A high-fastness organic silicon high-elastic coating adhesive and preparation method thereof

Abstract

The invention discloses a high-fastness organosilicon high-elastic coating adhesive and a preparation method thereof, and specifically relates to the technical field of textile coating processing. The coating adhesive is prepared from the following raw materials: 800-1200 parts of α,ω-dihydroxy-terminated polydimethylsiloxane, 10-20 parts of p-toluenesulfonic acid, 8-16 parts of triethanolamine, 1-3 parts of α,ω-terminated hydroxyl silicone oil, 65-75 parts of toluene, 3-6 parts of cross-linking agent, 1-3 parts of coupling agent, and 2-4 parts of catalyst. The high-fastness organosilicon high-elastic coating adhesive for fabric coating of the invention has the characteristics of high resilience, wrinkle resistance, high elasticity, crisp hand feeling and smoothness, and has good coating fastness, especially when adding color coating, it has high dry and wet friction fastness and water washing fastness.

Description

Technical Field

[0001] The invention relates to the technical field of textile coating processing, and in particular to a high-fastness organic silicon high-elastic coating adhesive for fabric coating and a preparation method thereof. Background Art

[0002] Silicone coating adhesives have been widely used in the textile industry due to their excellent mechanical properties, high elasticity, high and low temperature resistance, weather resistance, smoothness, water repellency and physiological inertness. Among them, the paper-like adhesive coating with silicone high-elastic coating adhesive as the main body has a strong paper texture, good elasticity, hard but not brittle, and straight but not folded after coating. At the same time, it has excellent waterproof and breathable properties, and enhances the tear strength and wrinkle resistance of the fabric. This kind of style coating has been widely used, especially on cotton and linen fabrics with color paste for scraping coating, and then made into ready-made clothes after washing. Its texture is draped and straight, rebounds and wrinkle-resistant, and is breathable and breathable, making the fabric more suitable for wearing. However, its disadvantage is that the existing silicone high-elastic coating adhesives often have average fastness and poor color fixing effect. Especially when used as dark coatings, the color fades heavily after washing, which greatly reduces the effect and causes waste of pigment paste.

[0003] Patent CN103898766A discloses "a highly elastic and scratchy organic silicone fabric coating agent and its preparation method", which uses a mixture of hydroxy silicone oil, methyl silicone oil and hydrogen-containing silicone oil as the main coating glue, and adds coupling agents, organic tin catalysts and other additives to mix to obtain a highly elastic and scratchy organic silicone fabric coating agent. After coating, the fabric can obtain a highly elastic and scratchy and smooth and oily feel. The hydroxy silicone oil used in the main glue has a low viscosity (50000-200000mPa·s) and is a linear body. It is combined with hydrogen-containing silicone oil for dehydrogenation reaction to produce cross-linking, and the cross-linking density and fastness of the resulting film are low; and a large amount of methyl silicone oil is added to the main glue for plasticization and lubrication, which also reduces the elasticity and fastness of the film, and cannot meet the fastness requirements during color coating.

[0004] Patent CN110158321A discloses "a kind of organic silicon textile coating adhesive and its preparation method". α,ω-dihydroxy-terminated polydimethylsiloxane and fumed white carbon black are stirred under vacuum conditions to obtain a main adhesive, a crosslinking agent, a coupling agent, and a composite catalyst of organic titanium and organic bismuth are added, and then stirred under vacuum conditions to obtain a single-component decarboxylation type organic silicon textile coating adhesive with fast curing and good storage stability, which can effectively improve the adhesion to the surface of the fabric. The α,ω-dihydroxy-terminated polydimethylsiloxane used in the main adhesive has a low viscosity (8000-150000mPa·s) and is linear. The crosslinking density of the formed adhesive film is low and the elasticity is insufficient. Moreover, adding a large number of white carbon black as a reinforcing agent will affect the elastic feel after film formation; after adding more white carbon black, the viscosity of the glue is greatly increased, and it is not easy to penetrate into the inside of the fabric to form a coating crosslinking. Especially when the thicker fabric is coated, the fastness is poor and cannot meet the fastness requirements during color coating. Summary of the invention

[0005] To this end, the present invention provides a high-fastness organic silicon high-elastic coating adhesive for fabric coating and a preparation method thereof, so as to solve the problems that the existing coating adhesive has low elasticity and fastness and cannot meet the needs. The present invention uses the coating adhesive to coat the fabric, so that the fabric has a paper texture, high resilience, wrinkle resistance, and smoothness, and has good dry and wet friction fastness and washing fastness when color coating.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] According to one aspect of the present invention, a high-fastness organic silicone high-elastic coating glue is provided, which is prepared from the following raw materials: 800-1200 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 glue), 10-20 parts of p-toluenesulfonic acid, 8-16 parts of triethanolamine, 1-3 parts of α,ω-terminated hydroxyl silicone oil (linear body), 65-75 parts of toluene, 3-6 parts of crosslinking agent, 1-3 parts of coupling agent, and 2-4 parts of catalyst.

