CN103224765A - Fluorine-silicon-modified acrylate adhesive, preparation method and application thereof - Google Patents

Abstract

The invention discloses a fluorosilicon modified acrylate adhesive, which is prepared from the following raw materials in parts by weight: 50 parts of water, 0.1-1 part of anionic emulsifier, 10-20 parts of acrylate polymerized monomer, 0.2 -1 part of acrylic acid, 0.5-5 parts of fluorine-containing silicone monomer, 0.1-2 parts of co-emulsifier and 0.1-1 part of initiator. The fluorosilicon-modified acrylate adhesive of the present invention is a stable fluorosilicon-modified acrylate emulsion, which can be used for paint printing, has soft hand feeling, high color fastness, good system stability, and stable product quality, which effectively solves the existing problems. Acrylic adhesives have contradictory hand feeling and fastness, as well as hot sticky and cold brittle problems. The invention also discloses a preparation method of a fluorosilicon-modified acrylate adhesive. A stable fluorosilicon-modified acrylate emulsion is prepared by miniemulsion polymerization, which is simple to prepare, easy to implement and operate, and easy to industrialized large-scale production. have a broad vision of application.

Description

A kind of fluorine silicon modified acrylate adhesive and its preparation method and application

technical field

The invention relates to the field of adhesives, in particular to an environment-friendly fluorosilicon-modified acrylate adhesive, a preparation method thereof, and an application as a pigment printing adhesive.

Background technique

Pigment printing is a method of mechanically fixing the paint that has no affinity and reactivity to fibers on the surface of the fabric with the help of adhesives. It only needs to fix the color and does not need to be washed. Therefore, it has the advantages of energy saving, water saving, and emission reduction, and is widely used by printing and dyeing enterprises. It is also listed by the National Economic and Trade Commission as one of the processes for promoting clean production in the textile industry.

However, the handling properties such as feel and rubbing fastness of pigment printed fabrics largely depend on the performance of pigment printing adhesives. At present, the most widely used in our country is polyacrylate pigment printing adhesive, which has the characteristics of good film-forming property, high bonding strength, heat resistance, oxidation resistance, etc. It is difficult to have both hand feel and fastness. Moreover, N-methylolacrylamide is mostly used as a crosslinking monomer, and high-temperature baking will release a large amount of free formaldehyde that is harmful to the human body and the environment, and will also damage the physical and mechanical properties of textile fibers.

Therefore, it is of great significance to research and develop environmentally friendly pigment printing adhesives with soft handfeel and high color fastness.

The Chinese invention patent application with the publication number CN101423734A discloses a method for preparing a silicone-modified acrylate adhesive. The raw materials include: basic monomers, silane monomers, coupling agents, modified monomer catalysts, basic monomers Catalyst, emulsifier and deionized water, wherein, the basic monomer includes hard monomer, soft monomer and cross-linking monomer. The preparation method includes: (1) silane monomer, coupling agent, modified monomer catalyst, Prepolymerization of emulsifier and deionized water to prepare silicone prepolymerization emulsion; (2) emulsification of the silicone prepolymerization emulsion and basic monomer to prepare intermediate preemulsion; (3) intermediate preemulsion, basic Polymerization of monomer catalyst and deionized water to prepare environmentally friendly silicone-modified acrylate adhesive. In this technical scheme, the siloxane chain segment of the silane monomer is relatively long, which makes it have strong water repellency, and it is difficult to realize the migration process of the monomer in ordinary emulsion polymerization, so that the final conversion rate of the organic silicon is not high. high.

Contents of the invention

The invention provides a fluorine-silicon modified acrylate adhesive, which is a stable fluorine-silicon modified acrylate emulsion, which can be used for paint printing, has soft hand feeling and high color fastness, and effectively solves the problem of existing acrylate adhesives. There are contradictions between the feel and fastness of the adhesive, as well as the problem of hot stickiness and cold brittleness.

