A kind of organic silicon hand feeling additive and its preparation method and application

Abstract

The present invention provides an organosilicon feel aid and a preparation method and application thereof. The organosilicon feel aid comprises a polymer prepared from the following raw material components according to weight percentage: (A) 15-35% acrylate-based polysiloxane monomer, wherein the acrylate-based polysiloxane monomer chain segment has at least one hydrophilic group; (B) 5-25% acrylate-terminated silane oligomer; (C) 1-5% surfactant; (D) 0.5-1% initiator; (E) balance water; application of the organosilicon feel aid in fabric finishing. The organosilicon feel aid is obtained by free radical polymerization of acrylate-based polysiloxane monomer and acrylate-terminated silane oligomer; the organosilicon feel aid can not only give fabrics better softness and smoothness, but also give fabrics better water resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of organic silicon, and specifically relates to an organic silicon feel additive and a preparation method and application thereof. Background Art

[0002] When natural fiber fabrics, such as cotton, linen, and wool, are made into fabrics, they usually need to go through bleaching, dyeing, printing, and other processing techniques or functional finishing. During the above processing, the fibers of the fabrics will be damaged to a certain extent, and the fabrics will become rough. The hand feel of synthetic fiber fabrics is usually worse than that of natural fiber fabrics. After high-temperature shaping, the hand feel becomes particularly rough and hard. Therefore, both natural fiber fabrics and synthetic fiber fabrics need to be softened to obtain good soft hand feel and performance.

[0003] Silicone-based hand-feel finishing agents are one of the hand-feel finishing agents with excellent performance, outstanding effects and wide applications. They can be divided into four generations according to their development stages: the main component of the first generation is dimethyl silicone oil, which is emulsified by mechanical emulsion method, but dimethyl silicone oil emulsion itself does not contain active groups, is not firmly bonded to fabrics, is not water-resistant, and the effect of using it alone is not ideal; the second generation is hydroxyl silicone oil emulsion and hydrogen silicone oil emulsion, but they are prone to demulsification and oil bleaching during use and are not widely used; the third generation is the introduction of polyether, epoxy, amino and other groups into polysiloxane, but generally it needs to be compounded with monofunctional polysiloxane to achieve the desired treatment effect, and the compounding ratio is difficult to grasp, which has a great impact on the application; the fourth generation is based on the finishing effect required by the fabric, and the third generation of silicone-based hand-feel finishing agents is further modified to introduce more active groups.

[0004] With the development of the industry, people have put forward higher requirements on the quality of silicone-based hand finishing agents. However, the current silicone-based hand finishing agents still have problems such as poor water fastness and poor wettability.

[0005] Therefore, developing a silicone-based hand-feel finishing agent with good hand feel, good water-based fastness and good wettability is a technical problem that needs to be solved in the art. Summary of the invention

[0006] In view of the deficiencies of the prior art, the object of the present invention is to provide a silicone feel aid for fabric finishing having good feel, good water fastness and good wettability.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an organosilicon feel finishing agent, wherein the organosilicon feel finishing agent comprises, by weight percentage, a polymer prepared from the following raw material components:

[0009] (A) 15-35% of an acrylate polysiloxane monomer, wherein the acrylate polysiloxane monomer chain segment has at least one hydrophilic group;

[0010] (B) 5~25% acrylate-terminated silane oligomer;

[0011] (C) 0.5~3% surfactant;

[0012] (D) 0.5~1% initiator;

[0013] (E) Excess water.

[0014] The above-mentioned 15~35% can be 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% and the like.

[0015] The above-mentioned 5~25% can be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, etc.

[0016] Preferably, in the component (A), the hydrophilic group is one or more of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0017] Preferably, the number average molecular weight of the component (A) is 1000-4000 g / mol.

[0018] Preferably, the number average molecular weight of the component (B) is 500-2000 g / mol.

[0019] Preferably, the solid content of the silicone feel aid is 20-45wt%.

[0020] Preferably, the surfactant includes one or a combination of two or more of anionic emulsifiers, nonionic emulsifiers and cationic emulsifiers.

[0021] Preferably, the initiator comprises a peroxide initiator.

[0022] Preferably, the preparation raw material components also include 0.5-2% neutralizer.

[0023] In a second aspect, the present invention provides a method for preparing the above-mentioned silicone feel additive, the preparation method comprising the following steps:

[0024] S1. The water in the preparation component is divided into a first part of water and a second part of water, and the surfactant is divided into a first part of the surfactant and a second part of the surfactant;

[0025] S2. The first part of water, the first part of the surfactant, the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer are mixed and emulsified. After the emulsification is completed, an initiator is added and mixed to obtain a pre-emulsion;

[0026] S3. Add the second part of water and the second part of surfactant into the reactor, stir and heat, then drop the pre-emulsion into the reactor, keep warm and react to obtain the organosilicon feel additive.

