Special hand feeling modified silica gel for textile fabrics and preparation method thereof

Abstract

The invention discloses hand feeling modified silica gel special for textiles and a preparation method of the hand feeling modified silica gel, and belongs to the field of functional textile coating materials. The high-temperature-resistant silicone oil composition is prepared from the following components in parts by weight: 45 to 65 parts of phenyl silicone oil matrix, 10 to 20 parts of polyether block copolymer, 5 to 12 parts of CaCO3 / glass bead compound, 1.5 to 3 parts of closed polyurethane siloxane, 2 to 4 parts of rosin derivative grafted vinyl silane and 0.5 to 1.5 parts of Pt / I-catalyst. The coating is endowed with low-temperature flexibility and initial high friction property through phenyl silicone oil; the polyether block copolymer realizes humidity response adjustment; nano CaCO3 and glass beads are compounded through KH-550 to form a gradient micro-nano structure, so that the air permeability is high, and the frictional resistance is reduced; closed polyurethane siloxane (120 DEG C deblocking-NCO) and rosin derivative silane (160 DEG C methoxy condensation) are subjected to sequential synergistic bonding of the chemical fiber, and high adhesive force is provided; the comprehensive performance of the coating is obviously improved.

Description

Technical Field

[0001] This invention belongs to the field of functional textile coating materials, specifically relating to textile-specific hand-feel modified silicone and its preparation method. Background Technology

[0002] In the textile industry, silicone coatings are widely used in functional products such as anti-slip underwear straps, lace socks, and sportswear due to their excellent anti-slip properties, elasticity, environmental friendliness, and aesthetics.

[0003] Patent application CN119101465A discloses a liquid silicone rubber feel treatment agent, its preparation method, and its application. The liquid silicone rubber feel treatment agent, by weight, comprises 80-100 parts vinyl silicone oil, 10-20 parts polydimethyl silicone oil, 10-20 parts reinforcing filler, 5-15 parts modified hydrogen-containing silicone oil A, 2-6 parts modified hydrogen-containing silicone oil B, 0.1-0.5 parts platinum catalyst, and 0.01-0.1 parts inhibitor. Through the synergistic effect of the dual modified hydrogen-containing silicone oils (Type A / B), it balances abrasion resistance (POSS enhancement) and mildew resistance (chitosan / curcumin), making it suitable for humid and hot environments. The platinum catalyst system ensures a strong bond with the silicone leather substrate, resulting in outstanding scratch resistance. However, its process is relatively complex. Modified hydrogen-containing silicone oil B requires three-step synthesis, and special raw materials such as POSS-vinyl are expensive and difficult to mass-produce. Patent application CN118956159A discloses a silicone slip-feeling additive for improving the smooth feel of silicone and its application. The silicone slip-feeling additive for improving the smooth feel of silicone includes the following components in parts by weight: 100 parts of ethylene silicone; 190-210 parts of inorganic filler; 1.1-1.3 parts of composite silicone oil; and 27-33 parts of composite modifier. The composite modifier is a compound of cerium oxide, lead cyanurate, and zinc borate. However, its lead-containing compound (lead cyanurate) may be subject to regulations. Moreover, its function is relatively simple, focusing only on slip-feeling and not taking into account extended needs such as antibacterial / anti-fouling.

[0004] Therefore, it is of great significance to develop a textile-specific modified silicone that combines excellent hand feel, long-lasting adhesion, and breathability and comfort. Summary of the Invention

[0005] The purpose of this invention is to provide a special hand-feel modified silicone for textiles and its preparation method, so as to improve anti-slip properties and improve the softness of silicone.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] Textile-specific hand-feel modified silicone, by weight, comprises 45-65 parts phenyl silicone oil matrix, 10-20 parts polyether block copolymer, 5-12 parts CaCO3 / glass microsphere composite, 1.5-3 parts blocked polyurethane siloxane, 2-4 parts rosin derivative grafted vinyl silane, and 0.5-1.5 parts Pt / I- catalyst.

[0008] Furthermore, the polyether block copolymer is prepared by the following steps:

[0009] PEG-PPG-PEG, hydrogen-containing silicone oil, and ethynylcyclohexanol were heated to 78-82℃ under nitrogen protection, and Pt-DVTMS catalyst was slowly added dropwise. The temperature was then raised to 94-96℃, and the reaction was carried out for 4-4.5 hours. After the reaction was completed, the temperature was lowered to 58-62℃, activated carbon was added, and the mixture was stirred. After filtration, washing, and devolatilization and drying, the polyether block copolymer was obtained.

