A composite modified darkening emulsion and preparation method thereof

Abstract

The invention discloses a composite modified darkening emulsion and a preparation method thereof, which belongs to the technical field of textile printing and dyeing auxiliaries, and comprises the following components by weight percentage: 3-6% polyethylene glycol-200, 1-3% 2-(1-hydroxypropyl-2-thio)propane-1-ol, 5-9% hexamethylene diisocyanate, 1-2% N-methyldiethanolamine, 3-9% hydroxyethyl acrylate, 15-20% methyl methacrylate, 1-2% KH-570, 1-2% glacial acetic acid, 0.5-1% water-soluble initiator, and the balance is water. The present invention adopts the above-mentioned composite modified darkening emulsion and a preparation method thereof, and the prepared darkening emulsion combines sulfur, polyurethane, and organosilicon composite modified acrylate emulsion, and after being applied to fabric finishing, the resin layer has the characteristics of high refractive index and multi-layer refraction, thereby significantly improving the color depth of the fabric.

Description

Technical Field

[0001] The invention relates to the technical field of textile printing and dyeing auxiliaries, in particular to a composite modified darkening emulsion and a preparation method thereof. Background Art

[0002] After years of development, a variety of methods have been proposed to deepen the color depth of dyed fiber products. Among them, the industrially recognized and widely used treatment method is mainly through the post-finishing process, through the padding of materials with a deepening effect to enhance the color of the fiber. Conventional deepening materials include polyurethane, silicone, acrylate and other materials. The main principle is to form a fine uneven resin layer on the surface of the dyed fiber. Since this type of material has a low refractive index, the visible light is partially absorbed after refraction and multiple reflections of the resin layer, and finally the light energy received by the human eye is weakened, thereby achieving a deepening effect.

[0003] However, the refractive index parameters of the commonly used deepening materials are limited, and the molecular structure is too regular, so the crystallinity is too strong. Therefore, the process control requirements during the application process are too high, which can easily cause uneven deepening of the treated fiber fabric area and a low final product qualification rate. At the same time, since the resin layer on the surface of the treated fiber fabric is too crystallinity, the treated fabric feels dry and the hydrophilicity of the fabric is greatly reduced. Summary of the invention

[0004] The purpose of the present invention is to provide a composite modified darkening emulsion and a preparation method thereof. The prepared darkening emulsion combines sulfur-based, polyurethane, and silicone composite modified acrylate emulsions. After being applied to fabric finishing, the resin layer has the characteristics of high refractive index and multi-layer refraction, thereby significantly improving the color depth of the fabric.

[0005] To achieve the above-mentioned purpose, the present invention provides a composite modified darkening emulsion, which comprises the following components by weight percentage: 3-6% of polyethylene glycol-200, 1-3% of 2-(1-hydroxypropan-2-ylthio)propan-1-ol, 5-9% of hexamethylene diisocyanate, 1-2% of N-methyldiethanolamine, 3-9% of hydroxyethyl acrylate, 15-20% of methyl methacrylate, 1-2% of KH-570, 1-2% of glacial acetic acid, 0.5-1% of a water-soluble initiator, and the balance is water.

[0006] Preferably, the water-soluble initiator is ammonium persulfate.

[0007] The present invention also provides a method for preparing the composite modified darkening emulsion, comprising the following steps:

[0008] Step 1, adding weighed polyethylene glycol-200, 2-(1-hydroxypropan-2-ylthio)propan-1-ol, and N-methyldiethanolamine into a reaction bottle, gradually heating up, then adding weighed hexamethylene diisocyanate, keeping warm for reaction, then adding weighed hydroxyethyl acrylate, and continuing keeping warm for reaction to obtain a polyurethane prepolymer;

[0009] Step 2: After the polyurethane prepolymer obtained in step 1 is cooled, glacial acetic acid, methyl methacrylate, KH-570, ammonium persulfate and deionized water are added to obtain a pre-emulsion after high-speed dispersion;

[0010] Step 3: Take a portion of the pre-emulsion obtained in step 2 and add it to the reaction bottle, gradually increase the temperature, and then dropwise add the remaining pre-emulsion;

[0011] Step 4: After the addition is completed, the reaction temperature is controlled to carry out heat preservation treatment, and then the stirring is stopped after the temperature drops, and the material is filtered to obtain a composite modified darkening emulsion.

[0012] Preferably, in step 1, the heating temperature is 75-80° C., the first insulation time is 2-3 h, and the insulation time after adding hydroxyethyl acrylate is 1-2 h.

