method known in the art for emulsification of amino silicone oil can be adopted.

[0038] According to the preparation method provided by the present invention, there is no special requirement for the water addition operation in step (2), and any method known in the art can be used. For example, water can be added slowly until completion, thereby effectively performing emulsification.

[0039] In a third aspect, the present invention provides the use of modified amino silicone oil emulsion in fabric finishing.

[0040] According to the application provided by the present invention, the modified amino silicone oil emulsion is prepared into a working solution with a modified amino silicone oil concentration of 5-40 g / L.

[0041] The present invention has the following advantages: the modified aminosilicone oil emulsion of the present invention can improve the feel and yellowing resistance of fabrics, and can also improve the stability of aminosilicone oil during processing, avoiding the occurrence of oil spots in aminosilicone oil. In addition, the aminosilicone oil emulsion utilizes two low-viscosity oils to generate a high-viscosity modified aminosilicone oil in an emulsification kettle, thereby solving the problems of difficult packaging and large loss of high-viscosity silicone oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1is a photograph of the modified amino silicone oil emulsion prepared in Example 2 of the present invention, wherein from left to right are samples EF1, EF2, EF3, and EF4;

[0043] Figure 2 are photographs of the working solutions prepared in Example 2 of the present invention, wherein a is prepared from Formulation EF1, b is prepared from Formulation EF2, c is prepared from Formulation EF3, and d is prepared from Formulation EF4;

[0044] Figure 3 These are photos of the alkali resistance test of the working solution prepared in Example 2 of the present invention, wherein a and e are formula EF1, b and f are formula EF2, c and g are formula EF3, and d and h are formula EF4;

[0045] Figure 4 These are pictures of the working solution (DS2) prepared using Comfortsil FLD C845 in Example 2 of the present invention and photos of the alkali resistance test, where a is the appearance picture, b is the appearance picture when heated to 60°C, and c is the appearance picture when heated to 80°C. DETAILED DESCRIPTION

[0046] The present invention will be further described below with reference to specific examples, but they do not constitute any limitation to the present invention.

[0047] In the examples and comparative examples, the raw materials and reagents used are as follows:

[0048] COMFORTSIL FLD C803, amino silicone oil, ammonia value 0.42, viscosity 300 mPa·s, Elkem Silicones;

[0049] COMFORTSIL FLD C845, amino silicone oil, ammonia value 0.4, viscosity 4500 mPa·s, Elkem Silicones;

[0050] COMFORTSIL FLD C910, amino silicone oil, ammonia value 0.8, viscosity 1500 mPa·s, Elkem Silicones;

[0051] COMFORTSIL FLD L15W15P, low-yellowing amino silicone oil, ammonia value 0.15, viscosity 150,000 mPa·s, Elkem Silicones;

[0052] Emulsifier 1360, isomeric tridecanol polyoxyethylene ether (6), HLB value is 11.4, cloud point is 69-71 (10%, in 25% BDG solution), Sasol Chemical Company.

[0053] Unless otherwise specified, the remaining raw materials used in the present invention can be made in-house or commercially available, and the present invention is not particularly limited thereto. For example, acetic acid, sodium hydroxide, and sodium acetate trihydrate are all commercially available.

[0054] The experimental equipment used in the examples and comparative examples include: an IKA stirrer, an IKA magnetic stirrer, a RUBI padder, a RUBI setting machine, a washing machine, and an X-Rite CI7500.

[0055] Example 1

[0056] This example is used to illustrate the improved amino silicone oil and its preparation method.

[0057] According to the ratio listed in Table 1, amino silicone oil and carboxyl silicone oil were added to a reactor equipped with an IKA stirrer, and the mixture was stirred at 25°C and 300 rpm for reaction until the viscosity stabilized to obtain modified amino silicone oil. The results are shown in Table 1.

[0058] At the same time, the viscosity of amino silicone oil and carboxyl silicone oil before reaction was measured as a control.

[0059] Table 1 Preparation formula and viscosity of modified amino silicone oil in Example 1

[0060]

[0061] As can be seen from Table 1, the mixed reaction of amino silicone oil and carboxyl silicone oil can significantly increase the viscosity of the modified amino silicone oil. When the reactive group molar ratio (carboxyl / amino group) is 1:1-3:1, the viscosity increase is greater, and the highest is 43.78 times when the reactive group molar ratio (carboxyl / amino group) is 2:1. Without wishing to be limited by theory, it is believed that the compounding reaction of carboxyl silicone oil and amino silicone oil can increase the viscosity of the system. The greater the viscosity, the greater the molecular weight, and the better the feel.