[0010] Furthermore, the weight ratio of the PEG-PPG-PEG, hydrogen-containing silicone oil, ethynylcyclohexanol, Pt-DVTMS catalyst and activated carbon is (68-70):(30-32):(16-17):(0.015-0.025):(3-4).

[0011] Furthermore, the devolatilization drying is carried out under reduced pressure of -(0.05-0.055) MPa for 30-40 min, and under deep devolatilization of -(0.09-0.095) MPa for 1.5-2 h.

[0012] Furthermore, the CaCO3 / glass microsphere composite is prepared by the following steps:

[0013] Nano-CaCO3 was added to anhydrous ethanol and sonicated to obtain a suspension. Glass microspheres were soaked in dilute hydrochloric acid, washed with water and dried to obtain pretreated glass microspheres. KH-550 was added to the suspension, heated and stirred, the pretreated glass microspheres were added, stirring was continued, the mixture was filtered and dried under vacuum to obtain the CaCO3 / glass microsphere composite.

[0014] Furthermore, the ratio of the amount of nano-CaCO3, anhydrous ethanol, KH-550 and pretreated glass microspheres is (190-210):(300-320):(5.5-6.5):(95-105).

[0015] Furthermore, the nano-CaCO3 particles have a diameter of 45-55 nm; the glass microspheres have a diameter of 8-12 μm.

[0016] Furthermore, the blocked polyurethane siloxane is prepared by the following steps:

[0017] Hydroxysilicone oil and toluene were dehydrated and cooled, then HDI and DBTL were added. The mixture was heated and reacted under nitrogen protection, cooled and diluted, and filtered to obtain a terminal NCO intermediate. The terminal NCO intermediate and xylene were heated and stirred, toluene ethyl ketone oxime was added dropwise, the mixture was heated and reacted, precipitated, separated by centrifugation, and dried under vacuum to obtain a blocked polyurethane siloxane.

[0018] Furthermore, the weight ratio of the hydroxyl silicone oil, HDI and DBTL is (90-110):(16-18):(0.03-0.06); the weight ratio of the terminal NCO intermediate and toluene acetone oxime is (90-110):(22-27).

[0019] Furthermore, the rosin derivative grafted with vinylsilane is prepared by the following steps:

[0020] After dissolving rosin acrylate and THF, mercaptopropyltrimethoxysilane and AIBN were added. The mixture was heated and stirred in the dark under nitrogen protection, cooled to precipitate, and then centrifuged and vacuum dried to obtain the rosin derivative grafted vinylsilane.

[0021] Furthermore, the weight ratio of the rosin acrylate, THF, mercaptopropyltrimethoxysilane and AIBN is (330-350):(240-260):(80-90):(3-4).

[0022] Furthermore, the phenyl silicone oil matrix is ​​a vinyl-terminated silicone oil with a phenyl content of 15% to 20%.

[0023] Furthermore, the Pt / I- catalyst is a mixture of platinum catalyst and diphenyliodohexafluorophosphate in a molar ratio of 1:(1.5-2).

[0024] A method for preparing hand-feel modified silicone for textiles includes the following steps:

[0025] S1. The phenyl silicone oil matrix, polyether block copolymer, and rosin derivative grafted vinyl silane are stirred evenly under vacuum. Then, CaCO3 / glass microsphere composite, blocked polyurethane siloxane and Pt / I-catalyst are added and mixed evenly to obtain a premixed adhesive.

[0026] S2. Apply the premixed adhesive with a scraper; expose to a 300-400nm light source for 3-5 seconds, and heat in a tunnel oven according to a gradient program: 80±2℃ hot air curing for 2-2.5min, 120±3℃ hot air curing for 1-1.5min, and 160±5℃ hot air curing for 30-60s.

[0027] S3. After curing, immerse in citric acid solution, use ultrasound assistance, neutralize and wash with water, and dry with hot air to obtain textile-specific hand-feel modified silicone.

[0028] The beneficial effects of this invention are:

[0029] (1) The phenyl silicone oil matrix used in this invention provides low-temperature flexibility and initial high friction, while the humidity-responsive characteristics of the polyether block copolymer enable the hydrophilic segments of the coating to migrate and form a hydration layer in a humid environment, reducing the wet friction coefficient. Specifically, the polyether block copolymer forms an interpenetrating network with the siloxane backbone through a precise block reaction between PEG-PPG-PEG and hydrogen-containing silicone oil, giving the coating a skin-like soft feel. At the same time, the introduction of ethynylcyclohexanol enhances the compatibility with phenyl silicone oil and improves the tensile resilience.

[0030] (2) In the filler system used in this invention, nano-CaCO3 and glass microspheres are composited by KH-550 coupling agent to form a micro-nano multi-level structure in the matrix. This reduces frictional resistance through the rolling effect of microspheres and improves wear resistance by filling with nanoparticles. Moreover, the amount of composite filler is low, avoiding the deterioration of air permeability caused by traditional high filling.

