A ternary compound type anti-migration water-based impregnating resin and a preparation method thereof

Abstract

The application discloses a ternary compound type anti-migration water-based impregnation resin and a preparation method thereof, and belongs to the technical field. The impregnation resin is made of raw materials with the following mass percentages, based on 100% of the total mass of the raw materials of the impregnation resin: 50-70% of an anionic water-based polyurethane emulsion, 5-10% of a self-film-forming anionic hand agent, 0.5-2% of an anionic emulsifier, 0.5-1% of a neutralizing agent, and the balance of deionized water; and the self-film-forming anionic hand agent is composed of water-soluble amino silicon oil and water-soluble epoxy silicon oil. The impregnation resin can be applied to the impregnation processing of artificial leather, synthetic leather and real leather, and can also be widely applied to the hand feeling finishing of various textile fabrics such as cotton, hemp, polyester and polyamide, and excellent soft, smooth and elastic hand feelings can be achieved, and there is no migration and no greasy feeling, so that the application range of the product is effectively expanded.

Description

Technical Field

[0001] This invention relates to the field of fabric additives technology, and more specifically, to a ternary compound anti-migration waterborne impregnation resin and its preparation method. Background Technology

[0002] In existing technologies, the impregnation process for synthetic leather, genuine leather, and textile fabrics often employs physically blended silicone oils to improve the feel. Due to the significant polarity difference between silicone oil and the polyurethane matrix, driven by entropic elasticity, silicone oil molecules easily migrate to the surface, leading to "oil shedding" and a loss of feel. To address this issue, existing technologies have attempted to blend epoxy-modified silicone oil with amino resins; however, these typically undergo pre-crosslinking below 80°C, resulting in a short shelf life (<3 months), failing to meet the requirements for industrial transportation and storage. Furthermore, traditional silicone oils often harden after crosslinking, compromising the fabric's softness. Therefore, there is an urgent need for a water-based impregnation resin that is stable at room temperature and can form a soft, elastic network at high temperatures. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a ternary compound anti-migration waterborne impregnation resin and its preparation method.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A ternary compound anti-migration waterborne impregnation resin, based on 100% of the total mass of the impregnation resin raw materials, is made from the following raw materials in the following mass percentages: 50-70% anionic waterborne polyurethane emulsion, 5-10% self-forming film-forming anionic hand feel agent, 0.5-2% anionic emulsifier, 0.5-1% neutralizer, and the balance being deionized water;

[0006] The self-forming anionic tactile agent is composed of water-soluble amino silicone oil and water-soluble epoxy silicone oil, with a mass ratio of (1.5-3):1.

[0007] The present invention is further configured such that the epoxy value of the water-soluble epoxy silicone oil is 0.2-0.5 mmol / g, and the ammonia value of the water-soluble amino silicone oil is 0.3-0.6 mmol / g.

[0008] The present invention is further configured such that the solid content of the anionic waterborne polyurethane emulsion is 30-40%.

[0009] The present invention is further configured such that the anionic emulsifier is one or a combination of two of sodium dodecylbenzenesulfonate and sodium fatty alcohol polyoxyethylene ether sulfate.

[0010] The present invention is further configured such that the neutralizing agent is one of triethanolamine and diethanolamine.

[0011] A method for preparing a ternary compound anti-migration waterborne impregnation resin involves mixing water-soluble amino silicone oil and water-soluble epoxy silicone oil to obtain a self-forming anionic tactile agent; adding an anionic emulsifier and continuing to mix to obtain a self-forming anionic tactile agent emulsion; mixing the self-forming anionic tactile agent emulsion with anionic waterborne polyurethane emulsion; adding a neutralizer and deionized water; continuing to mix; and filtering to obtain a ternary compound anti-migration waterborne impregnation resin.

[0012] In summary, the present invention has the following beneficial effects:

[0013] (1) Stable at room temperature and cross-linked film formation during application: This invention physically combines water-soluble amino silicone oil and water-soluble epoxy silicone oil, and combines them with water-based polyurethane to form an impregnation resin. The impregnation resin does not undergo cross-linking reaction at room temperature and can be left to stand for more than 6 months without layering or floating oil, showing excellent storage stability. When applied to leather, genuine leather, and textile fabrics, it can cause the silicone oil to undergo epoxy-amino cross-linking film formation while the polyurethane is curing, achieving the design goal of "no cross-linking during storage and film formation during application", solving the problem of storage aging of traditional pre-cross-linked hand feel agents.