[0008] Furthermore, the viscosity of the α,ω-dihydroxy-terminated polydimethylsiloxane (107 glue) is 20000-120000 mPa·s at 25°C.

[0009] Furthermore, the viscosity of the α,ω-terminated hydroxyl silicone oil is 50-120 mPa·s at 25°C.

[0010] Furthermore, the crosslinking agent is one or more of methyltriacetoxysilane, ethyltriacetoxysilane, and propyltriacetoxysilane.

[0011] Furthermore, the coupling agent is one or more of γ-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and γ-piperazinepropylmethyldimethoxysilane.

[0012] Furthermore, the catalyst is bismuth isooctanoate and / or zinc isooctanoate.

[0013] According to another aspect of the present invention, a method for preparing a high-fastness organic silicone high-elastic coating adhesive is provided, the method comprising:

[0014] Step 1, first take 800-1200 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber), 10-20 parts of p-toluenesulfonic acid, and 8-16 parts of triethanolamine, knead and catalyze, perform low-temperature polycondensation, and neutralize to obtain raw rubber;

[0015] Step 2: Take 24-32 parts of raw rubber, 1-3 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 65-75 parts of toluene in a stainless steel kettle and stir the materials to obtain a base rubber;

[0016] Step 3: Add 3-6 parts of a crosslinking agent, 1-3 parts of a coupling agent, and 2-4 parts of a catalyst into the base glue and stir evenly to obtain a high-fastness organic silicone high-elastic coating glue.

[0017] As an example, the preparation method of the high-fastness organosilicon high-elastic coating adhesive of the present invention is:

[0018] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) and 10-20 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, then discharge the material, place it in a -5 to -15°C cold storage for 24 to 48 hours, then return it to the kneader, add 8 to 16 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0019] 2. Take 24-32 parts of raw rubber (I), 1-3 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 65-75 parts of toluene, add them into a stainless steel kettle to make a glue, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 3-6 parts of cross-linking agent, 1-3 parts of coupling agent, and 2-4 parts of catalyst and stir evenly to obtain the product.

[0020] Since the addition of crosslinking agent, coupling agent and catalyst will give the product a certain shelf life, they should be added to the base rubber (II) before use to obtain the final product.

[0021] The α,ω-dihydroxy-terminated polydimethylsiloxane (107 glue) preferably has a viscosity of 20000-120000 mPa·s (25° C.);

[0022] The α,ω-terminated hydroxyl silicone oil (linear body) preferably has a viscosity of 50-120 mPa·s (25° C.);

[0023] The crosslinking agent is methyl triacetoxysilane, ethyl triacetoxysilane or propyl triacetoxysilane;

[0024] The coupling agent is γ-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane or γ-piperazinepropylmethyldimethoxysilane;

[0025] The catalyst is bismuth isooctanoate or zinc isooctanoate;

[0026] Product technical indicators:

[0027] Appearance: colorless, transparent, viscous liquid;

[0028] Solid content: 25-35%;

[0029] Viscosity: 30000-60000 mPa·s (25°C).

[0030] The present invention has the following advantages:

[0031] The high-fastness organic silicone high-elastic coating adhesive of the present invention adopts linear medium-viscosity α, ω-dihydroxy polydimethylsiloxane (107 adhesive), catalyzes condensation under acidic conditions to produce a certain degree of cross-linking reaction, so that the hydroxyl groups in the molecular chain are changed from linear two ends to multi-end types, and then continues to catalyze condensation under low temperature conditions to form a network cross-linked structure with ultra-large molecular weight, and finally obtains a stable high-viscosity ultra-large molecular raw rubber (viscosity of more than 10 million) through neutralization, which has excellent elasticity and a multi-hydroxy cross-linked skeleton; after toluene sol-gelation, a basic glue with moderate viscosity and content can be obtained, which has good fluidity and coatability, and can quickly penetrate into the interior of the fabric after being coated on the surface of the fabric; at the same time, it is equipped with an appropriate amount of small-molecule α, ω-terminated hydroxyl silicone oil (linear body), which increases a sufficient amount of silanol groups as cross-linking points, and under the action of a cross-linking agent and a coupling agent, a firm and dense macromolecular film is quickly formed on the surface and inside of the fabric after high-temperature catalysis, which greatly improves the elasticity and wrinkle resistance of the coated fabric, and has good bonding fastness, friction fastness and water washing resistance.