A fluorosilicon modified acrylate adhesive, made of the following raw materials in parts by weight:

50 parts of water;

Anionic emulsifier 0.1 to 1 part;

Acrylate polymerized monomer 10-20 parts;

Acrylic acid 0.2 to 1 part;

Fluorine-containing silicone monomer 0.5-5 parts;

Co-emulsifier 0.1-2 parts;

Initiator 0.1 to 1 part;

The acrylate polymerization monomer is one or more of butyl acrylate, hydroxyethyl acrylate, isooctyl acrylate, methyl methacrylate and glycidyl methacrylate.

As a preference, the fluorosilicon-modified acrylate adhesive is made of the following raw materials in parts by weight:

50 parts of water;

Anionic emulsifier 0.1-0.9 parts;

Acrylate polymerized monomer 10.5-15.1 parts;

Acrylic acid 0.4-0.8 parts;

Fluorine-containing silicone monomer 0.5-4 parts;

Co-emulsifier 0.2-1.5 parts;

Initiator 0.1-0.9 parts.

The fluorosilicon modified acrylate adhesive is applied to pigment printing, which has softer hand feeling and higher color fastness.

Anionic emulsifiers are negatively charged, attached to the surface of latex particles, and generate electrostatic repulsion between each other. Therefore, it can prevent small monomers from colliding with each other into large droplets, thereby stabilizing the microemulsion. Preferably, the anionic emulsifier is sodium lauryl sulfate or sodium dodecylsulfonate, and the above two anionic emulsifiers can better stabilize the miniemulsion.

Acrylic acid is used as the raw material, because the carboxyl group in the acrylic acid molecule is a strong polar group (negatively charged), which can make the outer layer of the latex particles have an electrostatic charge, and the latex particles are not easy to aggregate due to electrostatic repulsion, thereby improving the viscosity of the emulsion. stability. At the same time, as a cross-linking monomer, acrylic acid can significantly improve the film-forming performance of the adhesive, increase the attraction to fibers, improve the adhesion, and provide cross-linking points to play a role in self-catalysis, so it can improve the fastness of pigment printing. Spend. Therefore, the use of acrylic acid can improve the stability of the emulsion and improve the printing fastness of the paint.

Preferably, the fluorine-containing silicone monomer is a vinyl-terminated fluorine-containing polysiloxane, which is a compound of formula I;

Formula I;

Wherein, n is the average degree of polymerization, n=3-50.

Fluorine-containing silicone monomer (namely, vinyl-terminated fluorine-containing polysiloxane), obtained by copolymerization of vinyl-containing silicone macromolecules and small-molecule vinyl monomers by free radical polymerization, adopting the formula I structure Fluorinated silicone monomers modify acrylates.

Co-emulsifiers can form interface barriers on the droplet surface, reduce the degradation of monomer droplets due to Ostwald ripening, and delay the migration of monomers from small droplets to large droplets, thereby improving the stability of the emulsion. Preferably, the co-emulsifier is n-hexadecane or n-hexadecanol, and the above two co-emulsifiers can better improve the stability of the emulsion.

The initiator is an oil-soluble initiator or a water-soluble initiator, which can be decomposed to generate free radicals, thereby initiating free-radical copolymerization of vinyl monomers. As preferably, the oil-soluble initiator is azobisisobutyronitrile, and azobisisobutyronitrile mainly exists in the monomer droplets, and when the reaction starts, all the monomer droplets initiate simultaneously, and the polymerization reaction speed is faster; the water-soluble initiator is Ammonium persulfate or potassium persulfate, ammonium persulfate or potassium persulfate mainly exists in the water phase, monomer droplets initiate polymerization by capturing free radicals in the water phase, the polymerization process is relatively stable, and no implosion phenomenon occurs. That is, the initiator is azobisisobutyronitrile, ammonium persulfate or potassium persulfate.

The invention also provides a preparation method of the fluorosilicon-modified acrylate adhesive. A stable fluorosilicon-modified acrylate emulsion is prepared through miniemulsion polymerization, and the preparation is simple and easy to implement.