[0062] Example 2

[0063] This example is used to illustrate a modified amino silicone oil emulsion and a preparation method thereof.

[0064] 1. Preparation of modified amino silicone oil emulsion

[0065] (1) According to the formula shown in Table 2, 10 parts by weight of emulsifier 1360 and 0.4 parts by weight of acetic acid were added to a reaction kettle equipped with an IKA stirrer and filled with 20 parts by weight of the modified amino silicone oil prepared in Example 1. The mixture was stirred at 300 rpm at 25°C for 30 minutes.

[0066] (2) Add 69.6 parts by weight of deionized water and continue stirring for 60 minutes to obtain a modified amino silicone oil emulsion. Figure 1 .

[0067] Table 2 Example 2 modified amino silicone oil emulsion formula

[0068]

[0069] 2. Add deionized water to the modified amino silicone oil emulsion and dilute it to a working solution with a modified amino silicone oil content of 10g / L. Figure 2 .

[0070] 3. Under stirring conditions, add NaOH aqueous solution (10%) to the working solution, adjust the pH value to 12, and heat to boiling. Figure 3 .

[0071] According to the above steps 1 and 2, use COMFORTSIL FLD C845 to replace the modified amino silicone oil to prepare the working fluid. Its appearance is shown in Figure 4 a. Add NaOH aqueous solution (10%) to the working solution and adjust the pH value to 12. When heated to 60℃, the appearance of the solution will be Figure 4 b. When heated to 80℃, its appearance is Figure 4 c.

[0072] from Figure 4 It can be seen that the unmodified amino silicone oil working fluid becomes turbid when heated to 60℃ and becomes oily when heated to 80℃. Figure 1-3 It can be seen that the modified amino silicone oil emulsion of the present invention has improved alkali resistance stability.

[0073] Example 3

[0074] This example is used to illustrate the performance of modified amino silicone oil emulsion.

[0075] The modified amino silicone oil emulsion prepared in Example 2 was formulated into a working solution with a concentration of 10 g / L, and nylon white knitted fabric and polyester-viscose nylon (80 / 17 / 3) were padded at room temperature using a Rubi padder, and then dried at 130°C*2min using a Rubi setting machine and set at 180°C*1min to obtain a finished fabric sample.

[0076] The fabric was folded into four layers using an X-Rite tester, and the average value of the four test points was taken. The results are shown in Table 3.

[0077] Five hand feel evaluation professionals comprehensively evaluated the finished fabric samples based on softness and smoothness. The original fabric hand feel was rated as 1 point, and the best hand feel evaluation was 5 points. The results are shown in Table 3.

[0078] Table 3 Whiteness and hand feel properties

[0079]

[0080] As can be seen from Table 3, the modified aminosilicone oil of the present invention has good whiteness, yellowing resistance, and hand feel. It is believed that in the modified aminosilicone oil prepared by the reaction of carboxyl silicone oil and amino silicone oil, the carboxyl group reacts with the active hydrogen on the amino group, improving the problem of oxidative yellowing of the aminosilicone oil. At the same time, the high molecular weight modified aminosilicone oil generated by the reaction of carboxyl silicone oil and amino silicone oil gives the fabric an ultra-slippery and elastic hand feel.

[0081] In addition, modified amino silicone oil emulsion was used for finishing, and no oil spots appeared on the finished fabric samples.

[0082] Example 4

[0083] COMFORTSIL FLD C803 was used instead of COMFORTSIL FLD C845 in Example 1 to prepare modified amino silicone oil to obtain modified amino silicone oil. The results are shown in Table 4.

[0084] Table 4 Preparation formula and properties of modified amino silicone oil in Example 4

[0085]

[0086] The modified amino silicone oil prepared in Example 4 was used to prepare a modified amino silicone oil emulsion according to the method disclosed in Example 2, and a working fluid was prepared. The alkali resistance stability was tested. When heated to boiling, if there was no phase separation phenomenon such as confusion and oil floating, the alkali resistance was qualified and recorded as "OK"; otherwise, it was unqualified and recorded as "X". The results are shown in Table 4.

[0087] Example 5

[0088] COMFORTSIL FLD C910 was used instead of COMFORTSIL FLD C845 in Example 1 to prepare modified amino silicone oil. The results are shown in Table 5.