[0032] The cross-linking agent used in the high-fastness organic silicone high-elastic coating adhesive of the present invention is a deacidified methyl / ethyl / propyl triacetoxysilane, which undergoes condensation cross-linking with the silanol groups in the main adhesive after drying and catalysis to form a macromolecular network structure. Compared with the traditional dealcoholized silane cross-linking agent, it has better bonding performance with the fabric; the selected coupling agents are all amino-containing types. While undergoing condensation cross-linking with the main adhesive, the active amino group and epoxy group at the other end can undergo cross-linking reaction with the active groups on the fiber surface, such as hydroxyl, amino, carboxyl, ester, etc., to form a stable chemical bond, thereby improving the coating's bonding strength to the fabric, thereby improving the fabric's resistance to friction and washing.

[0033] The catalysts used in the preparation process of the high-fastness organic silicone high-elastic coating adhesive of the present invention are selected from zinc isooctanoate and bismuth isooctanoate, which are environmentally friendly catalysts, comply with various domestic and foreign laws and regulations, can replace organic tin catalysts, have a relatively mild catalytic rate, and the catalytic effect can reach the level of organic tin catalysts.

[0034] The high-fastness organosilicon high-elastic coating adhesive for fabric coating of the present invention has the characteristics of high resilience, wrinkle resistance, high elasticity, crisp hand feeling and smoothness, and has good coating fastness, especially high dry and wet friction fastness and washing fastness when adding color coating. DETAILED DESCRIPTION

[0035] The following is a description of the implementation of the present invention by specific embodiments. People familiar with the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] The embodiments of the present invention are all formulated according to the mass ratio of raw materials.

[0037] Example 1

[0038] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0039] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 20000 mPa·s and 10 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 48 hours, return it to the kneader, add 8 parts of triethanolamine, knead for 1 hour, and obtain raw rubber (I) after sufficient neutralization;

[0040] 2. Take 24 parts of raw rubber (I), 1 part of α,ω-terminated hydroxyl silicone oil (linear body), and 75 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 3 parts of methyltriacetoxysilane, 1 part of γ-aminopropyltriethoxysilane, and 2 parts of bismuth isooctanoate and stir evenly to obtain the product.

[0041] Example 2

[0042] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0043] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 50000 mPa·s and 10 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 48 hours, return it to the kneader, add 8 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0044] 2. Take 24 parts of raw rubber (I), 1 part of α,ω-terminated hydroxyl silicone oil (linear body), and 75 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 4 parts of ethyltriacetoxysilane, 2 parts of N-aminoethyl-3-aminopropylmethyldimethoxysilane, and 2 parts of zinc isooctanoate and stir evenly to obtain the product.

[0045] Example 3

[0046] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0047] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 50000 mPa·s and 15 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 36 hours, return it to the kneader, add 12 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0048] 2. Take 28 parts of raw rubber (I), 2 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 70 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 5 parts of propyl triacetoxy silane, 2 parts of γ-aminopropyl triethoxy silane, and 3 parts of bismuth isooctanoate and stir evenly to obtain the product.

[0049] Example 4

[0050] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0051] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 80000 mPa·s and 15 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 36 hours, return it to the kneader, add 12 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0052] 2. Take 28 parts of raw rubber (I), 2 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 70 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 4 parts of methyltriacetoxysilane, 2 parts of γ-piperazinepropylmethyldimethoxysilane, and 3 parts of zinc isooctanoate and stir evenly to obtain the product.

[0053] Example 5

[0054] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0055] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 80000 mPa·s and 20 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 24 hours, return it to the kneader, add 16 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0056] 2. Take 32 parts of raw rubber (I), 3 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 65 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 5 parts of ethyltriacetoxysilane, 3 parts of γ-aminopropyltriethoxysilane, and 4 parts of bismuth isooctanoate and stir evenly to obtain the product.

