Fabric low-color-change softening agent and preparation method thereof

Abstract

The invention relates to a fabric low-color-change softening agent and a preparation method thereof. The low-color-change fabric softening agent is prepared by the following steps: preparing an emulsion polymer from 5-15% by mass of divinyl-terminated polydimethylsiloxane, 5-15% by mass of double-bond single-terminated polyurethane, 3-15% by mass of poly (ethylene glycol) (methyl) acrylate and 2-10% by mass of allyl polyoxyethylene ether in the presence of an emulsifier, and then adding 0.05-0.5% by mass of an additive. Compared with conventional softeners, the fabric low-color-change softener prepared by the invention has small influence on colored light of dyed fabrics, especially sensitive yarn-dyed fabrics, small yellowing on white fabrics, excellent hand feeling and good hydrophilicity.

Description

Technical Field

[0001] This invention relates to a functional finishing agent and its preparation method, particularly a fabric low-color-change softener and its preparation method. Background Technology

[0002] Among the dyeing and printing auxiliaries, there are many varieties of silicone softeners with complete functions, which can meet the finishing requirements of different fabrics with different hand feel styles.

[0003] Amino silicone oil is a common type of organosilicon finishing agent. Its molecular structure contains amino active groups, which allows silicone oil molecules to quickly and firmly distribute on the fiber surface to form a smooth film, reducing the friction between fibers and improving the hand feel. However, fabrics treated with amino silicone oil are prone to yellowing, and the degree of yellowing increases with the increase of ammonia value. In addition, its hydrophilicity is poor, and its emulsion stability and shear resistance are poor, which can easily lead to oil floating and demulsification, causing problems such as sticking to rollers and oil spots during processing.

[0004] Currently, most softeners on the market and in research are linear block silicone oils. These are formed by block copolymerization of amino groups, polyethers and polysiloxanes to create ternary linear macromolecules, which improves the problems of amino silicone oils such as easy yellowing, poor hydrophilicity and poor emulsion stability. For example, the journal article "Preparation and Properties of Linear Polyether Block Amino Silicone Oil" by Xu Chengshu et al. used bi-terminated amino polyether and bi-terminated epoxy polyether silicone oil as reactants, and isopropanol as solvent, to prepare linear block polyether amino silicone oil through a one-step ring-opening polymerization reaction. This linear block polyether amino silicone oil was then used for softening cashmere fabrics. The results showed that its emulsion had excellent stability, good hand feel and hydrophilicity, and minimal yellowing. Another example is the journal article "Synthesis Study of Hydrophilic Block Silicone Oil Finishing Agent" by Tang Jinwei et al., which used terminal epoxy silicone oil and terminal amino polyether as raw materials to synthesize a ternary copolymer block silicone oil in isopropanol. Further cationic modification with a quaternizing agent further improved its hydrophilicity. The results showed that the prepared hydrophilic block silicone oil had good hand feel and hydrophilicity, good stability, and also improved yellowing and color change of fabrics to some extent. All of the above studies used traditional difunctional terminal amino polyethers, which showed some improvement in yellowing compared to amino silicone oils, but the impact on color change of some sensitive colored fabrics was still relatively large.

[0005] In summary, there is considerable research on low-yellowing softeners, and corresponding solutions exist. However, research on low-color-change softeners, especially low-color-change silicone oils for sensitive colors, is relatively limited. The low-color-change softener for fabrics of this invention is primarily used for softening and finishing sensitive-colored fabrics, particularly catering to the high-end needs of branded apparel. After softening, it has minimal impact on the fabric's color and requires no further color correction, thus possessing promising market prospects. Summary of the Invention

[0006] One aspect of the present invention is to provide a fabric low-color-change softener, which is prepared from the following raw materials in weight percentage:

[0007] Divinyl-terminated polydimethylsiloxane 5-15%

[0008] Polyurethane with single-ended double bonds: 5-15%

[0009] Poly(ethylene glycol) (meth)acrylate 3-15%

[0010] Allyl polyoxyethylene ether 2-10%

[0011] Emulsifier 5-20%

[0012] Additives 0.05-0.5%

[0013] Water balance

[0014] The total mass of the above raw materials is taken as 100% by mass.

[0015] Another aspect of the present invention is to provide a method for preparing a fabric low-color-change softener, the method comprising the following steps:

[0016] a) Prepare an aqueous emulsion of divinyl-terminated polydimethylsiloxane, single-terminated polyurethane, poly(ethylene glycol)(meth)acrylate and allyl polyoxyethylene ether at 40-60°C in the presence of an emulsifier.