[0013] Preferably, the polyurethane prepolymer in step 2 is cooled to 30-50° C., and the rotation speed of high-speed dispersion is 1500-2000 rpm.

[0014] Preferably, in step 3, 20-40% of the pre-emulsion is first taken and the temperature is gradually raised to 75-80°C. When the temperature reaches 78°C, the remaining pre-emulsion is added dropwise, and the addition is completed in 2-3 hours. During the addition, the temperature of the reaction bottle is controlled at 80-85°C.

[0015] Preferably, in step 4, the insulation treatment temperature is 85-90°C, the insulation time is 30-60min, and the stirring is stopped after the temperature drops to 30-50°C.

[0016] Therefore, the present invention adopts the above-mentioned composite modified darkening emulsion and its preparation method, which has the following beneficial effects:

[0017] (1) modifying polyurethane material by doping with sulfur, and then subjecting the modified polyurethane, silicone and acrylate to soap-free emulsion polymerization to obtain a composite modified darkening emulsion;

[0018] (2) Since sulfur has excellent color light absorption, its introduction into the structure can significantly increase the refractive index of the material. At the same time, the crystallinity of the hybrid modified composite material is improved. When applied to the darkening treatment of fiber fabrics, the darkening effect of the fabrics is excellent and the darkening stability is good;

[0019] (3) By utilizing the hydrophilic long chain and quaternary ammonium salt structure in the polyurethane structure, the treated fabric has a good feel and its hydrophilicity is significantly improved.

[0020] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The invention discloses a composite modified darkening emulsion and a preparation process thereof. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0023] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0024] like Figure 1 As shown, the present invention provides a composite modified darkening emulsion, which includes the following components in weight percentage: 3-6% of polyethylene glycol-200, 1-3% of 2-(1-hydroxypropan-2-ylthio)propan-1-ol, 5-9% of hexamethylene diisocyanate, 1-2% of N-methyldiethanolamine, 3-9% of hydroxyethyl acrylate, 15-20% of methyl methacrylate, 1-2% of KH-570, 1-2% of glacial acetic acid, 0.5-1% of a water-soluble initiator, and the balance is water, wherein the water-soluble initiator is ammonium persulfate.

[0025] The preparation method of the above-mentioned composite modified darkening emulsion comprises the following steps:

[0026] Step 1: Add weighed polyethylene glycol-200, 2-(1-hydroxypropan-2-ylthio)propan-1-ol and N-methyldiethanolamine into a reaction bottle, gradually raise the temperature to 75-80°C, then add weighed hexamethylene diisocyanate, keep warm for 2-3h, then add weighed hydroxyethyl acrylate, continue to keep warm for 1-2h to obtain a polyurethane prepolymer.

[0027] Step 2: After the polyurethane prepolymer obtained in step 1 is cooled to 30-50° C., glacial acetic acid, methyl methacrylate, KH-570, ammonium persulfate and deionized water are added, and a pre-emulsion is obtained after high-speed dispersion, and the speed of high-speed dispersion is 1500-2000 rpm.

[0028] Step 3: Take 20-40% of the pre-emulsion obtained in step 2 and add it to the reaction bottle, gradually heat it to 75-80°C, when it reaches 78°C, start to drop the remaining pre-emulsion, and finish dropping it in 2-3 hours. During the dropping process, control the temperature of the reaction bottle at 80-85°C.

[0029] Step 4: After the addition is completed, the reaction temperature is controlled to carry out heat preservation treatment, the heat preservation treatment temperature is 85-90°C, the heat preservation time is 30-60min, and then the stirring is stopped after the temperature drops to 30-50°C, and the material is filtered to obtain a composite modified darkening emulsion.

[0030] Example 1

[0031] Step 1: Add 3 g of polyethylene glycol-2000, 1 g of 2-(1-hydroxypropyl-2-thio)propan-1-ol, and 1 g of N-methyldiethanolamine into a reaction bottle, gradually heat to 75°C, add 5 g of hexamethylene diisocyanate, and keep warm for 2 hours, add 3 g of hydroxyethyl acrylate, and continue to keep warm for 1 hour to obtain a polyurethane prepolymer.

[0032] Step 2: After the polyurethane prepolymer is cooled to 30° C., 1 g of glacial acetic acid, 15 g of methyl methacrylate, 1 g of KH-570, 0.5 g of ammonium persulfate and the remaining deionized water are added, and the mixture is dispersed at 1500 rpm for 60 minutes to obtain a pre-emulsion.