[0031] (3) The closed polyurethane siloxane and rosin derivative grafted vinyl silane used in this invention synergistically strengthen the interface during the curing process: at 120°C, the closed polyurethane siloxane de-encapsulates and releases -NCO, forming covalent bonds with polyester / nylon; at 160°C, the methoxyl groups of the rosin derivative grafted vinyl silane undergo methoxyl hydrolysis and condensation, further densifying the interface network and improving adhesion retention. The catalytic system employs a Pt / I- dual-component synergy, with the platinum catalyst dominating the hydrosilylation reaction, while the iodide salt promotes the crosslinking of the polyurethane siloxane through the Lewis acid effect, thereby improving curing efficiency. Detailed Implementation

[0032] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0033] Example 1

[0034] This embodiment provides a special hand-feel modified silicone for textiles, which is prepared through the following steps:

[0035] S1. 68.8 parts of PEG-PPG-PEG, 31.2 parts of hydrogen-containing silicone oil and 0.02 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.6 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0036] S2. Add 200 parts of nano-CaCO3 (average particle size 50nm) to 300 parts of anhydrous ethanol and sonicate (power 800W, frequency 40kHz) for 30min to obtain a uniform suspension A; soak 100 parts of glass microspheres (average particle size 10μm) in 5% dilute hydrochloric acid for 10min, wash with water until neutral, dry at 120℃, add 6 parts of KH-550 to suspension A, stir at 60℃ for 2h (speed 500rpm), add pretreated glass microspheres, continue stirring for 1h, filter, and vacuum dry at 120℃ for 4h to obtain CaCO3 / glass microsphere composite.

[0037] S3. Dehydrate 100 parts of hydroxyl silicone oil and 80 parts of toluene at 120℃ / -0.095MPa for 2 hours, cool to 60℃, add 16.8 parts of HDI and 0.05 parts of DBTL, heat to 85℃ under nitrogen protection, react for 3 hours, cool the reaction solution to 50℃, add 70 parts of toluene to dilute, filter through a 0.2μm filter membrane to obtain the NCO-terminated intermediate (viscosity 9500cP / 25℃);

[0038] 100 parts of terminal NCO intermediate and 50 parts of xylene were stirred at 60 °C, and 24.3 parts of toluene ethyl ketone oxime were added dropwise. The mixture was heated to 100 °C and reacted for 5 h. After the reaction was completed, the mixture was cooled to 40 °C, and 300 parts of n-hexane were added to precipitate the product. The product was then centrifuged (8000 rpm × 10 min) and dried under vacuum at 60 °C for 6 h to obtain a blocked polyurethane siloxane.

[0039] S4. Dissolve 340 parts of rosin acrylate and 250 parts of THF at 80°C, add 85.5 parts of mercaptopropyltrimethoxysilane and 3.4 parts of AIBN, stir at 80°C in the dark for 4 hours under nitrogen protection, cool to 40°C, add 500 parts of n-hexane to precipitate, centrifuge (6000 rpm × 10 min), and vacuum dry at 60°C for 6 hours to obtain rosin derivative grafted vinylsilane.

[0040] S5. Mix 55 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 15 parts of polyether block copolymer, and 3 parts of rosin derivative grafted vinyl silane under vacuum until homogeneous. Add 8 parts of CaCO3 / glass microsphere composite, 2 parts of blocked polyurethane siloxane, and 1 part of Pt / I-catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0041] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3 MPa, coating thickness 0.2 mm, dot pattern diameter 1 mm / spacing 2 mm); a 365 nm light source (intensity 80 mW / cm²) was used. 2 Expose for 4 seconds, then heat in a tunnel oven according to a gradient program: 80℃ hot air curing for 2 minutes, 120℃ hot air curing for 1 minute, and 160℃ hot air curing for 30 seconds.

[0042] After curing, the material is immersed in a 60°C citric acid solution, ultrasonically assisted (200W, 30min), neutralized and washed with water, and dried with hot air at 80°C for 10min to obtain a special hand-feel modified silicone for textiles.

[0043] Example 2

[0044] Compared with Example 1, the difference in this embodiment is that the amount of PEG-PPG-PEG in S1 is reduced, and the other components are adjusted. The specific implementation steps of S1 are as follows:

[0045] S1. 68.1 parts of PEG-PPG-PEG, 31.5 parts of hydrogen-containing silicone oil and 0.015 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.5 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0046] The remaining raw materials and preparation process are the same as in Example 1.