[0014] (2) Molecular chain entanglement and fixation, completely solving the problem of softener migration: The elastic film layer formed by silicone oil cross-linking and the molecular chain after polyurethane curing are tightly physically entangled, firmly fixing the softening components in the composite film layer, fundamentally solving the problems of weak bonding force between traditional softeners and the matrix, easy migration, precipitation, and floating oil. The fabric hand feel is stable and lasting, and there is no obvious problem of decreased hand feel after being left at room temperature for more than 6 months.

[0015] (3) The self-forming anionic hand feel agent compounded in this invention has soft and elastic properties. Only 5 to 10 parts are needed to achieve excellent hand feel. No other hand feel agent needs to be added. This completely avoids the oily and sticky phenomenon of the fabric caused by the large amount of hand feel agent added in the traditional process, and improves the appearance and user experience of the fabric.

[0016] (4) Excellent compatibility of anionic system and strong self-film forming property: The entire impregnation resin is anionic, which has excellent compatibility with leather, textile fabric and water-based impregnation bath solution, without demulsification or delamination; the silicone oil crosslinking film layer and the polyurethane film layer form a film together, and the fabric surface after impregnation is smooth and uniform, with high fullness and no defects, and the film layer has high firmness and excellent abrasion resistance (dry and wet rubbing color fastness reaches ≥4 level). Detailed Implementation

[0017] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0018] This invention provides a ternary compound anti-migration waterborne impregnation resin that can be directly applied to the impregnation processing of artificial leather, synthetic leather, genuine leather or textile fabrics. Based on 100% of the total mass of the impregnating resin raw materials, the impregnating resin is made from the following raw materials in the following mass percentages: 50-70% anionic waterborne polyurethane emulsion (solid content 30-40%), 5-10% self-forming anionic tactile agent, 0.5-2% anionic emulsifier (preferably at least one of sodium dodecylbenzenesulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, sodium 2-ethylhexanoate hydroxyethyl sulfonate + sodium 2-ethylhexanoate isotridecyl ethoxylate sulfate), 0.5-1% neutralizer (preferably one of triethanolamine and diethanolamine), and the balance being deionized water; the self-forming anionic tactile agent is compounded from water-soluble amino silicone oil (ammonia value 0.3-0.6 mmol / g) and water-soluble epoxy silicone oil (epoxy value 0.2-0.5 mmol / g), with a mass ratio of water-soluble amino silicone oil to water-soluble epoxy silicone oil of (1.5-3):1.

[0019] Unlike traditional physically blended silicone oils, this invention utilizes the micellar shielding effect and thermally triggered latent curing mechanism to resolve the contradiction between the storage stability and high-temperature crosslinking of silicone oils in aqueous systems. The main mechanism is as follows:

[0020] (1) Micellar shielding and kinetic inertness: At room temperature and during storage, water-soluble amino silicone oil and water-soluble epoxy silicone oil are encapsulated by anionic emulsifiers to form stable micelle particles, and at room temperature, they are insufficient to trigger epoxy hydrolysis, so that the system remains stable in the range of 25℃-100℃.

[0021] (2) Thermally triggered interfacial crosslinking: When the impregnated fabric enters the shaping zone (135-145℃), the moisture evaporates rapidly, the micelle walls break, and the contact area between water-soluble amino silicone oil and water-soluble epoxy silicone oil increases dramatically at high temperature; at this time, the system changes from "aqueous phase dispersion" to "melt blending state", and the epoxy and amino groups undergo rapid ring-opening crosslinking reaction under thermal excitation, and a three-dimensional network structure is generated within 30-60 seconds.