[0033] Step 3: Take 30% of the above pre-emulsion and add it into the reaction bottle, gradually raise the temperature to 75-80°C, when the temperature rises to 78°C, start to drop the remaining pre-emulsion, and finish dropping it in 2 hours; during the dropping process, control the temperature of the reactor at 80°C.

[0034] Step 4: After the addition is completed, the temperature is controlled to 85° C. and kept warm for 60 minutes, then cooled to 50° C., stirring is stopped, and the material is filtered to obtain the composite modified darkening emulsion.

[0035] Example 2

[0036] Step 1: Add 6 g of polyethylene glycol-2000, 3 g of 2-(1-hydroxypropyl-2-thio)propan-1-ol, and 2 g of N-methyldiethanolamine into a reaction bottle, gradually heat to 80°C, add 9 g of hexamethylene diisocyanate, and keep warm for 3 hours, add 9 g of hydroxyethyl acrylate, and continue to keep warm for 2 hours to obtain a polyurethane prepolymer.

[0037] Step 2: After the polyurethane prepolymer is cooled to 35° C., 2 g of glacial acetic acid, 20 g of methyl methacrylate, 2 g of KH-570, 1 g of ammonium persulfate and the remaining deionized water are added, and the mixture is dispersed at 2000 rpm for 60 minutes to obtain a pre-emulsion.

[0038] Step 3: Take 30% of the above pre-emulsion and add it into the reaction bottle, gradually raise the temperature to 75-80°C, when the temperature rises to 78°C, start to drop the remaining pre-emulsion, and finish dropping it in 3 hours; during the dropping process, control the temperature of the reactor at 85°C.

[0039] Step 4: After the addition is completed, the temperature is controlled to 90° C. and kept warm for 60 minutes, then cooled to 50° C., stirring is stopped, and the material is filtered to obtain the composite modified darkening emulsion.

[0040] Example 3

[0041] Step 1: Add 4 g of polyethylene glycol-2000, 2 g of 2-(1-hydroxypropyl-2-thio)propan-1-ol, and 1.5 g of N-methyldiethanolamine into a reaction bottle, gradually raise the temperature to 78°C, add 7 g of hexamethylene diisocyanate, and keep the temperature for reaction for 2.5 hours, add 6 g of hydroxyethyl acrylate, and continue to keep the temperature for reaction for 2.5 hours to obtain a polyurethane prepolymer.

[0042] Step 2: After the polyurethane prepolymer is cooled to 33° C., 1.5 g of glacial acetic acid, 18 g of methyl methacrylate, 1.5 g of KH-570, 0.8 g of ammonium persulfate and the remaining deionized water are added, and the mixture is dispersed at 1800 rpm for 60 minutes to obtain a pre-emulsion.

[0043] Step 3: Take 30% of the above pre-emulsion and add it into the reaction bottle, gradually raise the temperature to 75-80°C, when the temperature rises to 78°C, start to drop the remaining pre-emulsion, and finish dropping it in 2.5 hours; during the dropping process, control the temperature of the reactor at 82°C.

[0044] Step 4: After the addition is completed, the temperature is controlled to 88° C. and kept warm for 60 minutes, then cooled to 50° C., stirring is stopped, and the material is filtered to obtain the composite modified darkening emulsion.

[0045] Comparative Example

[0046] Conventional polyurethane darkening emulsion, silicone darkening emulsion and acrylate darkening emulsion on the market were selected as comparative examples.

[0047] Examples 1-3 and the comparative example were applied to the darkening treatment of dispersed black polyester dyed fiber and reactive black pure cotton dyed fiber, and the specific treatment process was as follows:

[0048] Emulsion dosage: 40g / L;

[0049] Treatment process: 2 dips and 2 rolls, liquid rate is 75-90%;

[0050] Baking conditions:

[0051] Disperse black polyester dyed fiber: 160℃, 35s;

[0052] Reactive black cotton dyed fiber: 160℃, 50s.

[0053] App Reviews:

[0054] (1) Darkening effect: The K / S value of untreated fabrics and fabrics treated with different additives was tested using a Datacolor 500 colorimeter. The lower the K / S value, the better the darkening effect.

[0055] (2) Hydrophilicity: Drop 0.5 mL of pure water onto the test fabric and record the absorption time of the water drop. If the absorption time is greater than 2 minutes, the fabric is considered water-repellent.

[0056] (3) Hand feel evaluation: A five-person evaluation system is used with a score range of 0-5, with 5 being the best hand feel of the fabric. The sum of the scores of the five people is the hand feel score of the tested fabric. The higher the score, the better the hand feel.

