Pigment printing thickening agent with cross-linking agent function and preparation method thereof

Abstract

The invention provides a pigment printing thickener with a cross-linking agent function and a preparation method thereof, and relates to the technical field of thickeners, the pigment printing thickener comprises the following components by mass: 80%-99% of an acrylic monomer raw material A and 20%-1% of a monomer B with a cross-linking active group; the acrylic monomer raw material A and the monomer B with the cross-linking active group are subjected to inverse emulsion polymerization to synthesize a polymer, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B with the cross-linking active group accounts for 30-40wt% of the emulsion system; the acrylic monomers and a small amount of monomers with cross-linking active groups are used as raw materials, the polymer is synthesized by adopting an inverse emulsion polymerization method, and the polymer can be used as a pigment printing thickening agent, can also play a role of a cross-linking agent and can improve hydrophobicity and wear resistance, so that the color fixation effect can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of thickeners, and in particular to a coating printing thickener with a cross-linking agent function and a preparation method thereof. Background Art

[0002] Acrylic synthetic thickeners for pigment printing are functional polymer materials made of acrylic monomers as the main component, which are neutralized and polymerized by inverse emulsion polymerization. They have good thickening ability and certain rheological properties, so they are widely used.

[0003] At present, there are two main types on the market, conventional and concentrated, and the difference lies in the solid content. The concentrated type generally has a solid content of more than 60%, and the dosage can be reduced by more than 40%. However, no matter what type it is, its performance is limited to thickening, and because it does not contain cross-linking active groups, it has no additive effect on the color fastness of printing. If the dosage is too much, its water solubility will also affect the final color fastness. Therefore, the present invention proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof to solve the problems existing in the prior art. Summary of the invention

[0004] In view of the above problems, the present invention proposes a paint printing thickener with a cross-linking agent function and a preparation method thereof. The paint printing thickener with a cross-linking agent function can not only be used as a paint printing thickener, but also can play the role of a cross-linking agent to improve the hydrophobic and wear resistance, thereby improving the color fixing effect.

[0005] To achieve the purpose of the present invention, the present invention is implemented by the following technical scheme: a pigment printing thickener with a cross-linking agent function, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group;

[0006] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by reverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system.

[0007] A further improvement is that the acrylic monomer raw material A is a combination of one or more of acrylic acid AA, methacrylic acid MAA, itaconic acid IA, β-acryloxypropionic acid β-CEA, and maleic anhydride MAn:

[0008] A further improvement is that the monomer B having a cross-linking active group is a combination of one or more of diacetone acrylamide DAAM, glycidyl acrylate GMA, hydroxymethyl acrylamide NAM, N-(isobutyloxy)methacrylamide IBMA, and ethylene glycol acetoacetate methacrylate AAEM.

[0009] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0010] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise until the pH value is 5.5-7.0 to obtain a neutralized solution, and then add the oxidant and the internal cross-linking monomer;

[0011] Put monomer B with cross-linking active groups, emulsifier and oil phase into an emulsifying kettle and stir evenly;

[0012] The neutralized liquid is transferred into an emulsifying kettle and stirred at high speed to form an emulsion system to obtain an emulsion;

[0013] Transfer the emulsion into the reactor, stir at a low speed, add the reducing agent solution, initiate the polymerization reaction, and turn on the cooling water to control the reaction temperature not exceeding 70°C;

[0014] When the temperature stops rising, turn off the cooling water, keep warm for 3-4 hours, transfer to the blending kettle, add the reverse emulsifier, stir evenly, and you will get the finished product.

[0015] Further improvement is that the parameters of high-speed stirring are 2000-2800r / min, and the parameters of low-speed stirring are 50-200r / min.

[0016] A further improvement is that the neutralizing agent is aqueous ammonia with a concentration of 20-25%.

[0017] A further improvement is that the emulsifier is Span-80 and the inverse emulsifier is AEO-9.

[0018] A further improvement is that the oil phase is white oil D60.

[0019] A further improvement is that the internal cross-linking monomer is N,N-methylenebisacrylamide MBA.

[0020] A further improvement is that the oxidant is ammonium persulfate and the reducing agent is sodium bisulfite.

[0021] The beneficial effects of the present invention are:

[0022] 1. The present invention uses acrylic monomers and a small amount of monomers with cross-linking active groups as raw materials and adopts the method of inverse emulsion polymerization to synthesize polymers, which can not only be used as a thickener for paint printing, but also can play the role of a cross-linking agent to improve hydrophobicity and wear resistance, thereby improving the color fixing effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0024] In order to deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

[0025] Embodiment 1

[0026] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0027] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0028] Specific: Only select acrylic acid AA, 320 parts.

[0029] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0030] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0031] Embodiment 2

[0032] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0033] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0034] Specifically: select 300 parts of acrylic acid AA and 20 parts of diacetone acrylamide DAAM.

[0035] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0036] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0037] Embodiment 3

[0038] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0039] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0040] Specifically: 300 parts of acrylic acid AA and 20 parts of ethylene glycol acetoacetate methacrylate AAEM were selected.

[0041] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0042] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0043] Embodiment 4

[0044] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0045] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0046] Specifically: 300 parts of acrylic acid AA and 20 parts of N-(isobutyloxy)methacrylamide IBMA were selected.

[0047] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0048] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0049] Embodiment 5

[0050] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0051] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0052] Specifically: 300 parts of acrylic acid AA; 10 parts of diacetone acrylamide DAAM; and 10 parts of ethylene glycol acetoacetate methacrylate AAEM were selected.