[0089] Table 5 Preparation formula and properties of modified amino silicone oil in Example 5

[0090]

[0091] The modified amino silicone oil prepared in Example 5 was used to prepare a modified amino silicone oil emulsion and a working fluid according to the method listed in Example 2. The alkali resistance stability was tested. When heated to boiling, if there was no phase separation phenomenon such as confusion and oil floating, the alkali resistance was qualified and recorded as "OK"; otherwise, it was unqualified and recorded as "X". The results are shown in Table 5.

[0092] Example 6

[0093] COMFORTSIL FLD L15W15P was used instead of COMFORTSIL FLD C845 in Example 1 to prepare modified amino silicone oil. The results are shown in Table 6.

[0094] Table 6 Preparation formula and properties of modified amino silicone oil in Example 6

[0095]

[0096] The modified amino silicone oil prepared in Example 6 was used to prepare a modified amino silicone oil emulsion according to the method listed in Example 2, and a working fluid was prepared. The alkali resistance stability was tested. When heated to boiling, if there was no phase separation phenomenon such as confusion and floating oil, the alkali resistance was qualified and recorded as "OK"; otherwise, it was unqualified and recorded as "X". The results are shown in Table 6.

[0097] In summary, the modified aminosilicone oil emulsion of the present invention improves the feel and yellowing resistance of fabrics, while also improving the stability of aminosilicone oil during processing and avoiding the occurrence of oil spots on aminosilicone oil. In addition, the aminosilicone oil emulsion utilizes two low-viscosity silicone oils to react to generate a high-viscosity modified aminosilicone oil, effectively solving the problems of difficult packaging and high loss of high-viscosity silicone oil.

Claims

1. Modified amino silicone oil emulsion, wherein: The modified amino silicone oil emulsion comprises: 10-40 parts by weight of modified amino silicone oil, 5-15 parts by weight of emulsifier, 0.1-0.8 parts by weight of pH regulator and water; the modified amino silicone oil comprises the reaction product of amino silicone oil and carboxyl silicone oil, wherein the molar ratio of the carboxyl group in the carboxyl silicone oil to the amino group in the amino silicone oil is 1:2-3:

1.

2. The modified amino silicone oil emulsion according to claim 1, wherein The amino value of the amino silicone oil is 0.1-0.8, preferably 0.4-0.8; And / or, the viscosity of the amino silicone oil is 300-150000 mPa·s, preferably 300-5000 mPa·s.

3. The modified amino silicone oil emulsion according to claim 1 or 2, wherein The acid value of the carboxyl silicone oil is 1-50, preferably 2-10, more preferably 2-5; And / or, the viscosity of the carboxyl silicone oil is 50-5000 mPa·s, preferably 250-500 mPa·s.

4. The modified amino silicone oil emulsion according to any one of claims 1 to 3, wherein The molar ratio of the carboxyl groups in the carboxyl silicone oil to the amino groups in the amino silicone oil is 1:1-3:1, preferably 1.5:1-2.5:

1.

5. The modified amino silicone oil emulsion according to any one of claims 1 to 4, wherein The modified amino silicone oil is prepared by a method comprising the following steps: mixing amino silicone oil and carboxyl silicone oil, and stirring to react; Preferably, the stirring reaction conditions include: a temperature of 15-30° C.; and / or a stirring speed of 100-500 rpm, preferably 200-400 rpm.

6. The modified amino silicone oil emulsion according to any one of claims 1 to 5, wherein The content of the modified amino silicone oil in the modified amino silicone oil emulsion is 15-25 parts by weight.

7. The modified amino silicone oil emulsion according to any one of claims 1 to 6, wherein The emulsifier is isomeric tridecanol polyoxyethylene ether; And / or, the amount of the emulsifier is 8-12 parts by weight.

8. The modified amino silicone oil emulsion according to any one of claims 1 to 7, wherein The pH regulator is acetic acid; and / or, the amount of the pH adjuster is 0.3-0.5 parts by weight; And / or, the amount of water is 60-85 parts by weight.

9. The method for preparing the modified amino silicone oil emulsion according to any one of claims 1 to 8, wherein: The preparation method comprises the following steps: (1) adding an emulsifier and a pH adjuster to the modified amino silicone oil and stirring; (2) Add water and stir to obtain modified amino silicone oil emulsion.

10. Use of the modified amino silicone oil emulsion according to any one of claims 1 to 8 in fabric finishing.

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