[0017] b) Add a free radical initiator at 60-80℃ to initiate the polymerization reaction;

[0018] c) Raise the temperature to 75-95℃ and keep it warm for 1-5 hours;

[0019] d) Cool to 30-50℃, add additives, stir for 1-2 hours to obtain a fabric low-color-change softener.

[0020] The fabric low-color-change softener of the present invention has little impact on the color of dyed fabrics, especially sensitive color fabrics, with minimal yellowing, excellent hand feel, and good hydrophilicity. Detailed Implementation

[0021] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0022] In this invention, "(meth)acrylic acid" refers to at least one of "acrylic acid" and "methacrylic acid". "(meth)acrylate" has the same meaning.

[0023] In this invention, "EO" represents the oxyethylene structural unit.

[0024] In a preferred embodiment, the fabric low-color-change softener of the present invention is prepared from the following raw materials by weight percentage:

[0025] Divinyl-terminated polydimethylsiloxane 8-13%

[0026] Polyurethane with single-ended double bonds: 6-12%

[0027] Poly(ethylene glycol) (meth)acrylate 4-10%

[0028] Allyl polyoxyethylene ether 3-8%

[0029] Emulsifier 6-15%

[0030] Additives 0.1-0.4%

[0031] Water balance

[0032] The total mass of the above raw materials is taken as 100% by mass.

[0033] In a preferred embodiment, the divinyl-terminated polydimethylsiloxane has a viscosity of 80-500 mPa·s and a vinyl content of 0.15-0.4 mmol / g.

[0034] In a preferred embodiment, the structure of the single-ended polyurethane with double bonds is represented by Formula I:

[0035] Formula I

[0036] In Formula I:

[0037] R1 is H or CH3;

[0038] n is 2 or 3;

[0039] k is an integer between 0 and 7;

[0040] PU is a residue of waterborne polyurethane prepolymer.

[0041] In a preferred embodiment, the structure of the poly(ethylene glycol)(meth)acrylate is represented by Formula II:

[0042] Formula II

[0043] In Formula II:

[0044] R2 is H or CH3;

[0045] p is an integer from 5 to 30.

[0046] In a preferred embodiment, the structure of the allyl polyoxyethylene ether is represented by Formula III:

[0047] CH2=CHCH2O(CH2CH2O) m H type III

[0048] In Formula III:

[0049] m is an integer from 1 to 100.

[0050] In a preferred embodiment, the emulsifier is a mixture of hyperbranched Gemini quaternary ammonium cationic surfactant and isomeric alcohol polyoxyethylene ether, and the mass ratio of the hyperbranched Gemini quaternary ammonium cationic surfactant to the isomeric alcohol polyoxyethylene ether is 1:(0.5-3.5), preferably 1:(0.8-3). The isomeric alcohol polyoxyethylene ether has an EO number of 3-9.

[0051] In a preferred embodiment, the additive is at least one of bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and nano-titanium dioxide.

[0052] In a preferred embodiment, the additive is a composition of one of bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and nano-titanium dioxide.

[0053] In a preferred embodiment, the fabric low-color-change softener of the present invention has an average particle size of 50-150 nm.

[0054] The fabric color-changing softener of the present invention is prepared by preparing an emulsion polymer in the presence of an emulsifier using divinyl-terminated polydimethylsiloxane, single-terminated polyurethane, poly(ethylene glycol)(meth)acrylate, and allyl polyoxyethylene ether, and then adding additives.

[0055] In another preferred embodiment of the present invention, the method for preparing the above-mentioned low-color-change softener for fabrics includes the following steps:

[0056] a) Prepare an aqueous emulsion of divinyl-terminated polydimethylsiloxane, single-terminated polyurethane, poly(ethylene glycol)(meth)acrylate and allyl polyoxyethylene ether at 40-60°C in the presence of an emulsifier.

[0057] b) Add a free radical initiator at 60-80℃ to initiate the polymerization reaction;

[0058] c) Raise the temperature to 75-95℃ and keep it warm for 1-5 hours;

[0059] d) Cool to 30-50℃, add additives, stir for 1-2 hours to obtain a fabric low-color-change softener.

[0060] In a preferred embodiment, the free radical initiator comprises persulfate, more preferably ammonium persulfate. The amount of the free radical initiator is 0.2-1 by mass relative to the total mass of the divinyl-terminated polydimethylsiloxane, the double-bond-single-terminated polyurethane, the poly(ethylene glycol)(meth)acrylate, and the allyl polyoxyethylene ether.