[0022] (3) Soft elastic interpenetrating network (IPN): This three-dimensional cross-linked network retains the main chain structure of polysiloxane and has a modulus as low as 1-10 MPa, giving the material rubber elasticity; at the same time, the network interpenetrates and physically entangles with the polyurethane molecular chains that are being cured, physically locking the siloxane chain segments, thereby preventing the high-temperature migration of silicone oil.

[0023] Example 1

[0024] By weight, the ternary compound anti-migration waterborne impregnation resin of this embodiment is made of the following components: 55 parts of anionic waterborne polyurethane emulsion (solid content 35wt%, number average molecular weight 20000, purchased from Shaoxing Huanye New Material Technology Co., Ltd., model HY-6508), 9 parts of self-forming film anionic hand feel agent (6 parts of water-soluble amino silicone oil (ammonia value 0.3mmol / g, purchased from Shaoxing Huanye New Material Technology Co., Ltd., model HY-801) + 3 parts of water-soluble epoxy silicone oil (epoxy value 0.2mmol / g, purchased from Shaoxing Huanye New Material Technology Co., Ltd., model HY-835), 1.2 parts of emulsifier sodium fatty alcohol polyoxyethylene ether sulfate (AES surfactant, purchased from Shandong Zisheng Chemical Co., Ltd.), 0.6 parts of neutralizing agent diethanolamine, and 34.2 parts of deionized water.

[0025] Preparation method:

[0026] (1) Add the anionic waterborne polyurethane emulsion into the reactor and stir at 900 r / min for 10 min at 35°C to make the emulsion uniformly dispersed.

[0027] (2) Weigh water-soluble amino silicone oil and water-soluble epoxy silicone oil, stir at 300 r / min for 20 min at room temperature, and after mixing evenly, obtain a self-forming anionic hand feel agent;

[0028] (3) Add the self-forming anionic tactile agent and emulsifier to the reactor, maintain a speed of 900 r / min, and continue stirring for 25 min to make the tactile agent evenly dispersed and without obvious oil droplets;

[0029] (4) Add a neutralizing agent to the emulsion obtained in step (3), stir for 12 minutes (at which point the pH value reaches 7.2), then add 34.2 parts of deionized water to adjust the solid content to 28%, and continue stirring for 15 minutes; filter through a 1 μm filter membrane to obtain the finished impregnated resin. The finished product is a milky white emulsion with anionic properties. No abnormal phenomena such as stratification or floating oil occurred after standing at room temperature (25℃) for 7 months, and the storage stability is excellent.

[0030] Application: The synthetic leather base fabric (purchased from Hubei Jinfuxiang Technology Co., Ltd., model 00) is impregnated with impregnating resin for two dips and two nips (each dip bath ratio is 1:30, the dip temperature is 25℃, the dip time is 30s, and the liquid retention rate after two dips and two nips is controlled to be 75%). Then it is set at 160℃ for 40s (during this process, when the temperature exceeds 110℃, water-soluble amino silicone oil and water-soluble epoxy silicone oil crosslink and form a film quickly, which is simultaneously cured with polyurethane and forms molecular chain entanglement). It is washed with water until neutral and dried to obtain impregnated synthetic leather.

[0031] The synthetic leather after impregnation is soft, smooth, and supple to the touch, with a delicate and fleshy feel, without any stickiness or greasiness. After being left to stand at room temperature (25℃) for 7 months, there is no migration of the softener, the feel is long-lasting, and the fullness and flexibility of the leather products are significantly improved. The color fastness to dry rubbing reaches grade 4.5 and the color fastness to wet rubbing reaches grade 4 (tested according to GB / T 3920-2008 standard).

[0032] Example 2

[0033] By weight, the ternary compound anti-migration waterborne impregnation resin of this embodiment is made of the following components: 65 parts of anionic waterborne polyurethane emulsion, 5.5 parts of self-forming film anionic hand feel agent (4 parts of water-soluble amino silicone oil + 1.5 parts of water-soluble epoxy silicone oil), 0.7 parts of emulsifier (0.4 parts of sodium dodecylbenzene sulfonate + 0.3 parts of sodium fatty alcohol polyoxyethylene ether sulfate), 1.0 part of neutralizing agent triethanolamine, and 27.8 parts of deionized water.