A preparation method of fluorosilicon modified acrylate adhesive, comprising the following steps:

1) Mix the anionic emulsifier and water evenly to prepare a pre-emulsion;

2) Mix acrylate polymer monomer, acrylic acid, fluorine-containing silicone monomer, co-emulsifier and initiator, and then add it dropwise to the pre-emulsion. After dropping, mix evenly to obtain an emulsion, and then ultrasonically Pulverize to obtain a fine emulsion;

3) React the fine emulsion at 50°C-90°C for 1-8 hours to obtain a fluorosilicon-modified acrylate emulsion, that is, a fluorosilicon-modified acrylate adhesive.

In step 1), as a preference, the anionic emulsifier and water are stirred at a speed of 500r/min-1500r/min (rev/min) for 5-30 minutes and mixed evenly, so that the anionic emulsifier and water can be fully mixed evenly.

In step 2), as a preference, the acrylate polymerized monomer, acrylic acid, fluorine-containing silicone monomer, co-emulsifier and initiator are mixed uniformly and dropped into the pre-emulsion for 3 minutes to 10 minutes, so that the acrylate polymerized monomer , acrylic acid, fluorine-containing silicone monomer, co-emulsifier and initiator are mixed to form a mixed solution, which is uniformly dispersed in the pre-emulsion.

Preferably, after dripping, stir at a rotation speed of 500r/min to 1500r/min for 5 to 30 minutes and mix evenly to obtain an emulsion, so that the components in the emulsion are fully mixed uniformly to obtain a stable emulsion.

Preferably, the emulsion is ultrasonically pulverized in an ice-water bath for 5-20 minutes, and the ice-water bath can absorb a large amount of heat generated during the ultrasonic process to stabilize the monomer, thereby making the formed submicron monomer droplets more stable.

In step 3), as a preference, the fine emulsion is reacted at 60°C-80°C for 1-6 hours, and a constant temperature water bath can be selected specifically. If the reaction temperature is too low, it is difficult to initiate monomer polymerization, and if the reaction temperature is too high, the reaction is too fast, and implosion is prone to occur Phenomenon, the above-mentioned reaction conditions can make the polymerization reaction proceed smoothly.

The reaction is carried out under the atmosphere of protective gas, and the protective gas is nitrogen or inert gas.

The application of the fluorosilicon modified acrylate adhesive as a pigment printing adhesive, the specific application includes the following steps:

(1) Prescription of printing paste (parts by weight): 2 parts of pigment, 10-20 parts of fluorosilicone modified acrylate adhesive, 1-2 parts of thickener, 20-40 parts of water.

(2) Printing process: printing → pre-baking (80°C, 5 minutes) → baking (160°C, 3 minutes).

Compared with prior art, the present invention has following advantage:

The fluorosilicon-modified acrylate adhesive of the present invention is a stable fluorosilicon-modified acrylate emulsion, has good system stability and stable product quality. In Example 1, the particle size of the emulsion is 60-70 nm, distributed at about 1, and the particle size distribution of the latex particles is uniform. The glass transition temperature of the latex film modified by fluorosilicone drops to -15°C, and the contact angle to water can reach 102°. The situation of other embodiments is basically the same as that of Embodiment 1.

The present invention modifies the polyacrylate pigment printing adhesive through the fluorine-containing silicone monomer, and adjusts other components and contents accordingly, so that the fluorine-silicon modified acrylate adhesive of the present invention can be used as a pigment printing adhesive When the agent is used, the dry rubbing fastness of the obtained printed fabric can reach 4-5 grades, the wet rubbing fastness can reach 3-4 grades, the K/S value can reach more than 13.5, the color fastness is high, the hand feels soft, and there is no formaldehyde release.

The preparation method of the fluorosilicon-modified acrylate adhesive of the present invention is simple in preparation, easy in implementation and operation, easy in industrialized large-scale production, and has broad application prospects.