[0061] The fabric softener prepared by this invention has little impact on the color of dyed fabrics, especially sensitive colored fabrics, with minimal yellowing, excellent hand feel, and good hydrophilicity.

[0062] Compared with existing silicone softeners and their preparation methods, the originality of this invention is reflected in the following aspects: 1) The addition of divinyl-terminated polydimethylsiloxane and single-terminated polyurethane has a synergistic effect, providing the fabric with an excellent hand feel; 2) It does not contain the traditional block silicone oil raw material polyetheramine, which significantly reduces yellowing and color change of sensitive fabrics; 3) The addition of poly(ethylene glycol) (meth)acrylate and allyl polyoxyethylene ether greatly enhances hydrophilicity; 4) The amount of emulsifier used is greatly reduced in the preparation process, and no solvent is added, further reducing yellowing and color change of sensitive fabrics, and the emulsification effect is excellent and the emulsion stability is good; 5) The additives reduce yellowing of the fabric during high-temperature setting and application.

[0063] Example

[0064] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0065] Unless otherwise specified, the reagents and devices used in the examples are commercially available products commonly used in the art.

[0066] The resulting product was tested and its application and performance in textiles were determined as follows:

[0067] (a) Product performance testing

[0068] 1) Particle size determination:

[0069] The sample was prepared into a 1% by mass emulsion solution, and its average particle size and polydispersity index (PDI) were measured using a Zetasizer Nano S90 (Malvern) nanoparticle size analyzer. The smaller the polydispersity index, the more uniform the particle size distribution.

[0070] 2) Stability determination:

[0071] a. Dispersion stability: Weigh 3.0g of each sample and disperse it in 100ml of tap water. Observe whether oil floats, layering, or precipitation occurs. If so, it is determined to be unstable; otherwise, it is determined to be stable.

[0072] b. Shear stability: Weigh 3.0g of each sample and disperse it in water. Use a JSF-400 stirring mill dispersion machine at 3000r / min and shear for 10min. Observe whether oil floats, stratification or sedimentation occurs. If so, it is judged as unstable; otherwise, it is judged as stable.

[0073] c. Centrifugation stability: Centrifuge at 3000 rpm for 30 minutes using a medical centrifuge (TDZ5-WS) and observe whether oil floats, stratification, or precipitation occurs. If so, it is considered unstable; otherwise, it is considered stable.

[0074] (II) Application and performance testing in textiles:

[0075] 1) Application

[0076] Fabrics: Reactive turquoise dyed cotton fabric, disperse fluorescent yellow dyed polyester fabric, undyed cotton fabric, undyed polyester fabric

[0077] Formula: 15g / L of fabric softener

[0078] Process: One dip and one roll (90% roll-off) → Drying (90℃×2min) → Baking (160℃×2min)

[0079] 2) Standards for testing the performance of textiles:

[0080] Color change: Determined according to GB / T 250-2008 Textiles - Tests for color fastness - Evaluation of color change - Gray scale, rated from 1 to 5, with 1 indicating the greatest color change and 5 indicating the least color change;

[0081] Feel: The test was conducted by multiple people touching the surface. Five people were in a group to score the test, and the average score was taken as the evaluation result. 5 points was the best and 1 point was the worst.

[0082] Yellowing: Fold the fabric into 4 layers (keeping the fabric surface texture as consistent as possible and the fabric flat), and test the CIE values ​​of 4 different locations on the fabric under a Datacolor 400 colorimeter and a D65 / 10 light source. Take the average value, which is the whiteness. The higher the whiteness, the less yellowing.

[0083] Hydrophilicity: According to AATCC 79-2000, the shorter the wetting time, the better the hydrophilicity.