[0047] Example 3

[0048] Compared with Example 1, the difference in this embodiment is that the amount of PEG-PPG-PEG in S1 is increased, and the other components are adjusted. The specific implementation steps of S1 are as follows:

[0049] S1. 69.8 parts of PEG-PPG-PEG, 30.4 parts of hydrogen-containing silicone oil and 0.025 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.2 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 4 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0050] The remaining raw materials and preparation process are the same as in Example 1.

[0051] Example 4

[0052] Compared with Example 1, the difference in this embodiment is that the amount of hydroxyl silicone oil in S3 is reduced, and the other components are adjusted. The specific implementation steps of S3 are as follows:

[0053] S3. 92 parts of hydroxyl silicone oil and 80 parts of toluene were dehydrated at 120℃ / -0.095MPa for 2 hours, cooled to 60℃, 17.2 parts of HDI and 0.06 parts of DBTL were added, and the mixture was heated to 85℃ under nitrogen protection and reacted for 3 hours. The reaction solution was cooled to 50℃, diluted with 70 parts of toluene, and filtered through a 0.2μm filter membrane to obtain the NCO-terminated intermediate (viscosity 9500cP / 25℃).

[0054] 92 parts of terminal NCO intermediate and 46 parts of xylene were stirred at 60 °C, and 25.8 parts of toluene ethyl ketone oxime were added dropwise. The mixture was heated to 100 °C and reacted for 5 h. After the reaction was completed, the mixture was cooled to 40 °C, and 300 parts of n-hexane were added to precipitate the product. The product was then centrifuged (8000 rpm × 10 min) and dried under vacuum at 60 °C for 6 h to obtain a blocked polyurethane siloxane.

[0055] The remaining raw materials and preparation process are the same as in Example 1.

[0056] Example 5

[0057] Compared with Example 1, the difference in this embodiment is that the amount of hydroxyl silicone oil in S3 is increased, and the other components are adjusted. The specific implementation steps of S3 are as follows:

[0058] S3. Dehydrate 109 parts of hydroxyl silicone oil and 85 parts of toluene at 120℃ / -0.095MPa for 2 hours, cool to 60℃, add 16.1 parts of HDI and 0.03 parts of DBTL, heat to 85℃ under nitrogen protection, react for 3 hours, cool the reaction solution to 50℃, add 70 parts of toluene to dilute, filter through a 0.2μm filter membrane to obtain the NCO-terminated intermediate (viscosity 9500cP / 25℃);

[0059] 109 parts of terminal NCO intermediate and 60 parts of xylene were stirred at 60 °C, and 23.1 parts of toluene ethyl ketone oxime were added dropwise. The mixture was heated to 100 °C and reacted for 5 h. After the reaction was completed, the mixture was cooled to 40 °C, and 300 parts of n-hexane were added to precipitate the product. The product was then centrifuged (8000 rpm × 10 min) and dried under vacuum at 60 °C for 6 h to obtain a blocked polyurethane siloxane.

[0060] The remaining raw materials and preparation process are the same as in Example 1.

[0061] Example 6

[0062] Compared with Example 1, the difference in this embodiment is that the amount of rosin acrylate in S4 is reduced, and the other components are adjusted. The specific implementation steps of S4 are as follows:

[0063] S4. Dissolve 333 parts of rosin acrylate and 255 parts of THF at 80°C, add 88.5 parts of mercaptopropyltrimethoxysilane and 3.8 parts of AIBN, stir at 80°C in the dark for 4 hours under nitrogen protection, cool to 40°C, add 500 parts of n-hexane to precipitate, centrifuge (6000 rpm × 10 min), and vacuum dry at 60°C for 6 hours to obtain rosin derivative grafted vinylsilane.

[0064] The remaining raw materials and preparation process are the same as in Example 1.

[0065] Example 7

[0066] Compared with Example 1, the difference in this embodiment is that the amount of rosin acrylate in S4 is increased, and the other components are adjusted. The specific implementation steps of S4 are as follows:

[0067] S4. Dissolve 350 parts of rosin acrylate and 260 parts of THF at 80°C, add 82.5 parts of mercaptopropyltrimethoxysilane and 3.1 parts of AIBN, stir at 80°C in the dark for 4 hours under nitrogen protection, cool to 40°C, add 500 parts of n-hexane to precipitate, centrifuge (6000 rpm × 10 min), and vacuum dry at 60°C for 6 hours to obtain rosin derivative grafted vinylsilane.

[0068] The remaining raw materials and preparation process are the same as in Example 1.

