Hydrophilic deepening agent and preparation method thereof

Abstract

The invention relates to the technical field of preparation of deepening agents, in particular to a hydrophilic deepening agent and a preparation method thereof. The preparation method comprises the following steps: S1, preparing an emulsifier and alkyl glycoside into a compound emulsifier; the preparation method comprises the following steps: blending vinyl acetate, butyl acrylate, 2-ethylhexyl acrylate and hydroxyethyl acrylate with a polyether amine monomer to prepare a mixed solution; s2, adding part of the compound emulsifier into the mixed solution, and mixing and emulsifying to prepare a pre-emulsion; reacting the residual compound emulsifier with part of the initiator to prepare a seed emulsion; and S3, adding the pre-emulsion, a silane coupling agent and the residual initiator into the seed emulsion, and carrying out a reaction to obtain the hydrophilic deepening agent. According to the preparation method, the hydrophilicity, washing resistance, rubbing fastness and hand feeling of the fabric finished by the deepening agent can be effectively improved, and meanwhile, a better deepening effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of a depth enhancing agent, and in particular to a hydrophilic depth enhancing agent and a preparation method thereof. Background Art

[0002] At present, the darkening agents on the market are mostly silicone resins or organic fluorine resins due to material problems. However, both are hydrophobic, which causes the hydrophilicity of the finished fabric to decrease. In response to this, researchers have proposed a hydrophilic darkening agent - polyacrylate emulsion darkening agent.

[0003] The polyacrylate emulsion darkening agent has a high glass transition temperature and can form hard "microspheres" on the fabric surface, improve the surface roughness of the fabric, increase its diffuse reflection effect of visible light, and achieve the effect of visual darkening. The Chinese invention patent with publication number CN106478859A discloses a method for preparing a dyed polyester fabric darkening agent, which uses a cationic emulsifier, a nonionic emulsifier, methyl methacrylate, styrene, acrylonitrile, ethylene glycol methacrylate, a fluorine-containing monomer, an organosilicon monomer, an initiator, and deionized water, and uses a semi-continuous seed emulsion polymerization method to prepare a "soft core and hard shell" core-shell structure darkening agent emulsion. Although it has an excellent darkening effect, its hard "shell" structure will reduce the softness of the treated fiber fabric, reduce the friction color fastness and hydrophilicity. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a hydrophilic darkening agent which has good darkening effect and can improve the hand feel of finished fabrics and a preparation method thereof.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preparing a hydrophilic depth enhancing agent, comprising the following steps: S1: preparing a composite emulsifier by mixing an emulsifier and an alkyl polyglycoside; blending vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate with a polyetheramine monomer to prepare a mixed solution; S2: adding part of the composite emulsifier to the mixed solution and mixing and emulsifying to obtain a pre-emulsion; reacting the remaining composite emulsifier with part of the initiator to obtain a seed emulsion; S3: adding the pre-emulsion, the silane coupling agent and the remaining initiator into the seed emulsion to react and obtain a hydrophilic deepening agent.

[0006] Another technical solution adopted by the present invention is: a hydrophilic depth enhancing agent prepared by the preparation method of the hydrophilic depth enhancing agent.

[0007] The beneficial effects of the present invention are as follows: the preparation method of the present invention uses silicone-modified polyacrylate as an emulsion to prepare a darkening agent, and at the same time adds a certain polyether segment into its molecular structure, which can effectively improve the hydrophilicity, water wash resistance, friction fastness and hand feel of the fabric after being treated with the darkening agent, and at the same time give the darkening agent a better darkening effect, and has a wide range of applications. DETAILED DESCRIPTION

[0008] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in conjunction with the implementation modes.

[0009] A method for preparing a hydrophilic depth enhancing agent comprises the following steps: S1: preparing a composite emulsifier by mixing an emulsifier and an alkyl polyglycoside; blending vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate with a polyetheramine monomer to prepare a mixed solution; S2: adding part of the composite emulsifier to the mixed solution and mixing and emulsifying to obtain a pre-emulsion; reacting the remaining composite emulsifier with part of the initiator to obtain a seed emulsion; S3: adding the pre-emulsion, the silane coupling agent and the remaining initiator into the seed emulsion to react and obtain a hydrophilic deepening agent.

[0010] As can be seen from the above description, the beneficial effects of the present invention are: acrylate emulsion, as the base resin of water-based acrylic coating, is widely used due to its excellent weather resistance, acid and alkali resistance and corrosion resistance. However, it has many disadvantages, such as poor water resistance, poor adhesion, low temperature brittleness, high temperature viscosity, etc., which limit its application. In the main chain structure of polysiloxane molecules, the Si-O bond energy is very high, and there is a large molecular volume and low cohesive energy density, so it has good high and low temperature resistance, weather resistance and low surface tension. The use of organosiloxane-modified acrylates can effectively combine the advantages of organosiloxane and acrylic resin.