[0084] Example 1

[0085] Add 10g of vinyl-terminated polydimethylsiloxane MP200 (Shanghai Sibao High-Tech Materials Co., Ltd., viscosity 205 mPa.s, vinyl content 0.25 mmol / g), 7g of double-bond single-terminated polyurethane (self-made according to "Patent CN105504178B", structure as shown in Formula I, where R1 is H; n is 2; k is 3, PU prepolymer is Shanghai Sisheng Polymer Materials Co., Ltd. EC-605), 5g of poly(ethylene glycol) methacrylate (Hubei Jusheng Technology Co., Ltd., weight average molecular weight approximately 400), 5g of poly(ethylene glycol) methacrylate, and 5g of poly(ethylene glycol) methacrylate to a four-necked flask. 5g of allyl polyoxyethylene ether (purchased from Shanghai Taijie Chemical Co., Ltd., structure as shown in Formula III, m=40), 5g of hyperbranched Gemini quaternary ammonium salt cationic surfactant DC-551 (Henan Daochun New Material Technology Co., Ltd., content 50%), 4g of isomeric tridecyl alcohol polyoxyethylene ether TO5 (purchased from BASF (China) Co., Ltd.), and 63.8g of deionized water were added. The mixture was stirred and heated to 50℃ for 1.5h to form an aqueous emulsion. The temperature was then raised to 78℃, and 5.5g of 3% (w / w) ammonium persulfate aqueous solution was added dropwise. Stirring continued until the initiator was completely added. The temperature was then raised to 93℃ and maintained for 2 hours. The temperature was lowered to 40℃, and 0.1g of bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide and 0.1g of nano-titanium dioxide DXN-RT30 (purchased from Darcy Nanotechnology (Changzhou)) were added. The company, anatase type (3-5 nm), continued stirring for 1 hour to obtain fabric low color change softener 1, with an average particle size of 99.2 nm and a polydispersity index (PDI) of 0.108.

[0086] Example 2

[0087] Add the following to a four-necked flask: 12g of divinyl-terminated polydimethylsiloxane MP300 (Shanghai Sibao High-Tech Materials Co., Ltd., viscosity 310 mPa.s, vinyl content 0.21 mmol / g), 10g of double-bond single-terminated polyurethane (self-made according to "Patent CN105504178B", structure as shown in Formula I, where R1 is H; n is 2; k is 3, PU prepolymer is Shanghai Sisheng Polymer Materials Co., Ltd. EC-605), 7g of poly(ethylene glycol) acrylate (Hubei Jusheng Technology Co., Ltd., weight average molecular weight approximately 500), 6g of allyl polyoxyethylene ether (purchased from Shanghai Taijie Chemical Co., Ltd., structure as shown in Formula III, m=50), and 4g of hyperbranched Gemini quaternary ammonium salt cationic surfactant DC-551A (Henan Daochun New Materials Co., Ltd.). The following ingredients were added: 50% (content), 6g of isomeric tridecyl alcohol polyoxyethylene ether TO7 (purchased from BASF (China) Co., Ltd.), and 54.7g of deionized water. Stirring was started, and the temperature was raised to 55℃. Stirring was continued for 1.5h to prepare an aqueous emulsion. The temperature was raised to 80℃, and 7g of 3% ammonium persulfate aqueous solution was added dropwise. Stirring continued until the initiator was completely added. The temperature was then raised to 90℃ and kept at that temperature for 2h. The temperature was lowered to 40℃, and 0.2g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] and 0.1g of nano titanium dioxide DXN-RT30 (purchased from Darcy Nanotechnology (Changzhou) Co., Ltd., anatase type, 3-5nm) were added. Stirring was continued for 1h to obtain fabric low-color-change softener 2 with an average particle size of 88.5nm and a polydispersity index (PDI) of 0.104.

[0088] Example 3

[0089] Add 9g of vinyl-terminated polydimethylsiloxane MP450 (Shanghai Sibao High-Tech Materials Co., Ltd., viscosity 445 mPa.s, vinyl content 0.16 mmol / g), 9g of double-bond single-terminated polyurethane (self-made according to "Patent CN105504178B", structure as shown in Formula I, where R1 is H; n is 2; k is 3, and the PU prepolymer is Shanghai Sisheng Polymer Materials Co., Ltd. EC-600), 8g of poly(ethylene glycol) acrylate (Hubei Jusheng Technology Co., Ltd., weight average molecular weight approximately 500), 6g of allyl polyoxyethylene ether (purchased from Shanghai Taijie Chemical Co., Ltd., structure as shown in Formula III, m=40), and 6g of hyperbranched Gemini quaternary ammonium salt cationic surfactant DC-551A (Henan Daochun New Materials Co., Ltd.) to a four-necked flask. A technology company, with a content of 50%, 7g of isomeric tridecyl alcohol polyoxyethylene ether TO7 (purchased from BASF (China) Co., Ltd.), 54.8g of deionized water, started stirring, heated to 50℃, and stirred for 1.5h to prepare an aqueous emulsion; heated to 78℃, and started adding 6.5g of 3% ammonium persulfate aqueous solution, continued stirring, and after the initiator was completely added, heated to 90℃, kept at that temperature for 2 hours, cooled to 40℃, added 0.1g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] and 0.1g of nano titanium dioxide DXN-RT30 (purchased from Darcy Nanotechnology (Changzhou) Co., Ltd., anatase type, 3-5nm), and continued stirring for 1h to obtain fabric low color change softener 3, with an average particle size of 100.5nm and a polydispersity index (PDI) of 0.131.

