阅读说明：本技术 一种水性聚丙烯酸酯乳液树脂及其制备方法与应用 (A kind of water polyacrylic acid emulsion resin and the preparation method and application thereof ) 是由 张天 刘凌利 桂雪峰 孙龙凤 许正敏 方燕 许凯 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种水性聚丙烯酸酯乳液树脂及其制备方法与应用。本发明是利用含有双键且多羧基的功能单体与丙烯酸树脂接枝聚合,并采用反应型乳化剂与双键多羧酸的功能单体共同在丙烯酸树脂链段中共同引入大量阴离子,同时,在丙烯酸树脂分子链上接入水溶性聚合物长链,采用长链丙烯酸单体接入长链侧基的分子后得到。本发明的水性丙烯酸酯乳液树脂对炭黑的分散性和稳定性更佳,成膜效果好,且可以有效减少在研磨炭黑制备色浆过程中对其他有机助剂的使用,降低VOC含量与溶剂类原料用量,更环保节约,且对稀释剂乙醇有更好的耐受性,制备的水性油墨色浆良好分散多份量高色素炭黑,可形成分散均匀、高遮光率的稳定漆膜。(The invention discloses a kind of water polyacrylic acid emulsion resins and the preparation method and application thereof.The present invention is graft-polymerized using the function monomer containing double bond and more carboxyls and acrylic resin, and a large amount of anion are collectively incorporated into acrylic resin segment using reactive emulsifier and the polycarboxylic function monomer of double bond jointly, simultaneously, water-soluble polymer long-chain is accessed in acrylic molecular chain, is obtained after the molecule using long-chain acrylic monomers access long-chain side group.Water-and acrylate emulsion resin of the invention to the dispersibility and stability of carbon black more preferably, film-formation result is good, and use during grinding carbon black and preparing mill base to other organic additives can be effectively reduced, reduce VOC content and solvent raw material dosage, more environmentally friendly saving, and have a better tolerance to diluent ethanol, the more deal high-carbon black pigments of water-based ink mill base fine dispersion of preparation, can be formed be uniformly dispersed, the stabilization paint film of high shading rate.)

1. a kind of preparation method of water polyacrylic acid emulsion resin, which comprises the following steps:

(1) preparation of water-based acrylic resin pre-emulsion

By 20~50 mass parts soft monomers, 25~80 mass parts hard monomers, 5~10 mass parts long-chain acrylic monomers, 0.5~5 Mass of water-soluble linear polymer, 2~5 mass parts reactive emulsifiers, 50~90 mass parts water mix, while stirring pre- cream Change, obtains pre-emulsion；

(2) preparation of water polyacrylic acid emulsion resin

Pre-emulsion that 20~45 mass parts steps (1) obtain, 2~5 mass parts are contained into the acid of double bond and more carboxyls, 30~80 matter It measures part water, 0.2~0.5 mass parts buffer, 2~5 mass parts reactive emulsifiers to be added in reaction vessel, leads to nitrogen, heating To 72~80 DEG C, 0.2~1 mass parts initiator is added, reacts while stirring, obtains the prepolymer of water-based acrylic resin；It will Pre-emulsion and 0.3~1 mass parts initiator that remaining step (1) obtains are added drop-wise to the prepolymer of water-based acrylic resin simultaneously In, 82~86 DEG C of the reaction was continued 2~5h obtain water polyacrylic acid emulsion resin；

Hard monomer described in step (1) is one or both of methyl methacrylate and styrene；

Soft monomer described in step (1) is one of 2- Isooctyl acrylate monomer, butyl methacrylate and butyl acrylate Or at least two；

Long-chain acrylic monomers described in step (1) is in dodecyl acrylate, Process Conditions of Cetane Acrylate and octadecyl acrylate One kind or at least two；

Water-soluble linear polymer described in step (1) be one of poly glycol monomethyl ether and polypropylene glycol monomethyl ether or Two kinds；

Acid containing double bond and more carboxyls described in step (2) be one of methylene-succinic acid and maleic anhydride or Two kinds；

Reactive emulsifier described in step (1) and (2) is 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium, allyloxy One or both of nonylphenol polyoxyethylene ether ammonium sulfate and allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate.

2. the preparation method of water polyacrylic acid emulsion resin according to claim 1, it is characterised in that:

The molecular weight of water-soluble linear polymer described in step (1) is 400~600.

The allyloxy nonylphenol polyoxyethylene ether ammonium sulfate is Ai Di section, Japan SE-10N；

The allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate is Ai Di section, Japan SR-10；

Buffer described in step (2) is one or both of sodium bicarbonate and ammonium hydrogen carbonate；

Initiator described in step (2) is one or both of ammonium persulfate and potassium peroxydisulfate.

3. the preparation method of water polyacrylic acid emulsion resin according to claim 1, it is characterised in that:

Pre-emulsified condition described in step (1) are as follows: 10~20min of pre-emulsification under 1000~2500r/min revolving speed；

Reaction while stirring described in step (2) is stirred to react 20min~45min under the conditions of being 180~250r/min of revolving speed；

The temperature of the prepolymer of water-based acrylic resin described in step (2) is 78~85 DEG C.