[0057] Example 6

[0058] This embodiment provides a method for preparing a high-fastness organic silicone high-elastic coating adhesive:

[0059] 1. Add 1000 parts of α,ω-dihydroxy-terminated polydimethylsiloxane (107 rubber) with a viscosity of 120000 mPa·s and 20 parts of p-toluenesulfonic acid into a Z-type kneader, knead at room temperature for 1 hour, discharge the material, place it in a -5 to -15°C cold storage for 24 hours, return it to the kneader, add 16 parts of triethanolamine, knead for 1 hour, and fully neutralize to obtain raw rubber (I);

[0060] 2. Take 32 parts of raw rubber (I), 3 parts of α,ω-terminated hydroxyl silicone oil (linear body), and 65 parts of toluene, add them into a stainless steel kettle, stir evenly until there are no lumps and it is transparent, and obtain the base rubber (II); then add 6 parts of propyl triacetoxy silane, 3 parts of N-aminoethyl-3-aminopropyl methyl dimethoxy silane, and 4 parts of zinc isooctanoate, stir evenly, and obtain the product.

[0061] Comparative Example 1

[0062] The product used in this comparative example is solvent-based paper-feel coating adhesive TF-360 sold on the market by a certain company.

[0063] Comparative Example 2

[0064] The product used in this comparative example is DK-781, a solvent-based high-elastic coating adhesive commercially available from a certain company.

[0065] Comparative Example 3

[0066] This comparative example provides a kind of organic silicon textile coating adhesive according to the method of Example 1 of patent CN110158321A.

[0067] Experimental Example 1

[0068] This experimental example tests the application performance of high-fastness silicone high-elastic coating adhesive coating:

[0069] Take 100 parts of each of Examples 1-6 and Comparative Examples 1-3, add 10 parts of silica gel color paste to each, stir evenly to make color coating glue, and then coat on pure cotton (specification: 40*40 / 133*72 twill) and linen-viscose (specification: 7*7 / 30*30) base fabrics that have not been treated with water repellent, and bake at 160-170°C for 2 minutes;

[0070] Washing resistance test: According to GB / T 8629-2017 "Household washing and drying procedures for textile testing" (5N procedure, 10 times, drying); and GB / T 250-2008 "Grey scale for assessing color change in textile color fastness tests"

[0071] Dry and wet rubbing fastness: according to GB / T 3920-2008 "Textiles - Colour fastness - Rubbing fastness";

[0072] Evaluation of high elasticity and crispness effect: based on the comprehensive evaluation results of 6 people on the hand feel, +++++ is the best and + is the worst.

[0073] The test results are shown in Tables 1 and 2.

[0074] Table 1 Test data of pure cotton base fabric after coating

[0075]

[0076] Table 2 Test data of linen-viscose base fabric after coating

[0077]

[0078]

[0079] It can be seen from Table 1 and Table 2 that the fabrics coated with Examples 1-6 can basically reach the level of Grade 4 in the dry and wet friction fastness and water washing fastness tests, and are significantly better than the existing similar products on the market and the organic silicon textile coating adhesive provided in Example 1 of Patent CN110158321A. This shows that the high-fastness organic silicon high-elastic coating adhesive provided in the embodiments of the present invention has excellent dry and wet friction fastness, water washing fastness and high elasticity and crisp hand feel.

[0080] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A method for preparing a high-fastness organic silicone high-elastic coating adhesive, characterized in that: The method comprises: Step 1, first take 800-1200 parts of α,ω-dihydroxy-terminated polydimethylsiloxane, 10-20 parts of p-toluenesulfonic acid, and 8-16 parts of triethanolamine, knead and catalyze, perform low-temperature polycondensation, and neutralize to obtain raw rubber; Step 2: Take 24-32 parts of raw rubber, 1-3 parts of α,ω-terminated hydroxyl silicone oil linear body, and 65-75 parts of toluene in a stainless steel kettle and stir the materials to obtain a base rubber; Step 3, adding 3-6 parts of a crosslinking agent, 1-3 parts of a coupling agent, and 2-4 parts of a catalyst to the base glue and stirring evenly to obtain a high-fastness organic silicone high-elastic coating glue; The viscosity of the α,ω-dihydroxy-terminated polydimethylsiloxane is 20000-120000 mPa·s at 25° C.; The viscosity of the α,ω-terminated hydroxyl silicone oil linear body is 50-120 mPa·s at 25°C; The crosslinking agent is one or more of methyl triacetoxysilane, ethyl triacetoxysilane, and propyl triacetoxysilane; The coupling agent is one or more of γ-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and γ-piperazinepropylmethyldimethoxysilane.

2. The method for preparing a high-fastness organic silicone high-elastic coating adhesive according to claim 1, characterized in that: The catalyst is bismuth isooctanoate and / or zinc isooctanoate.

3. A high-fastness organic silicone high-elastic coating adhesive, characterized in that: Made by the method of claim 1 or 2.

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