[0011] The present invention provides a method for preparing a hydrophilic deepening agent based on organosilicon-modified polyacrylate emulsion. In order to further enhance the deepening effect of fabrics and improve the hand feel and hydrophilicity of the finished fabrics, organosilicon-modified polyacrylate emulsion is selected, and a certain polyether segment is added to the molecular structure, and the deepening agent is synthesized by semi-continuous seed emulsion polymerization. The deepening agent not only has an excellent deepening effect, but also can improve its water washing resistance and friction fastness, and the polyether segment can effectively improve its hydrophilicity.

[0012] The working principle of the preparation method of the present invention is as follows: Furthermore, the mass ratio of the emulsifier to the alkyl glycoside is 1.8-2.2:1.

[0013] Preferably, the mass ratio of the emulsifier to the alkyl glycoside is 2:1.

[0014] From the above description, it can be seen that the emulsifying ability of alkyl glycoside increases with the increase of the alkyl carbon chain, while the HLB value (hydrophile-lipophile balance) of alkyl glycoside decreases with the increase of the carbon chain. Changing the mass ratio of emulsifier to alkyl glycoside will affect its hydrophilicity and emulsification.

[0015] Furthermore, the mass ratio of vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate to the polyetheramine monomer is 33:33~34:16~17:2~3:7~28.

[0016] Preferably, the mass ratio of vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate to the polyetheramine monomer is 33:33.4:16.6:2.5:14.

[0017] From the above description, it can be seen that the increase in the amount of polyetheramine added will reduce the reactivity of the amino group in the molecule, forming a steric hindrance effect, resulting in a decrease in the reaction rate between it and the monomer, a decrease in the conversion rate of the product, and a decrease in the content of polyether segments in the darkening agent. Therefore, the amount of polyetheramine added should not be too large.

[0018] Furthermore, the mass ratio of the partial composite emulsifier to the mixed liquid is 2~2.5:99~100.

[0019] From the above description, it can be seen that the hydroxyethyl acrylate monomer in the mixed liquid participates in the copolymerization and makes the polymer main chain have -OH groups. If the proportion of the mixed liquid is too large, the chain segment groups will not react fully.

[0020] Furthermore, the mass ratio of the remaining composite emulsifier to part of the initiator is 1-1.5:0.1-0.2.

[0021] From the above description, it can be seen that in the preparation of seed emulsion, if the amount of initiator added is too much, it will affect the decomposition of the initiator, affect the experimental reaction rate, and lead to inadequate experiments.

[0022] Furthermore, the mass ratio of part of the composite emulsifier to the remaining composite emulsifier is 1.8-2.2:1.

[0023] Preferably, the mass ratio of part of the composite emulsifier to the remaining composite emulsifier is 2:1.

[0024] Furthermore, the reaction temperature of the remaining composite emulsifier and part of the initiator is 75-85°C.

[0025] Preferably, the reaction temperature of the remaining composite emulsifier and part of the initiator is 80°C.

[0026] Furthermore, the mass ratio of the seed emulsion, pre-emulsion, silane coupling agent and initiator in S3 is: 1~1.5:101~102:0.01~0.04:0.3~0.4.

[0027] From the above description, it can be seen that if the mass proportion of silane coupling agent is too large, hydrolysis and condensation reactions will occur during the polymerization process, and latex particles will be induced to polymerize with each other, making the average particle size of the emulsion too large and the dispersibility will become worse.

[0028] Furthermore, the mass of the silane coupling agent in S3 is 1-3% of the mass of the seed emulsion.

[0029] Preferably, the mass of the silane coupling agent in S3 is 2% of the mass of the seed emulsion.

[0030] From the above description, it can be seen that when the mass fraction of the added silane coupling agent is 2%, the prepared emulsion has a better darkening effect.

[0031] Furthermore, the reaction temperature of S3 is 75-85°C.

[0032] Preferably, the reaction temperature of S3 is 80°C.

[0033] Another technical solution adopted by the present invention is: a hydrophilic depth enhancing agent prepared by the preparation method of the hydrophilic depth enhancing agent.

[0034] The raw materials in the following examples include: materials: vinyl acetate (VA), butyl acrylate (BA), isooctyl acrylate (EHA), hydroxyethyl acrylate (HEA), silane coupling agent (KH-1706), polyetheramine, azobisisobutylamidine hydrochloride (V50), octadecyltrimethylammonium chloride (STAC), alkyl polyglycoside (APG), and deionized water.