[0090] The stability and application effects of each embodiment were compared with those of commercially available amino silicone oil softener A and commercially available block silicone oil softener B. The results are shown in Tables 1, 2, 3 and 4.

[0091] Table 1 Stability

[0092]

[0093] Table 2 Application Effects - Reactive Turquoise Blue Dyed Cotton Fabrics

[0094]

[0095] Table 3 Application Effects - Disperse Fluorescent Yellow Dyed Polyester Fabrics

[0096]

[0097] Table 4 Application Effects - Undyed Cotton Fabrics, Undyed Polyester Fabrics

[0098]

[0099] As can be seen from the application comparison data in Tables 1-4, the fabric low-color-change softener of the present invention has good stability. When applied to cotton and polyester fabrics dyed with sensitive colors, the color change is minimal, the hydrophilicity is excellent, and the hand feel is soft. These properties are superior to commercially available amino silicone oil softener A and block silicone oil softener B. Furthermore, it has high whiteness and minimal yellowing.

Claims

1. A fabric softener with low colorfastness, prepared from the following raw materials in weight percentages: Divinyl-terminated polydimethylsiloxane 5-15% Polyurethane with single-ended double bonds: 5-15% Poly(ethylene glycol) (meth)acrylate 3-15% Allyl polyoxyethylene ether 2-10% Emulsifier 5-20% Additives 0.05-0.5% Water balance The total mass of the above raw materials is taken as 100% by mass.

2. The fabric low-color-change softener as described in claim 1, characterized in that, The divinyl-terminated polydimethylsiloxane has a viscosity of 80-500 mPa·s and a vinyl content of 0.15-0.4 mmol / g.

3. The fabric low-color-change softener as described in claim 1, characterized in that, The structure of the polyurethane with single-ended double bonds is represented by Formula I: Equation I In Formula I: R1 is H or CH3; n is 2 or 3; k is an integer between 0 and 7; PU is a residue of waterborne polyurethane prepolymer.

4. The fabric low-color-change softener as described in claim 1, characterized in that, The structure of the poly(ethylene glycol)(meth)acrylate is represented by Formula II: Formula II In Formula II: R2 is H or CH3; p is an integer from 5 to 30.

5. The fabric low-color-change softener as described in claim 1, characterized in that, The structure of the allyl polyoxyethylene ether is represented by Formula III: CH2=CHCH2O(CH2CH2O) m H type III In Formula III: m is an integer between 1 and 100.

6. The fabric low-color-change softener as described in claim 1, characterized in that, The emulsifier is a mixture of hyperbranched Gimig quaternary ammonium salt cationic surfactant and isomeric alcohol polyoxyethylene ether, and the mass ratio of hyperbranched Gimig quaternary ammonium salt cationic surfactant to isomeric alcohol polyoxyethylene ether is 1:(0.5-3.5).

7. The fabric low-color-change softener as described in claim 1, characterized in that, The additive is a composition of one of bis(3,5-di-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and nano-titanium dioxide.

8. The fabric low-color-change softener according to any one of claims 1-7, characterized in that, The average particle size of the fabric low-color-change softener is 50-150 nm.

9. A method for preparing the fabric low-color-change softener according to any one of claims 1-8, the method comprising the following steps: a) Prepare an aqueous emulsion of divinyl-terminated polydimethylsiloxane, single-terminated polyurethane, poly(ethylene glycol)(meth)acrylate and allyl polyoxyethylene ether at 40-60°C in the presence of an emulsifier. b) Add a free radical initiator at 60-80℃ to initiate the polymerization reaction; c) Raise the temperature to 75-95℃ and keep it warm for 1-5 hours; d) Cool to 30-50℃, add additives, stir for 1-2 hours to obtain a fabric low-color-change softener.

10. The preparation method according to claim 9, characterized in that, The free radical initiator includes persulfate, and the amount of the free radical initiator used is 0.2-1 by mass relative to the total mass of the divinyl-terminated polydimethylsiloxane, the double-bond single-terminated polyurethane, the poly(ethylene glycol) (meth)acrylate, and the allyl polyoxyethylene ether.

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