[0034] A ternary compound anti-migration waterborne impregnation resin was prepared according to the method in Example 1. The finished product was a milky white emulsion with anionic properties. After standing at room temperature (25°C) for 9 months, no abnormal phenomena such as stratification or floating oil occurred, demonstrating excellent storage stability.

[0035] Application: The synthetic leather base fabric is impregnated with impregnating resin for two dips and two nips (each dip bath ratio is 1:30, the dip temperature is 25℃, the dip time is 30s, and the liquid retention rate after two dips and two nips is controlled to be 75%), then it is set at 170℃ for 35s, washed with water until neutral, and dried to obtain impregnated synthetic leather.

[0036] The impregnated synthetic leather has a smooth, supple, and delicate feel, without any stickiness or greasiness. After being left to stand at room temperature (25℃) for 9 months, the synthetic leather showed no softener migration (migration was verified using an accelerated aging test: the sample and the colored film were placed under 4.5 kg pressure in an environment of 70℃±2℃ for 168 hours. After removal, the staining grade of the colored film was ≥4, and there was no oily exudate or stickiness on the sample surface, which is equivalent to proving that there is no softener migration after long-term standing at room temperature). The feel remains good, and the dry rubbing color fastness reaches 4.5 and the wet rubbing color fastness reaches 4, meeting the quality requirements of high-end artificial leather.

[0037] Comparative Example 1

[0038] The impregnation resin was prepared according to Example 1, except that the weight ratio of water-soluble amino silicone oil to water-soluble epoxy silicone oil was adjusted to 4:1. The results showed that the impregnation resin emulsion was initially uniform, but after being stored at room temperature (25°C) for 120 days, the system showed stratification and flocculent precipitate was formed.

[0039] Example 3

[0040] By weight, the ternary compound anti-migration waterborne impregnation resin of this embodiment is made of the following components: 65 parts of anionic waterborne polyurethane emulsion, 5.5 parts of self-forming film anionic hand feel agent (4 parts of water-soluble amino silicone oil + 1.5 parts of water-soluble epoxy silicone oil), 0.7 parts of emulsifier (0.4 parts of sodium hydroxyethyl sulfonate of 2-ethylhexanoate + 0.3 parts of sodium ethoxylate of 2-ethylhexanoate), 1.0 part of neutralizing agent triethanolamine, and 27.8 parts of deionized water.

[0041] The preparation method is as follows:

[0042] (a) 2-Ethylhexanoic anhydride, isotretinoin, p-toluenesulfonic acid and anhydrous toluene (the ratio of 2-ethylhexanoic anhydride, isotretinoin and anhydrous toluene is 258.4 g: 200.36 g: 3 g: 300 mL) were added to the reaction vessel and refluxed at 110 °C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and 1.5 times the volume of 5% Na2CO3 solution was added. The mixture was stirred and allowed to stand for separation. The pH of the aqueous phase was adjusted to 2 with dilute hydrochloric acid and extracted three times with diethyl ether. The ether extract layers were combined, dried with anhydrous sodium sulfate, filtered, and the diethyl ether was recovered by distillation under normal pressure to obtain 2-ethylhexanoic acid. The organic phase was washed successively with distilled water and saturated sodium chloride solution, dried with anhydrous sodium sulfate, filtered, and the toluene was recovered by distillation under normal pressure. The fraction at 150-170 °C was collected by vacuum distillation to obtain 2-ethylhexanoic acid isotretinoate.

[0043] (b) Add 2-ethylhexanoic acid, sodium hydroxyethyl sulfonate, p-toluenesulfonic acid, and toluene (the ratio of 2-ethylhexanoic acid, sodium hydroxyethyl sulfonate, p-toluenesulfonic acid, and toluene is 1.79 mol: 1.8 mol: 1 g: 200 mL) to a reaction vessel, mix thoroughly, and reflux at 115 °C for 6 h. After the reaction, cool the reaction solution to 60 °C, add an equal volume of deionized water to dissolve the product, allow it to stand and separate into layers, discard the upper layer of toluene (which can be recovered), adjust the pH of the lower aqueous phase to 8 with 10% NaOH solution, then decolorize with activated carbon for 30 min, filter, remove 90% of the water by vacuum distillation of the filtrate, and then dry it under vacuum at 95 °C to constant weight to obtain sodium 2-ethylhexanoic acid hydroxyethyl sulfonate.