Description of drawings

Fig. 1 is the particle size distribution figure of the fluorosilicon modified acrylate emulsion prepared in embodiment 1;

Fig. 2 is the differential scanning calorimetry (DSC) spectrogram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in Example 1;

Fig. 3 is the contact angle diagram of the latex film formed by the fluorosilicon modified acrylate emulsion prepared in Example 1 to water.

Detailed ways

The following examples are further descriptions of the present invention, but the present invention is not limited to the following examples.

Example 1

(1) Dissolve 0.3 grams of emulsifier sodium dodecyl sulfate (SDS) in 50 grams of deionized water and stir at high speed (1000r/min) for 10 minutes, mix well, and make a pre-emulsion;

(2) Mix 6 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, 1.5 grams of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 8, synthesized by existing anionic polymerization method), 0.6 g of n-hexadecane and 0.15 g of azobisisobutyronitrile, mixed evenly and slowly added dropwise to the pre- In the emulsion, the dropping time is 5 minutes, stirred at high speed (1000r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 8 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain fluorosilicon modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

The particle size distribution diagram of the fluorosilicon-modified acrylate emulsion prepared in Example 1 is shown in Figure 1. The particle size of the latex particles in the emulsion is 60-70 nm, and the distribution is around 1.

The preparation method of the latex film is as follows: Weigh an appropriate amount of the fluorosilicon-modified acrylate adhesive prepared in this example (that is, the fluorosilicon-modified acrylate emulsion) and apply it on the PTFE board. After 7 days of storage, bake at 150°C for 3 minutes to form a latex film.

The differential scanning calorimetry (DSC) spectrum of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in Example 1 is shown in Figure 2. From Figure 2, it can be seen that the acrylate modified by fluorosilicon The glass transition temperature is consistent with that designed by the experimental formula, which is about -15°C.

The fluorosilicon-modified acrylate emulsion prepared in Example 1 forms a contact angle diagram of the latex film to water, as shown in Figure 3, the contact angle to water can reach 102°, indicating that the fluorosilicon-modified acrylate of this embodiment is bonded The latex film formed by the agent has excellent hydrophobic properties.

Example 2

(1) Dissolve 0.3 grams of emulsifier sodium dodecyl sulfate (SDS) in 50 grams of deionized water and stir at high speed (1000r/min) for 10 minutes, mix well, and make a pre-emulsion;

(2) Mix 6 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, 1.5 grams of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 16, synthesized by existing anionic polymerization method), 0.6 g of n-hexadecane and 0.15 g of ammonium persulfate, mixed evenly and slowly added dropwise to the emulsifier aqueous solution , the dropping time is 5 minutes, stirred at high speed (1000r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 8 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain fluorosilicon modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Example 3

(1) Dissolve 0.3 grams of emulsifier sodium dodecyl sulfate (SDS) in 50 grams of deionized water and stir at high speed (1000r/min) for 10 minutes, mix well, and make a pre-emulsion;

(2) 7 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 1 gram of glycidyl methacrylate, 0.8 grams of acrylic acid, 1.5 grams of fluorine-containing silicone monomer (formula I structure, average degree of polymerization n is 32 , synthesized by the existing anionic polymerization method), 0.6 g of n-hexadecane and 0.15 g of azobisisobutyronitrile, after mixing evenly, slowly drop them into the emulsifier aqueous solution, the dropping time is 5min, at high speed (1000r/ min) stirring for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 8 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain fluorosilicon modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Example 4

(1) Dissolve 0.3 g of emulsifier sodium dodecyl sulfate (SDS) in 50 g of deionized water and stir at 1000 r/min for 10 minutes, mix well, and make a pre-emulsion;

(2) Mix 6 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, 1.5 grams of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 50, synthesized by existing anionic polymerization method), 0.6 g of n-hexadecane and 0.15 g of azobisisobutyronitrile, mixed uniformly and slowly added dropwise for 5 minutes In the pre-emulsion, the dropping time is 5 minutes, stirred at high speed (1000r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 8 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain fluorosilicon modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Example 5

(1) Dissolve 0.3 g of emulsifier sodium dodecyl sulfate (SDS) in 50 g of deionized water and stir at 1000 r/min for 10 minutes, mix well, and make a pre-emulsion;