[0027] Preferably, in step S1, the mass ratio between the first part of water and the second part of water is 1:0.2-4; the mass ratio between the first part of surfactant and the second part of surfactant is 1:0.1-3.

[0028] Preferably, in step S3, the temperature of the insulation reaction is 70-85° C., and the time of the insulation reaction is 2-5 hours.

[0029] In a third aspect, the present invention provides the use of the above-mentioned hand-feel finishing auxiliary agent or the hand-feel finishing auxiliary agent prepared according to the above-mentioned method in fabric finishing.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The organic silicone feel aid for fabric finishing provided by the present invention is obtained by free radical polymerization of an acrylate-based polysiloxane monomer and an acrylate-terminated silane oligomer, wherein the acrylate-based polysiloxane monomer has a hydrophilic group, and the hydrophilic group of the acrylate-based polysiloxane monomer can give the acrylate-based polysiloxane monomer a certain emulsification property, and can be copolymerized with the acrylate-terminated silane oligomer. The obtained polymer has a high organic silicone content, a certain hydrophilicity and a silane group, and is applied to fabric finishing to not only give the fabric better softness and smoothness, but also give the fabric better water resistance. DETAILED DESCRIPTION

[0032] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0033] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0034] The acrylate-based polysiloxane monomer used in the following examples is prepared by referring to the preparation method of a UV-curable carboxyl silicone oil disclosed in Example 2 of patent CN110003475A. The specific method is as follows:

[0035] In a chamber equipped with a stirrer, condenser, and nitrogen 2 Add acrylic acid CH into the four-necked bottle with inlet and thermometer. 2 =CHCOOH (144.12 g, 2.00 mol), toluene (346.00 g), isopropanol (157.30 g), ACS-Pt-40 (0.40 g), n-hexanoic acid (4.72 g) and 170.40 g of hydrogen-containing polysiloxane were reacted at 60° C. for 1 h, then cooled to 50-60° C., and 3-acryloxypropylmethyldimethoxysilane (1091.60 g, 5.00 mol), inhibitor 701 (0.38 g) and trifluoromethanesulfonic acid (8.44 g), react for 2 to 3 hours under a vacuum degree of -0.095 to -0.10 MPa, then add methoxytrimethylsilane TMSOME (10.42 g, 0.1 mol), react for 3 hours, add ice toluene (1687.34 g), wash twice with ice water, take the oil layer, and distill under reduced pressure for 0.5 hours under a vacuum degree of -0.095 to -0.10 MPa and 80 to 85°C to obtain a colorless, transparent, viscous substance. Example 1

[0036] The raw materials for preparing a silicone feel additive include: 20g of acrylate-based polysiloxane monomer, 10g of acrylate-terminated silane oligomer (Guangzhou Dolphin New Materials Dolphin 3827, molecular weight 1500g / mol), 1g of anionic emulsifier (Clariant, Emulsogen EPA 073), 0.5g of nonionic emulsifier (Clariant, Emulsogen LCN 118), 0.7g of potassium persulfate and 66.8g of deionized water.

[0037] A preparation method of an organosilicon feel additive is as follows:

[0038] In a four-necked flask equipped with a stirrer, condenser, nitrogen N2 inlet and thermometer, add acrylic acid CH 2=CHCOOH (13.5 g), toluene (346.00 g), isopropanol (157.30 g), ACS-Pt-40 (0.40 g), hexanoic acid (4.72 g) and double-terminal hydrogenated polysiloxane (hydrogen content of 0.1 wt%, viscosity of 25 mPa.s) 170.40 g were reacted at 60 ° C for 1 h, cooled to 60 ° C, and 3-acryloxypropylmethyldimethoxysilane (109 .1g), inhibitor 701 (0.38g) and trifluoromethanesulfonic acid (8.44g), react for 3h under vacuum degree of -0.095~-0.10MPa, add methoxytrimethylsilane TMSOME (10.42g, 0.1mol), react for 3h, add ice toluene (1687.34g), wash twice with ice water, take the oil layer, and distill under reduced pressure for 0.5h under vacuum degree of -0.095~-0.10MPa and 85℃ to obtain acrylate polysiloxane monomer;

[0039] 20 g of the acrylate polysiloxane monomer obtained in step (1), 10 g of the acrylate-terminated silane oligomer, 40 g of deionized water, 0.7 g of anionic emulsifier and 0.3 g of nonionic emulsifier were added to a stirring kettle for shear emulsification. After the emulsification was completed, 0.7 g of potassium persulfate was added and mixed evenly to obtain a pre-emulsion;