[0069] Example 8

[0070] The difference between this embodiment and Embodiment 1 is that the amount of each component in S5 is adjusted. The specific implementation steps of S5 are as follows:

[0071] S5. Mix 60 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 12 parts of polyether block copolymer, and 4 parts of rosin derivative grafted vinyl silane under vacuum until homogeneous. Add 10 parts of CaCO3 / glass microsphere composite, 2.5 parts of blocked polyurethane siloxane, and 1 part of Pt / I-catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0072] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3MPa, coating thickness 0.2mm, dot pattern diameter 1mm / spacing 2mm); it was then exposed to a 365nm light source (intensity 80mW / cm2) for 4 seconds, and then heated in a tunnel oven according to a gradient program: 80℃ hot air curing for 2min, 120℃ hot air curing for 1min, and 160℃ hot air curing for 30s.

[0073] After curing, the material is immersed in a 60°C citric acid solution, ultrasonically assisted (200W, 30min), neutralized and washed with water, and dried with hot air at 80°C for 10min to obtain a special hand-feel modified silicone for textiles.

[0074] The remaining raw materials and preparation process are the same as in Example 1.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 1 is that citric acid solution impregnation is not performed. The specific implementation steps of S5 are as follows:

[0077] S5. Mix 55 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 15 parts of polyether block copolymer, and 3 parts of rosin derivative grafted vinyl silane under vacuum until homogeneous. Add 8 parts of CaCO3 / glass microsphere composite, 2 parts of blocked polyurethane siloxane, and 1 part of Pt / I-catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0078] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3 MPa, coating thickness 0.2 mm, dot pattern diameter 1 mm / spacing 2 mm); a 365 nm light source (intensity 80 mW / cm²) was used. 2 Expose for 4 seconds, then heat in a tunnel oven according to a gradient program: 80℃ hot air curing for 2 minutes, 120℃ hot air curing for 1 minute, and 160℃ hot air curing for 30 seconds; to obtain textile-specific hand-feel modified silicone.

[0079] The remaining raw materials and preparation process are the same as in Example 1.

[0080] Comparative Example 2

[0081] The difference between this comparative example and Example 1 is that the rosin derivative grafted with vinylsilane is replaced with polyhydroxy organosilicon BD-5005. The specific implementation steps are as follows:

[0082] S1. 68.8 parts of PEG-PPG-PEG, 31.2 parts of hydrogen-containing silicone oil and 0.02 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.6 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0083] S2. Add 200 parts of nano-CaCO3 (average particle size 50nm) to 300 parts of anhydrous ethanol and sonicate (power 800W, frequency 40kHz) for 30min to obtain a uniform suspension A; soak 100 parts of glass microspheres (average particle size 10μm) in 5% dilute hydrochloric acid for 10min, wash with water until neutral, dry at 120℃, add 6 parts of KH-550 to suspension A, stir at 60℃ for 2h (speed 500rpm), add pretreated glass microspheres, continue stirring for 1h, filter, and vacuum dry at 120℃ for 4h to obtain CaCO3 / glass microsphere composite.

[0084] S3. Dehydrate 100 parts of hydroxyl silicone oil and 80 parts of toluene at 120℃ / -0.095MPa for 2 hours, cool to 60℃, add 16.8 parts of HDI and 0.05 parts of DBTL, heat to 85℃ under nitrogen protection, react for 3 hours, cool the reaction solution to 50℃, add 70 parts of toluene to dilute, filter through a 0.2μm filter membrane to obtain the NCO-terminated intermediate (viscosity 9500cP / 25℃);

[0085] 100 parts of terminal NCO intermediate and 50 parts of xylene were stirred at 60 °C, and 24.3 parts of toluene ethyl ketone oxime were added dropwise. The mixture was heated to 100 °C and reacted for 5 h. After the reaction was completed, the mixture was cooled to 40 °C, and 300 parts of n-hexane were added to precipitate the product. The product was then centrifuged (8000 rpm × 10 min) and dried under vacuum at 60 °C for 6 h to obtain a blocked polyurethane siloxane.

[0086] S4. Mix 55 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 15 parts of polyether block copolymer, and 3 parts of polyhydroxy organosilicon BD-5005 under vacuum until homogeneous. Add 8 parts of CaCO3 / glass microsphere composite, 2 parts of blocked polyurethane siloxane, and 1 part of Pt / I-catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0087] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3MPa, coating thickness 0.2mm, dot pattern diameter 1mm / spacing 2mm); it was then exposed to a 365nm light source (intensity 80mW / cm2) for 4 seconds, and then heated in a tunnel oven according to a gradient program: 80℃ hot air curing for 2min, 120℃ hot air curing for 1min, and 160℃ hot air curing for 30s.