(2) Mix 6.5 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, and 1 gram of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 13.6, synthesized by existing anionic polymerization method), 0.6 g of n-hexadecane and 0.15 g of azobisisobutyronitrile, mix well and slowly add dropwise for 5 minutes In the pre-emulsion, the dropping time is 5 minutes, stirred at high speed (1000r/min) for 20 minutes, and then treated with an ultrasonic pulverizer (600W) in an ice-water bath for 8 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain fluorosilicon modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Example 6

(1) Dissolve 0.9 grams of emulsifier sodium dodecylsulfonate (SDS) in 50 grams of deionized water and stir at high speed (1500r/min) for 25 minutes, mix well, and make a pre-emulsion;

(2) Mix 8 grams of butyl acrylate, 4 grams of methyl methacrylate, 0.9 grams of hydroxyethyl acrylate, 0.9 grams of isooctyl acrylate, 1.3 grams of glycidyl methacrylate, 0.7 grams of acrylic acid, 4 grams of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 8, synthesized by the existing anionic polymerization method), 1.5 grams of n-hexadecane and 0.9 grams of azobisisobutyronitrile, mixed evenly and slowly added to the pre- In the emulsion, the dropping time is 10 minutes, stirred at high speed (1500r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 15 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 60°C to initiate polymerization for 6 hours to obtain fluorosilicon-modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Example 7

(1) Dissolve 0.1 g of emulsifier sodium dodecyl sulfate (SDS) in 50 g of deionized water and stir at high speed (500r/min) for 5 minutes, mix well, and make a pre-emulsion;

(2) Mix 6 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, 0.5 grams of fluorine-containing organic Silicon monomer (formula I structure, average degree of polymerization n is 8, synthesized by existing anionic polymerization method), 0.2 g of n-hexadecanol and 0.1 g of azobisisobutyronitrile, mixed evenly and slowly added dropwise to the pre-emulsification In the solution, the dropping time is 3 minutes, stirred at high speed (500r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 5 minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring paddle, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 80°C to initiate polymerization for 2 hours to obtain fluorosilicon-modified Acrylate emulsion, that is, fluorosilicon modified acrylate adhesive.

Formula I

According to the contact angle diagram of the latex film formed by the fluorosilicon-modified acrylate emulsion prepared in this example to water, it can be seen that the latex film formed by the fluorosilicon-modified acrylate adhesive in this example has excellent hydrophobic properties.

Comparative example 1

(1) Dissolve 0.3 grams of emulsifier sodium dodecyl sulfate (SDS) in 50 grams of deionized water and stir at high speed (1000r/min) for 10 minutes, mix well, and make a pre-emulsion;

(2) Mix 6 grams of butyl acrylate, 2.5 grams of methyl methacrylate, 0.6 grams of hydroxyethyl acrylate, 0.6 grams of isooctyl acrylate, 0.9 grams of glycidyl methacrylate, 0.4 grams of acrylic acid, 0.6 grams of Alkanes and 0.15 g of azobisisobutyronitrile, mixed evenly, slowly added dropwise to the pre-emulsion, the dropwise time was 5 minutes, stirred at high speed (1000r/min) for 20 minutes, and then treated with an ultrasonic pulverizer in an ice-water bath for 8 Minutes to obtain a fine emulsion;

(3) Pour the above fine emulsion into a four-necked flask equipped with a stirring blade, a thermometer and a condenser tube, pass high-purity nitrogen for 30 minutes to remove the air, and then heat in a constant temperature water bath at 70°C to initiate polymerization for 3 hours to obtain an acrylate emulsion. Namely, acrylate adhesive.

Application example

Printing process of pigment printing:

(1) Prescription of printing paste: 2 grams of paint blue, 15 grams of adhesive prepared in Examples 1-7 and Comparative Example 1, 1.5 grams of thickener, and 31.5 grams of water, totaling 50 grams.