[0044] (c) Add 2-ethylhexanoic acid isotridecyl ester and solid NaOH to the reactor, under nitrogen protection, and ethylene oxide (EO) is introduced at 155°C. After the EO is introduced, the reaction is carried out under nitrogen protection at 165°C for 2 hours. Then, the temperature is lowered to 80°C, and the system is neutralized with dilute hydrochloric acid to pH 7. Activated carbon is added and decolorized at 80°C for 30 minutes. The mixture is filtered, and the filtrate is dehydrated under vacuum at 95°C to a water content of 0.1%. The dehydrated product is diluted with anhydrous toluene (dilution volume ratio 1:1). Chlorosulfonic acid (2-ethylhexanoic acid isotridecyl ester, NaOH, ethylene oxide: chlorosulfonic acid in a volume ratio of 1 mol: 0.66 g: 5 mol: 1.05 mol) is added dropwise at 0°C. After the addition is complete, the temperature is raised to 35°C and the reaction continues for 2 hours. The reaction solution is neutralized with 30% NaOH solution to pH 7, allowed to stand and separate into layers, and the organic phase is desolventized under reduced pressure and spray-dried to obtain sodium sulfate ethoxylate of 2-ethylhexanoic acid isotridecyl ester.

[0045] (d) A ternary compound anti-migration waterborne impregnation resin was prepared according to the method in Example 1. The finished product showed no abnormal phenomena such as stratification or floating oil after standing at room temperature (25°C) for 12 months, demonstrating excellent storage stability.

[0046] Application: The impregnation treatment was carried out according to the method in Example 2. The impregnated synthetic leather has a smooth and delicate feel, without stickiness or greasiness; after being left to stand at room temperature (25°C) for 12 months, there was no migration of softener, the feel is long-lasting, and the color fastness to dry rubbing reaches grade 5 and the color fastness to wet rubbing reaches grade 4.5.

[0047] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A ternary compound anti-migration waterborne impregnation resin, characterized in that, Based on 100% of the total mass of the impregnating resin raw materials, the impregnating resin is made from the following raw materials in the following mass percentages: 50-70% anionic waterborne polyurethane emulsion, 5-10% self-forming film-forming anionic hand feel agent, 0.5-2% anionic emulsifier, 0.5-1% neutralizer, and the balance being deionized water; The self-forming anionic tactile agent is composed of water-soluble amino silicone oil and water-soluble epoxy silicone oil, with a mass ratio of (1.5-3):

1.

2. The ternary compound anti-migration waterborne impregnation resin according to claim 1, characterized in that, The water-soluble epoxy silicone oil has an epoxy value of 0.2-0.5 mmol / g, and the water-soluble amino silicone oil has an ammonia value of 0.3-0.6 mmol / g.

3. The ternary compound anti-migration waterborne impregnation resin according to claim 1, characterized in that, The solid content of the anionic waterborne polyurethane emulsion is 30-40%.

4. The ternary compound anti-migration waterborne impregnation resin according to claim 1, characterized in that, The anionic emulsifier is one or a combination of two of sodium dodecylbenzenesulfonate and sodium fatty alcohol polyoxyethylene ether sulfate.

5. The ternary compound anti-migration waterborne impregnation resin according to claim 1, characterized in that, The neutralizing agent is one of triethanolamine or diethanolamine.

6. A method for preparing a ternary compound anti-migration waterborne impregnation resin according to any one of claims 1-5, characterized in that, Water-soluble amino silicone oil and water-soluble epoxy silicone oil are mixed to obtain a self-forming anionic tactile agent. An anionic emulsifier is added and the mixture is further mixed to obtain a self-forming anionic tactile agent emulsion. The self-forming anionic tactile agent emulsion is mixed with anionic waterborne polyurethane emulsion, a neutralizer and deionized water are added, the mixture is further mixed, and then filtered to obtain a ternary compound anti-migration waterborne impregnation resin.