[0088] After curing, the material is immersed in a 60°C citric acid solution, ultrasonically assisted (200W, 30min), neutralized and washed with water, and dried with hot air at 80°C for 10min to obtain a special hand-feel modified silicone for textiles.

[0089] The remaining raw materials and preparation process are the same as in Example 1.

[0090] Comparative Example 3

[0091] The difference between this comparative example and Example 1 is that the blocked polyurethane siloxane is replaced with KH550. The specific implementation steps are as follows:

[0092] S1. 68.8 parts of PEG-PPG-PEG, 31.2 parts of hydrogen-containing silicone oil and 0.02 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.6 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0093] S2. Add 200 parts of nano-CaCO3 (average particle size 50nm) to 300 parts of anhydrous ethanol and sonicate (power 800W, frequency 40kHz) for 30min to obtain a uniform suspension A; soak 100 parts of glass microspheres (average particle size 10μm) in 5% dilute hydrochloric acid for 10min, wash with water until neutral, dry at 120℃, add 6 parts of KH-550 to suspension A, stir at 60℃ for 2h (speed 500rpm), add pretreated glass microspheres, continue stirring for 1h, filter, and vacuum dry at 120℃ for 4h to obtain CaCO3 / glass microsphere composite.

[0094] S3. Dissolve 340 parts of rosin acrylate and 250 parts of THF at 80°C, add 85.5 parts of mercaptopropyltrimethoxysilane and 3.4 parts of AIBN, stir at 80°C in the dark for 4 hours under nitrogen protection, cool to 40°C, add 500 parts of n-hexane to precipitate, centrifuge (6000 rpm × 10 min), and vacuum dry at 60°C for 6 hours to obtain rosin derivative grafted vinylsilane.

[0095] S4. Mix 55 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 15 parts of polyether block copolymer, and 3 parts of rosin derivative grafted vinyl silane under vacuum until homogeneous. Add 8 parts of CaCO3 / glass microsphere composite, 2 parts of KH550, and 1 part of Pt / I- catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0096] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3 MPa, coating thickness 0.2 mm, dot pattern diameter 1 mm / spacing 2 mm); a 365 nm light source (intensity 80 mW / cm²) was used. 2 Expose for 4 seconds, then heat in a tunnel oven according to a gradient program: 80℃ hot air curing for 2 minutes, 120℃ hot air curing for 1 minute, and 160℃ hot air curing for 30 seconds.

[0097] After curing, the material is immersed in a 60°C citric acid solution, ultrasonically assisted (200W, 30min), neutralized and washed with water, and dried with hot air at 80°C for 10min to obtain a special hand-feel modified silicone for textiles.

[0098] The remaining raw materials and preparation process are the same as in Example 1.

[0099] Comparative Example 4

[0100] Compared with Example 1, this comparative example differs in that the rosin derivative grafted vinyl silane is replaced with polyhydroxy organosilicon BD-5005, and the blocked polyurethane siloxane is replaced with KH550. The specific implementation steps are as follows:

[0101] S1. 68.8 parts of PEG-PPG-PEG, 31.2 parts of hydrogen-containing silicone oil and 0.02 parts of ethynylcyclohexanol were heated to 80°C under nitrogen protection, and 16.6 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0102] S2. Add 200 parts of nano-CaCO3 (average particle size 50nm) to 300 parts of anhydrous ethanol and sonicate (power 800W, frequency 40kHz) for 30min to obtain a uniform suspension A; soak 100 parts of glass microspheres (average particle size 10μm) in 5% dilute hydrochloric acid for 10min, wash with water until neutral, dry at 120℃, add 6 parts of KH-550 to suspension A, stir at 60℃ for 2h (speed 500rpm), add pretreated glass microspheres, continue stirring for 1h, filter, and vacuum dry at 120℃ for 4h to obtain CaCO3 / glass microsphere composite.

[0103] S3. Mix 55 parts of phenyl silicone oil matrix (vinyl-terminated silicone oil with 15% phenyl content), 15 parts of polyether block copolymer, and 3 parts of polyhydroxy organosilicon BD-5005 under vacuum until homogeneous. Add 8 parts of CaCO3 / glass microsphere composite, 2 parts of KH550, and 1 part of Pt / I- catalyst (platinum catalyst and diphenyliodohexafluorophosphate mixed in a molar ratio of 1:2) and mix well to obtain a premixed adhesive.

[0104] The premixed adhesive was applied to the substrate (polyester) using a doctor blade (pressure 0.3 MPa, coating thickness 0.2 mm, dot pattern diameter 1 mm / spacing 2 mm); a 365 nm light source (intensity 80 mW / cm²) was used. 2 Expose for 4 seconds, then heat in a tunnel oven according to a gradient program: 80℃ hot air curing for 2 minutes, 120℃ hot air curing for 1 minute, and 160℃ hot air curing for 30 seconds.