[0035] Embodiment 1 of the present invention is: a method for preparing a hydrophilic depth enhancing agent, the steps are as follows: S1: 2.2 g of emulsifier STAC and 1.1 g of alkyl polyglycoside are prepared into a composite emulsifier; at the same time, 33 g of vinyl acetate, 33.4 g of butyl acrylate, 16.6 g of isooctyl acrylate, 2.5 g of hydroxyethyl acrylate and 14 g of polyetheramine monomer are blended to prepare a mixed solution.

[0036] S2: Pour 2 / 3 of the composite emulsifier and the entire mixed liquid into a beaker, stir at 450 rpm for 27 min to obtain a milky pre-emulsion; pour the remaining 1 / 3 of the composite emulsifier into a four-necked flask, wait until the temperature reaches 80°C, add 0.167 g of initiator V50 to obtain a seed emulsion.

[0037] S3: Maintain the temperature at 80°C, add a mixture of pre-emulsion, silane coupling agent KH-1706 and 0.333g initiator V50 to the seed emulsion, drip it all over in 2 hours, keep it warm for 2 hours, and synthesize a hydrophilic deepening agent emulsion; the mass fraction of KH-1706 is 2%.

[0038] Embodiment 2 of the present invention is: The difference between Example 2 and Example 1 is that the mass of the polyetheramine monomer is 7 g.

[0039] Embodiment 3 of the present invention is: The difference between Example 3 and Example 1 is that the mass of the polyetheramine monomer is 28 g. Embodiment 4 of the present invention is: The difference between Example 4 and Example 1 is only that the mass fraction of KH-1706 is 1%.

[0040] Embodiment 5 of the present invention is: The difference between Example 5 and Example 1 is only that the mass fraction of KH-1706 is 3%.

[0041] The fabric was treated with the darkening agent of Examples 1 to 5, and the treatment steps were: two dips and two rolls (50 g / L darkening agent) → pre-baking (100°C) → baking (180°C, 60s) → moisture regain. The following performance tests were performed on the treated fabric: ① Apparent depth test (K / S value): Tested with a colorimeter. The larger the K / S value, the darker the color; the smaller the K / S value, the lighter the color. The deepening rate is calculated by the following formula:

[0042] In the formula, and They are the K / S values ​​of the fabric before and after deepening, respectively. The test results are shown in Table 2.

[0043] ②Hydrophilicity test: use a standard dropper (25 drops / mL) to absorb more than 5mL of clean water and drop a drop of water at a height of 2cm from the treated fabric surface. Test the time taken for the fabric to absorb water under static conditions. Drop more than 3 times at different positions and take the average value. The test results are shown in Table 1.

[0044] ③ Moisture regain test: Test the fabric in the test environment according to GB / T6529-2008 "Standard atmosphere for textile conditioning and testing". The test results are shown in Table 1.

[0045] Table 1

[0046] Table 2

[0047] As shown in Table 1, the decrease of polyetheramine monomer mass will reduce the hydrophilicity of the finished fabric, and the increase of polyetheramine monomer mass will reduce the moisture regain of the finished fabric. As shown in Table 2, when the mass fraction of KH-1706 is 2%, the prepared emulsion has a good darkening effect.

[0048] ④ Hand feel test: According to the graded scoring method, the basic hand feel intensity is rated, namely the hand feel value (HV), and the score is given in numbers, with 10 points being the best and 1 point being the worst. The fabric was tested for hand feel, and the test results are shown in Table 3.

[0049] Table 3

[0050] It can be seen from Table 3 that the darkening agent of the present invention has a significant improvement in the feel of the fabric. The more the polyetheramine monomer and KH-1706 are added, the worse the feel of the fabric is. Based on other data, the addition ratio used in Example 1 is the most suitable for the greatest improvement in the feel.

[0051] ⑤ Washing resistance test, according to the standard GB / T 8629-2017, taking into account the laboratory washing machine test conditions, using enzyme-containing fluorescent brightener-free washing powder [model JIS K 3371 (category 1)], the dosage is 1.33g / L, the temperature is 40±3℃, the water level is 40L, the time is 15min, the dehydration time is 3min, the fabric is washed three times, and then hung to dry. The washed fabric is tested for hydrophilicity, moisture regain and apparent depth, and the test results are shown in Tables 4 and 5.

[0052] Table 4

[0053] It can be seen from Table 4 that washing will greatly affect the hydrophilicity of the fabric treated with the darkening agent of the present invention, and slightly affect its moisture regain.

[0054] Table 5

[0055] It can be seen from Table 5 that washing has almost no effect on the darkening effect of the fabric treated with the darkening agent of the present invention.