[0040] Add the remaining deionized water, anionic surfactant and nonionic surfactant into the reactor, stir and heat to 75°C, add the pre-emulsion dropwise into the reactor at a uniform rate, complete the addition within 3 hours, continue to keep warm and react for 2 hours, cool to below 40°C, add ammonia water to adjust the pH to 7-7.5, discharge the material, and obtain a silicone feel additive. Example 2

[0041] The raw materials for preparing a silicone feel additive include: 25g of acrylate-based polysiloxane monomer, 15g of acrylate-terminated silane oligomer (Guangzhou Dolphin New Materials Dolphin 3827, molecular weight 1500g / mol), 0.7g of anionic emulsifier (Clariant, Emulsogen EPA 073), 0.3g of nonionic emulsifier (Clariant, Emulsogen LCN 118), 0.7g of potassium persulfate and 56.8g of deionized water.

[0042] A preparation method of an organosilicon feel additive is as follows:

[0043] In a chamber equipped with a stirrer, condenser, and nitrogen 2Propylene sulfonic acid (21.2 g), toluene (346.00 g), isopropanol (157.30 g), ACS-Pt-40 (0.40 g), hexanoic acid (4.72 g) and 170.40 g of double-terminal hydrogenated polysiloxane (hydrogen content of 0.1 wt %, viscosity of 25 mPa.s) were added to a four-necked bottle with an inlet and a thermometer. After reacting at 60 ° C for 1 h, the temperature was lowered to 50-60 ° C, and 3-acryloxypropylmethyldimethoxysilane (109.1 g), inhibitor 70 1 (0.38 g) and trifluoromethanesulfonic acid (8.44 g), react for 2 to 3 hours under a vacuum degree of -0.095 to -0.10 MPa, add methoxytrimethylsilane TMSOME (10.42 g, 0.1 mol), react for 3 hours, add ice toluene (1687.34 g), wash with ice water twice, take the oil layer, and distill under reduced pressure for 0.5 hours under a vacuum degree of -0.095 to -0.10 MPa and 80 to 85°C to obtain an acrylate-based polysiloxane monomer;

[0044] 20 g of the acrylate polysiloxane monomer obtained in step (1), 10 g of the acrylate-terminated silane oligomer, 35 g of deionized water, and 0.5 g of anionic emulsifier were added to a stirring kettle for shear emulsification. After the emulsification was completed, 0.2 g of potassium persulfate was added and mixed evenly to obtain a pre-emulsion;

[0045] Add the remaining deionized water, anionic surfactant and nonionic surfactant into the reactor, stir and heat to 75°C, add the pre-emulsion dropwise into the reactor at a uniform rate, complete the addition within 3 hours, continue to keep warm and react for 2 hours, cool to below 40°C, add ammonia water to adjust the pH to 7-7.5, discharge the material, and obtain a silicone feel additive. Example 3

[0046] The difference between this embodiment and embodiment 1 is that the amount of each component is different. The amount of each component is as follows: 35g acrylate polysiloxane monomer, 5g acrylate-terminated silane oligomer (Guangzhou Dolphin New Materials Dolphin3827, molecular weight 1500g / mol), 1g anionic emulsifier (Clariant, Emulsogen EPA 073), 0.5g nonionic emulsifier (Clariant, Emulsogen LCN 118), 0.7g potassium persulfate and 56.8g deionized water. Example 4

[0047] The difference between this embodiment and embodiment 1 is that the amount of each component is different. The amount of each component is as follows: 15g acrylate polysiloxane monomer, 25g acrylate-terminated silane oligomer (Guangzhou Dolphin New Materials Dolphin3827, molecular weight 1500g / mol), 1g anionic emulsifier (Clariant, Emulsogen EPA 073), 0.5g nonionic emulsifier (Clariant, Emulsogen LCN 118), 0.7g potassium persulfate and 56.8g deionized water.

[0048] Comparative Example 1

[0049] The difference between this comparative example and Example 1 is that in this comparative example, while keeping the total weight of the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer unchanged, the weight of the acrylate-based polysiloxane monomer is changed to 29g, and the weight of the acrylate-terminated silane oligomer is changed to 1g.

[0050] Comparative Example 2

[0051] The difference between this comparative example and Example 1 is that in this comparative example, while keeping the total weight of the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer unchanged, the weight of the acrylate-based polysiloxane monomer is changed to 1g, and the weight of the acrylate-terminated silane oligomer is changed to 29g.