[0105] After curing, the material is immersed in a 60°C citric acid solution, ultrasonically assisted (200W, 30min), neutralized and washed with water, and dried with hot air at 80°C for 10min to obtain a special hand-feel modified silicone for textiles.

[0106] The remaining raw materials and preparation process are the same as in Example 1.

[0107] Comparative Example 5

[0108] The difference between this comparative example and Example 1 is that ethynylcyclohexanol is not added. The specific implementation steps of S1 are as follows:

[0109] S1. 68.9 parts of PEG-PPG-PEG and 31.3 parts of hydrogen-containing silicone oil were heated to 80°C under nitrogen protection, and 16.6 parts of Pt-DVTMS catalyst were slowly added dropwise. The temperature was then raised to 95°C and the reaction was carried out for 4 hours. After the reaction was completed, the temperature was lowered to 60°C, 3 parts of activated carbon (200 mesh) were added and stirred, filtered and washed, and then de-devoured under reduced pressure of -0.05 MPa for 30 minutes and deep de-devoured at -0.095 MPa for 1.5 hours to obtain polyether block copolymer.

[0110] The remaining raw materials and preparation process are the same as in Example 1.

[0111] Performance testing

[0112] Dry / wet friction coefficient: The friction coefficient of the textile-specific hand-feel modified silicone obtained in the various embodiments and comparative examples of this application was tested according to GB / T 10006-2021 "Determination of friction coefficient of plastic films and sheets".

[0113] Air permeability (g / m2·24h): According to GB / T 12704-2019 "Test Method for Moisture Permeability of Textiles", the air permeability of the textile-specific hand-feel modified silicone obtained in the various embodiments and comparative examples of this application was tested.

[0114] Polyester adhesion (N / cm): The polyester adhesion of the textile-specific hand-feel modified silicone obtained in the various embodiments and comparative examples of this application was tested according to GB / T 532-2008 "Determination of adhesion strength between vulcanized rubber or thermoplastic rubber and fabric".

[0115] The results are shown in Table 1:

[0116] Table 1

[0117]

[0118]

[0119] As shown in Table 1, compared with Example 1, the reduced amount of polyether block copolymer in Examples 2-3 resulted in insufficient hydrophilic segments, a thinner wet hydration layer, and weakened friction modulating ability. Conversely, the increased amount of polyether block copolymer led to excessive PESi migration to the surface, insufficient dry polar group coverage, a slight decrease in initial friction, resulting in a lower dry friction coefficient and an increased wet friction coefficient. Examples 4-7 differed from Example 1 only in the adjustment of components within a reasonable range; reducing the amount resulted in insufficient interfacial reactivity, while excessive amounts led to interfacial stress concentration and performance degradation.

[0120] Compared to Example 1, Comparative Example 1, without citric acid solution impregnation, had residual CaCO3 clogging the micropores, resulting in decreased air permeability and increased wet friction coefficient. In Example 1, the dual-effect adhesion-enhancing mechanism of the rosin phenanthrene ring rigid framework and methoxyl hydrolysis condensation achieved high adhesion. However, Comparative Example 2 (replaced with BD-5005 hydroxyl silicone oil) relied solely on physical adsorption, resulting in a sharp drop in adhesion of 21.4% to 3.3 N / cm. Comparative Example 4 (replacing both RAR and BPS) further exhibited a significant decrease in adhesion due to the lack of chemical bonding at the interface. Because the blocked polyurethane siloxane decongested at 120°C, releasing -NCO, and forming covalent bonds (urethane bonds) with polyester / nylon, it exhibited high adhesion. Comparative Example 3 (replaced with KH550) relied on hydrogen bonding, resulting in a decreasing trend in adhesion. Comparative Example 5 (without inhibitors) showed a significant decrease in adhesion due to the hydrosilylation side reaction.

[0121] This solution achieves a balance of soft touch, long-lasting adhesion, and breathability and comfort while maintaining the inherent anti-slip properties of silicone, thus meeting the functional requirements of high-end textiles through material innovation and process synergy.

[0122] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A special hand-feel modified silicone for textiles, characterized in that, By weight, it comprises 45-65 parts of phenyl silicone oil matrix, 10-20 parts of polyether block copolymer, 5-12 parts of CaCO3 / glass microsphere composite, 1.5-3 parts of blocked polyurethane siloxane, 2-4 parts of rosin derivative grafted vinyl silane and 0.5-1.5 parts of Pt / I- catalyst.