[0056] Embodiment 6 of the present invention is: a method for preparing a hydrophilic depth enhancing agent, the steps are as follows: S1: 1.98 g of emulsifier STAC and 1.1 g of alkyl polyglycoside are prepared into a composite emulsifier; at the same time, 33 g of vinyl acetate, 33 g of butyl acrylate, 16 g of isooctyl acrylate, 2 g of hydroxyethyl acrylate and 14 g of polyetheramine monomer are blended to prepare a mixed solution.

[0057] S2: Pour 2 / 3 of the composite emulsifier and the entire mixed liquid into a beaker, stir at 450 rpm for 25 min to obtain a milky pre-emulsion; pour the remaining 1 / 3 of the composite emulsifier into a four-necked flask, wait until the temperature reaches 75°C, add 0.167 g of initiator V50 to obtain a seed emulsion.

[0058] S3: Maintain the temperature at 75°C, add a mixture of pre-emulsion, silane coupling agent KH-1706 and 0.333g initiator V50 to the seed emulsion, drip it all over in 2 hours, keep it warm for 2 hours, and synthesize a hydrophilic deepening agent emulsion; the mass fraction of KH-1706 is 2%.

[0059] Embodiment 7 of the present invention is: a method for preparing a hydrophilic depth enhancing agent, the steps are as follows: S1: 2.42 g of emulsifier STAC and 1.1 g of alkyl polyglycoside were prepared into a composite emulsifier; at the same time, 33 g of vinyl acetate, 34 g of butyl acrylate, 17 g of isooctyl acrylate, 3 g of hydroxyethyl acrylate and 14 g of polyetheramine monomer were blended to prepare a mixed solution.

[0060] S2: Pour 2 / 3 of the composite emulsifier and the entire mixed liquid into a beaker, stir at 450 rpm for 30 min to obtain a milky pre-emulsion; pour the remaining 1 / 3 of the composite emulsifier into a four-necked flask, wait until the temperature reaches 85°C, add 0.167 g of initiator V50 to obtain a seed emulsion.

[0061] S3: Maintain the temperature at 85°C, add a mixture of pre-emulsion, silane coupling agent KH-1706 and 0.333g initiator V50 to the seed emulsion, drip it all over in 2 hours, keep it warm for 2 hours, and synthesize a hydrophilic deepening agent emulsion; the mass fraction of KH-1706 is 2%.

[0062] Embodiment 8 of the present invention is: a hydrophilic deepening agent prepared by the preparation method of the above-mentioned hydrophilic deepening agent.

[0063] In summary, the hydrophilic depth enhancing agent and the preparation method thereof provided by the present invention have the following advantages: 1. The emulsion obtained by silicone-modified polyacrylate has a better darkening effect. The darkening agent can also improve the feel, washability and friction fastness of the fabric.

[0064] 2. By adding polyether segments into the modified emulsion, it has excellent deepening effect and excellent hydrophilic properties.

[0065] 3. The preparation method of the present invention is simple and quick and uses fluorine-free materials, which is more environmentally friendly.

[0066] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the specification of the present invention, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing a hydrophilic deepening agent, characterized in that: The following steps are involved: S1: preparing a composite emulsifier by mixing an emulsifier and an alkyl polyglycoside; blending vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate with a polyetheramine monomer to prepare a mixed solution; S2: adding part of the composite emulsifier to the mixed solution and mixing and emulsifying to obtain a pre-emulsion; reacting the remaining composite emulsifier with part of the initiator to obtain a seed emulsion; S3: adding the pre-emulsion, the silane coupling agent and the remaining initiator into the seed emulsion to react and obtain a hydrophilic deepening agent.

2. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the emulsifier to the alkyl glycoside is 1.8-2.2:

1.

3. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the vinyl acetate, butyl acrylate, isooctyl acrylate and hydroxyethyl acrylate to the polyetheramine monomer is 33:33-34:16-17:2-3:7-28.

4. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the partial composite emulsifier to the mixed liquid is 2-2.5:99-100.

5. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the remaining composite emulsifier to part of the initiator is 1-1.5:0.1-0.

2.

6. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the part of the composite emulsifier to the remaining composite emulsifier is 1.8-2.2:

1.

7. The method for preparing the hydrophilic depth enhancing agent according to claim 1, characterized in that: The reaction temperature of the remaining composite emulsifier and part of the initiator is 75-85°C.

8. The method for preparing the hydrophilic deepening agent according to claim 1, characterized in that: The mass ratio of the seed emulsion, pre-emulsion, silane coupling agent and initiator in S3 is: 1~1.5:101~102:0.01~0.04:0.3~0.

4.

9. The method for preparing the hydrophilic depth enhancing agent according to claim 1, characterized in that: The reaction temperature of S3 is 75-85°C.

10. A hydrophilic depth enhancing agent prepared by the preparation method of the hydrophilic depth enhancing agent according to any one of claims 1 to 9.

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