[0053] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0054] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0055] Embodiment 6

[0056] according to Figure 1 As shown, this embodiment proposes a coating printing thickener with a cross-linking agent function and a preparation method thereof, comprising the following components by mass ratio: 80%-99% acrylic monomer raw material A, 20%-1% monomer B with a cross-linking active group; preferred ratio: A = 85-95%, B = 15-5%;

[0057] The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by inverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system;

[0058] Specifically: select acrylic acid AA, 290 parts; diacetone acrylamide DAAM, 30 parts.

[0059] A method for preparing a pigment printing thickener with a cross-linking agent function comprises the following steps:

[0060] Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise to a suitable pH value (6.0-6.5) to obtain a neutralized solution, then add ammonium persulfate and N,N-methylenebisacrylamide (dosage 0.01%); add the monomer B with cross-linking active groups and the emulsifier Span 80 (dosage 2.3%) and oil phase D60 (dosage 20.0%) are put into an emulsifying kettle and stirred evenly; the neutralized solution is transferred to the emulsifying kettle; at the same time, the mixture is stirred at a high speed of 2000-2800 rpm to form an emulsion system to obtain an emulsion; the emulsion is transferred to a reaction kettle, stirred at a low speed of 50-200 rpm, and a sodium bisulfite solution is slowly added to initiate a polymerization reaction, and the cooling water is turned on to control the reaction temperature not exceeding 70°C; when the temperature no longer rises, the cooling water is turned off and the mixture is kept warm for 3-4 hours; the obtained product is transferred to a blending kettle, and an inverse emulsifier AEO-9 (dosage 2.2%) is added and stirred evenly to obtain a finished product.

[0061] Verify data:

[0062] Table 1: Main monomer formula of Examples 1-6

[0063]

[0064] Table 2: Test results of products in Examples 1-6

[0065]

[0066]

[0067] Take 4 grams of thickener, add 196 grams of pure water, stir evenly, and measure with NDJ-1S rotational viscometer;

[0068] Printing formula: 25% adhesive (HF-1801R, produced by Anhui Polyradiation Chemical Co., Ltd.), 3% thickener, 4% color paste (sapphire blue), 68% pure water.

[0069] The present invention uses acrylic monomers and a small amount of monomers with cross-linking active groups as raw materials and adopts a reverse emulsion polymerization method to synthesize a polymer. The polymer can not only be used as a coating printing thickener, but also can play a role of a cross-linking agent to improve hydrophobicity and wear resistance, thereby improving the color fixing effect. The friction color fastness of the obtained textile printing product can be improved by 1-2 levels.

[0070] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A pigment printing thickener with cross-linking agent function, characterized in that: The composition comprises the following components in mass ratio: 80%-99% of acrylic monomer raw material A, and 20%-1% of monomer B having cross-linking active groups; The acrylic monomer raw material A and the monomer B having cross-linking active groups are synthesized into a polymer by reverse emulsion polymerization, and the total amount of the mixture of the acrylic monomer raw material A and the monomer B having cross-linking active groups accounts for 30-40wt% in the emulsion system.

2. The pigment printing thickener with cross-linking agent function according to claim 1, characterized in that: The acrylic monomer raw material A is a combination of one or more of acrylic acid AA, methacrylic acid MAA, itaconic acid IA, β-acryloxypropionic acid β-CEA, and maleic anhydride MAn.

3. The pigment printing thickener with cross-linking agent function according to claim 1, characterized in that: The monomer B having cross-linking active groups is a combination of one or more of diacetone acrylamide DAAM, glycidyl acrylate GMA, hydroxymethyl acrylamide NAM, N-(isobutyloxy)methacrylamide IBMA, and ethylene glycol acetoacetate methacrylate AAEM.

4. A method for preparing a pigment printing thickener with a cross-linking agent function, applied to a pigment printing thickener with a cross-linking agent function as claimed in any one of claims 1 to 3, characterized in that: The following steps are involved: Put the acrylic monomer raw material A into the neutralization kettle, add the neutralizer dropwise until the pH value is 5.5-7.0 to obtain a neutralized solution, and then add the oxidant and the internal cross-linking monomer; Put monomer B with cross-linking active groups, emulsifier and oil phase into an emulsifying kettle and stir evenly; The neutralized liquid is transferred into an emulsifying kettle and stirred at high speed to form an emulsion system to obtain an emulsion; Transfer the emulsion into the reactor, stir at a low speed, add the reducing agent solution, initiate the polymerization reaction, and turn on the cooling water to control the reaction temperature not exceeding 70°C; When the temperature stops rising, turn off the cooling water, keep warm for 3-4 hours, transfer to the blending kettle, add the reverse emulsifier, stir evenly, and you will get the finished product.

5. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The parameters for high-speed stirring are 2000-2800r / min, and the parameters for low-speed stirring are 50-200r / min.

6. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The neutralizing agent is aqueous ammonia with a concentration of 20-25%.

7. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The emulsifier is Span-80, and the inverse emulsifier is AEO-9.

8. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The oil phase is white oil D60.

9. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The internal cross-linking monomer is N,N-methylenebisacrylamide MBA.

10. The method for preparing a pigment printing thickener with a cross-linking agent function according to claim 4, characterized in that: The oxidizing agent is ammonium persulfate, and the reducing agent is sodium bisulfite.

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