2. The textile-specific hand-feel modified silicone according to claim 1, characterized in that, The polyether block copolymer is prepared by the following steps: PEG-PPG-PEG, hydrogen-containing silicone oil, and ethynylcyclohexanol were heated to 78-82℃ under nitrogen protection, and Pt-DVTMS catalyst was slowly added dropwise. The temperature was then raised to 94-96℃, and the reaction was carried out for 4-4.5 hours. After the reaction was completed, the temperature was lowered to 58-62℃, activated carbon was added, and the mixture was stirred. After filtration, washing, and devolatilization and drying, the polyether block copolymer was obtained.

3. The textile-specific hand-feel modified silicone according to claim 2, characterized in that, The weight ratio of PEG-PPG-PEG, hydrogen-containing silicone oil, ethynylcyclohexanol, Pt-DVTMS catalyst, and activated carbon is (68-70):(30-32):(16-17):(0.015-0.025):(3-4); the devolatilization drying is carried out under reduced pressure of -(0.05-0.055) MPa for 30-40 min, and under deep devolatilization of -(0.09-0.095) MPa for 1.5-2 h.

4. The textile-specific hand-feel modified silicone according to claim 1, characterized in that, The CaCO3 / glass microsphere composite was prepared by the following steps: Nano-CaCO3 was added to anhydrous ethanol and sonicated to obtain a suspension. Glass microspheres were soaked in dilute hydrochloric acid, washed with water and dried to obtain pretreated glass microspheres. KH-550 was added to the suspension, heated and stirred, the pretreated glass microspheres were added, stirring was continued, the mixture was filtered and dried under vacuum to obtain a CaCO3 / glass microsphere composite. The ratio of nano-CaCO3, anhydrous ethanol, KH-550 and pretreated glass microspheres is (190-210):(300-320):(5.5-6.5):(95-105); the nano-CaCO3 has a particle size of 45-55 nm; and the glass microspheres have a particle size of 8-12 μm.

5. The textile-specific hand-feel modified silicone according to claim 1, characterized in that, The blocked polyurethane siloxane is prepared by the following steps: Hydroxysilicone oil and toluene were dehydrated and cooled, then HDI and DBTL were added. The mixture was heated and reacted under nitrogen protection, cooled and diluted, and filtered to obtain a terminal NCO intermediate. The terminal NCO intermediate and xylene were heated and stirred, toluene ethyl ketone oxime was added dropwise, the mixture was heated and reacted, precipitated, separated by centrifugation, and dried under vacuum to obtain a blocked polyurethane siloxane.

6. The textile-specific hand-feel modified silicone according to claim 5, characterized in that, The weight ratio of the hydroxyl silicone oil, HDI and DBTL is (90-110):(16-18):(0.03-0.06); the weight ratio of the terminal NCO intermediate and toluene acetone oxime is (90-110):(22-27).

7. The textile-specific hand-feel modified silicone according to claim 1, characterized in that, The rosin derivative grafted with vinylsilane is prepared by the following steps: After dissolving rosin acrylate and THF, mercaptopropyltrimethoxysilane and AIBN were added. The mixture was heated and stirred in the dark under nitrogen protection, cooled to precipitate, and then centrifuged and vacuum dried to obtain the rosin derivative grafted vinylsilane.

8. The textile-specific hand-feel modified silicone according to claim 7, characterized in that, The weight ratio of the rosin acrylate, THF, mercaptopropyltrimethoxysilane and AIBN is (330-350):(240-260):(80-90):(3-4).

9. The textile-specific hand-feel modified silicone according to claim 1, characterized in that, The phenyl silicone oil matrix is ​​a vinyl-terminated silicone oil with a phenyl content of 15% to 20%; the Pt / I- catalyst is a mixture of platinum catalyst and diphenyliodohexafluorophosphate in a molar ratio of 1:(1.5-2).

10. A method for preparing textile-specific hand-feel modified silicone as described in any one of claims 1-9, characterized in that, Includes the following steps: S1. The phenyl silicone oil matrix, polyether block copolymer, and rosin derivative grafted vinyl silane are stirred evenly under vacuum. Then, CaCO3 / glass microsphere composite, blocked polyurethane siloxane and Pt / I-catalyst are added and mixed evenly to obtain a premixed adhesive. S2. Apply the premixed adhesive with a scraper; expose to a 300-400nm light source for 3-5 seconds, and heat in a tunnel oven according to a gradient program: 80±2℃ hot air curing for 2-2.5min, 120±3℃ hot air curing for 1-1.5min, and 160±5℃ hot air curing for 30-60s. S3. After curing, immerse in citric acid solution, use ultrasound assistance, neutralize and wash with water, and dry with hot air to obtain textile-specific hand-feel modified silicone.

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