[0052] Comparative Example 3

[0053] The difference between this comparative example and Example 1 is that in this comparative example, while keeping the total weight of the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer unchanged, the weight of the acrylate-based polysiloxane monomer is changed to 30 g, and the weight of the acrylate-terminated silane oligomer is changed to 0 g.

[0054] Comparative Example 4

[0055] The difference between this comparative example and Example 1 is that in this comparative example, while keeping the total weight of the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer unchanged, the weight of the acrylate-based polysiloxane monomer is changed to 0g, and the weight of the acrylate-terminated silane oligomer is changed to 30g.

[0056] Application Examples 1~4

[0057] A fabric finishing liquid comprises 2 g of the organosilicon feel aid obtained in Examples 1 to 4 and 100 g of water.

[0058] Comparative Application Examples 1~4

[0059] A fabric finishing liquid comprises 2 g of the organosilicon feel aid obtained in Comparative Examples 1 to 4 and 100 g of water.

[0060] Performance Test:

[0061] 2g of the organosilicon feel aid obtained in Examples 1 to 4 and Comparative Examples 1 to 4 and 100g of water were mixed to prepare a fabric finishing liquid, and the fabric (cotton cloth sample) was treated with the liquid according to the following finishing process: soaking (25min) - two soaking and two rolling (rolling rate 90%) - pre-baking (5min, 100°C) - baking (2min, 160°C), and the following test was carried out. The specific test method is as follows:

[0062] (1) Softness: The treated fabric was cut into 10×10 cm specifications and tested using a computer softness tester. The smaller the force required for the test, the better the softness of the test fabric.

[0063] (2) Washability: Wash the test fabric sample according to GB / T 8629-2001 “Household Washing and Drying Procedure for Textile Testing” and test the softness again according to the above method (1) after washing 10 times.

[0064] (3) Surface friction performance: The test is carried out in accordance with standard FZ / T01054-2012 "Test method for surface friction performance of fabrics". The smaller the measured surface roughness value, the better the smoothness of the test fabric sample.

[0065] The specific test results are shown in Table 1, and the untreated fabric samples were used as blank samples for comparison.

[0066] Table 1

[0067]

[0068] As can be seen from Table 1, the organosilicon feel additive for fabric finishing obtained by the present invention can impart excellent softness, water washability and smoothness to fabrics, and can be widely used in fields such as fabric softening and finishing.

[0069] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A silicone feel additive, characterized in that: According to weight percentage, it is prepared from the following raw material components: (A) 15-35% of an acrylate polysiloxane monomer, wherein the acrylate polysiloxane monomer chain segment has at least one hydrophilic group; (B) 5~25% acrylate-terminated silane oligomer; (C) 0.5~3% surfactant; (D) 0.5~1% initiator; (E) Residual water; The number average molecular weight of the component (A) is 1000-4000 g / mol; The number average molecular weight of the component (B) is 500-2000 g / mol.

2. The organic silicon feel additive according to claim 1, characterized in that: In the component (A), the hydrophilic group is one or more of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

3. The organic silicon feel additive according to claim 1, characterized in that: The solid content of the organosilicon feel additive is 20-45wt%.

4. The organic silicon feel additive according to claim 1, characterized in that: The surfactant includes one or a combination of two or more of anionic emulsifiers, nonionic emulsifiers and cationic emulsifiers.

5. The organic silicon feel aid according to claim 1, characterized in that: The initiator includes a peroxide initiator.

6. The organic silicon feel aid according to claim 1, characterized in that: The raw material components for preparation also include 0.5-2% neutralizer.

7. A method for preparing the organosilicon feel additive according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: S1. The water in the preparation component is divided into a first part of water and a second part of water, and the surfactant is divided into a first part of the surfactant and a second part of the surfactant; S2. The first part of water, the first part of the surfactant, the acrylate-based polysiloxane monomer and the acrylate-terminated silane oligomer are mixed and emulsified. After the emulsification is completed, an initiator is added and mixed to obtain a pre-emulsion; S3. Add the second part of water and the second part of surfactant into the reactor, stir and heat, then drop the pre-emulsion into the reactor, keep warm and react, and obtain the silicone feel additive for fabric finishing.

8. The preparation method according to claim 7, characterized in that: In step S1, the mass ratio between the first part of water and the second part of water is 1:0.2-4; the mass ratio between the first part of surfactant and the second part of surfactant is 1:0.1-3.

9. The preparation method according to claim 7, characterized in that: In step S3, the temperature of the insulation reaction is 70-85° C., and the time of the insulation reaction is 2-5 hours.

10. Use of the organosilicon feel aid according to any one of claims 1 to 6 or the organosilicon feel aid prepared by the preparation method according to any one of claims 7 to 9 in fabric finishing.

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