[0057] Table 1 Disperse black polyester dyed fiber treatment results

[0058] Darkening effect (K / S) Hydrophilicity (seconds) Feel Untreated fabrics 35.26 5 25 Conventional polyurethane darkening emulsion 30.46 90 16 Silicone Deepening Lotion 28.57 Water repellent 18 Acrylate Darkening Emulsion 21.67 70 14 Example 1 17.86 40 20 Example 2 15.67 27 22 Example 3 16.32 32 20

[0059] Table 2 Reactive black pure cotton dyeing fiber treatment results

[0060] Darkening effect (K / S) Hydrophilicity (seconds) Feel Untreated fabrics 26.79 2 25 Conventional polyurethane darkening emulsion 24.56 60 15 Silicone Deepening Lotion 22.34 Water repellent 20 Acrylate Darkening Emulsion 23.68 40 12 Example 1 20.14 20 18 Example 2 18.65 15 21 Example 3 19.57 18 19

[0061] It can be seen from Tables 1 and 2 that the darkening emulsion prepared by the present invention has excellent darkening performance and hand feel after being applied to the fabric, and the hydrophilicity of the fabric is also significantly better than that of the fabric after the commercially available darkening emulsion is applied.

[0062] Therefore, the present invention adopts the above-mentioned composite modified darkening emulsion and its preparation method. The prepared darkening emulsion combines sulfur-based, polyurethane, and silicone composite modified acrylate emulsion. After being applied to fabric finishing, the resin layer has the characteristics of high refractive index and multi-layer refraction, thereby significantly improving the color depth of the fabric.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A composite modified darkening emulsion, characterized in that: The invention comprises the following components by weight percentage: 3-6% of polyethylene glycol-200, 1-3% of 2-(1-hydroxypropyl-2-thio)propan-1-ol, 5-9% of hexamethylene diisocyanate, 1-2% of N-methyldiethanolamine, 3-9% of hydroxyethyl acrylate, 15-20% of methyl methacrylate, 1-2% of KH-570, 1-2% of glacial acetic acid, 0.5-1% of a water-soluble initiator, and the balance is water.

2. A composite modified darkening emulsion according to claim 1, characterized in that: The water-soluble initiator is ammonium persulfate.

3. A method for preparing a composite modified darkening emulsion according to any one of claims 1 to 2, characterized in that: The following steps are involved: Step 1, adding weighed polyethylene glycol-200, 2-(1-hydroxypropan-2-ylthio)propan-1-ol, and N-methyldiethanolamine into a reaction bottle, gradually heating up, then adding weighed hexamethylene diisocyanate, keeping warm for reaction, then adding weighed hydroxyethyl acrylate, and continuing keeping warm for reaction to obtain a polyurethane prepolymer; Step 2: After the polyurethane prepolymer obtained in step 1 is cooled, glacial acetic acid, methyl methacrylate, KH-570, ammonium persulfate and deionized water are added to obtain a pre-emulsion after high-speed dispersion; Step 3: Take a portion of the pre-emulsion obtained in step 2 and add it to the reaction bottle, gradually increase the temperature, and then dropwise add the remaining pre-emulsion; Step 4: After the addition is completed, the reaction temperature is controlled to carry out heat preservation treatment, and then the stirring is stopped after the temperature drops, and the material is filtered to obtain a composite modified darkening emulsion.

4. The method for preparing a composite modified darkening emulsion according to claim 3, characterized in that: In step 1, the heating temperature is 75-80° C., the first insulation time is 2-3 hours, and the insulation time after adding hydroxyethyl acrylate is 1-2 hours.

5. The method for preparing a composite modified darkening emulsion according to claim 3, characterized in that: The polyurethane prepolymer in step 2 is cooled to 30-50° C., and the rotation speed of high-speed dispersion is 1500-2000 rpm.

6. The method for preparing a composite modified darkening emulsion according to claim 3, characterized in that: In step 3, first take 20-40% of the pre-emulsion and gradually heat it to 75-80°C. When the temperature reaches 78°C, start dripping the remaining pre-emulsion and finish dripping it in 2-3 hours. During the dripping process, control the temperature of the reaction bottle at 80-85°C.

7. The method for preparing a composite modified darkening emulsion according to claim 3, characterized in that: In step 4, the insulation treatment temperature is 85-90°C, the insulation time is 30-60min, and the stirring is stopped after the temperature drops to 30-50°C.

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