(2) Printing process: printing → pre-baking (80°C, 5 minutes) → baking (160°C, 3 minutes).

Adopt the printing effect of the adhesive for pigment printing synthesized by the present invention, test the dry and wet rubbing fastness according to GB/T3920-1997 "textile color fastness test color fastness to rubbing" test method; adopt LLY-01 type electronic stiffening Stiffness was measured by a degree meter; the color depth (K/S value) of the printed product was tested by a Datacolor SF600 computer color measuring and matching instrument, and the printing effect of the test is shown in Table 1.

Table 1

It can be seen from Table 1 that after the acrylate adhesives modified with different molecular weights and different contents of fluorosilicon (that is, the fluorosilicon modified acrylate adhesives of the present invention) are used for pigment printing, the dry rubbing of the printed fabrics is fast. The hardness can reach 4 to 5 grades, and the wet rubbing fastness can reach above 3 grades, which is higher than that of the unmodified acrylate adhesive. Therefore, the fluorosilicon modified acrylate adhesive of the present invention has high color fastness, In addition, the stiffness of the fluorosilicon-modified acrylate adhesive of the present invention decreases, the handle becomes softer, and the printing K/S value increases.

Claims (10)

1. A fluorosilicon modified acrylate adhesive, characterized in that it is made from the raw materials of the following parts by weight: 50 parts of water; Anionic emulsifier 0.1 to 1 part; Acrylate polymerized monomer 10-20 parts; Acrylic acid 0.2 to 1 part; Fluorine-containing silicone monomer 0.5-5 parts; Co-emulsifier 0.1-2 parts; Initiator 0.1 to 1 part; The acrylate polymerization monomer is one or more of butyl acrylate, hydroxyethyl acrylate, isooctyl acrylate, methyl methacrylate and glycidyl methacrylate. 2. The fluorosilicon-modified acrylate adhesive according to claim 1, wherein the anionic emulsifier is sodium lauryl sulfate or sodium lauryl sulfate. 3. The fluorine-silicon modified acrylate adhesive according to claim 1, wherein the fluorine-containing silicone monomer is vinyl-terminated fluorine-containing polysiloxane, which is a compound of formula I structure ; Formula I; Wherein, n is the average degree of polymerization, n=3-50. 4. The fluorosilicon-modified acrylate adhesive according to claim 1, wherein the co-emulsifier is n-hexadecane or n-hexadecanol. 5. The fluorosilicon-modified acrylate adhesive according to claim 1, wherein the initiator is azobisisobutyronitrile, ammonium persulfate or potassium persulfate. 6. The preparation method of the fluorosilicon-modified acrylate adhesive according to any one of claims 1 to 5, characterized in that it comprises the following steps: 1) Mix the anionic emulsifier and water evenly to prepare a pre-emulsion; 2) Mix acrylate polymer monomer, acrylic acid, fluorine-containing silicone monomer, co-emulsifier and initiator, and then add it dropwise to the pre-emulsion. After dropping, mix evenly to obtain an emulsion, and then ultrasonically Pulverize to obtain a fine emulsion; 3) React the fine emulsion at 50°C-90°C for 1-8 hours to obtain a fluorosilicon-modified acrylate emulsion, that is, a fluorosilicon-modified acrylate adhesive. 7. The preparation method of fluorosilicon-modified acrylate adhesive according to claim 6, characterized in that, in step 1), the anionic emulsifier and water are stirred at a speed of 500r/min to 1500r/min for 5 ~30 minutes to mix well. 8 . The preparation method of fluorosilicon-modified acrylate adhesive according to claim 6 , characterized in that, in step 2), the emulsion is ultrasonically pulverized in an ice-water bath for 5-20 minutes. 9 . The preparation method of fluorosilicon-modified acrylate adhesive according to claim 6 , characterized in that, in step 3), the fine emulsion is reacted at 60° C. to 80° C. for 1 to 6 hours. 10. The application of the fluorosilicon-modified acrylate adhesive according to any one of claims 1 to 5 as a pigment printing adhesive.

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