4. a kind of water polyacrylic acid emulsion resin, it is characterised in that pass through the described in any item preparation sides of claims 1 to 3 Method is prepared.

5. water polyacrylic acid emulsion resin as claimed in claim 4 is preparing the application in water-based ink mill base.

6. a kind of preparation method of water-based ink mill base, which comprises the following steps: weigh 40~55 mass parts Benefit require 1~3 described in any item water polyacrylic acid emulsion resins, 0.2~0.5 mass parts pH adjusting agent, 0.2~ 0.4 mass parts sodium chloride solution, 2~4 mass parts coalescing agents are uniformly mixed, and 0.2~0.4 mass parts defoaming agent, 5~30 is added 10~30 mass parts high-carbon black pigments are added in mass parts ethyl alcohol, 20~50 mass parts water, pre-grinding, grind 1~2h, obtain water Property ink mill base.

7. the preparation method of water-based ink mill base according to claim 6, it is characterised in that:

The pH adjusting agent is ammonium hydroxide, N, one of N- dimethylethanolamine and 2-amino-2-methyl-1-propanol or extremely It is two kinds few；

The coalescing agent is one of alcohol ester 12, diethylene glycol monobutyl ether, butyl glycol ether and dipropylene Or at least two；

The defoaming agent is in BASF ED2522 and Digao Foamex823, Digao Foamex825 and Digao Foamex833 One kind or at least two.

8. the preparation method of water-based ink mill base according to claim 6, it is characterised in that:

The pre-grinding is that zirconium pearl, 15~30min of pre-grinding is added；

The revolving speed of the grinding is 1500~2500r/min.

9. a kind of water-based ink mill base, it is characterised in that pass through the preparation method of the water-based ink mill base described in claim 6~8 It is prepared.

Technical field

The present invention relates to technical field of aqueous paint, in particular to a kind of water polyacrylic acid emulsion resin and its system Preparation Method and application.

Background technique

High-carbon black pigment has fabulous covering power, strong coloring force and high blackness as ink, the major colorants of coating Characteristic, the performance of the direct left and right ink of dispersion stabilization in system.And high-carbon black pigment usually has primary partial size (CN106749855A, one kind being suitable for high-carbon black pigment and grind the strong architectural characteristic of small, large specific surface area, interparticle force Water-based acrylic resin manufacture and purposes) and surface have a large amount of carboxyl, extremely strong aggregation, height between carbon black pellet Oil absorption, thus the dispersion of high-carbon black pigment belong in color paint pigment it is the most difficult.The method of current scatter carbon black is mostly to add Add a large amount of dispersing agent, but traditional dispersing agent is easily desorbed from particle surface, therefore scattered particle reassembles, to color The long-time stability of slurry system are unfavorable, and dispersing agent is excessively unfavorable for the film forming of slurry, more to paint film appearance, hardness and resistance to old There are adverse effects for the properties such as change, thus water-base resin are added in oriented colour paste system at present, the research of carbon black dispersion is helped to become Gesture.Only have water-soluble resin to be capable of providing such effect in existing water-base resin, relatively conventional is acrylic resin, But the dispersing agent directly prepared with water-soluble acrylic resin is poor to the dispersibility of carbon black, and causes the mill base ground not It can film forming.Lotion itself belongs to the system of thermodynamic instability, for grinding the lotion of high-carbon black pigment, especially traditional third Olefin(e) acid resin emulsion, can because adsorbed under the physicochemical characteristic high shear forces during the grinding process of carbon black by carbon black it is poly-, from And lead to the demulsification of lotion, so that the stability of pigment paste of preparation is bad.It would therefore be highly desirable to develop dispersed more preferable, stability more Good and film-formable water polyacrylic acid emulsion resin prepares mill base to grind high-carbon black pigment.

Summary of the invention

The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of water polyacrylic acid cream Liquid resin.

Another object of the present invention is to provide the preparation methods of above-mentioned water polyacrylic acid emulsion resin.

A further object of the present invention is to provide the applications of above-mentioned water polyacrylic acid emulsion resin.

The purpose of the invention is achieved by the following technical solution: a kind of preparation side of water polyacrylic acid emulsion resin Method specifically comprises the following steps:

(1) preparation of water-based acrylic resin pre-emulsion

By 20~50 mass parts soft monomers, 50~80 mass parts hard monomers, 5~10 mass parts long-chain acrylic monomers, 0.5 ~5 mass of water-soluble linear polymers, 2~5 mass parts reactive emulsifiers and the mixing of 50~90 mass parts water, while stirring Pre-emulsification obtains pre-emulsion；

(2) preparation of water polyacrylic acid emulsion resin

By pre-emulsion that 20~45 mass parts steps (1) obtain, 2~5 mass parts contain the acid of double bond and more carboxyls, 30~ 80 mass parts water, 0.2~0.5 mass parts buffer, 2~5 mass parts reactive emulsifiers are added in reaction vessel, lead to nitrogen, 72~80 DEG C are heated to, 0.2~1 mass parts initiator is added, reacts while stirring, obtains the pre-polymerization of water-based acrylic resin Object；The pre-emulsion that remaining step (1) obtains is added drop-wise to the pre- of water-based acrylic resin with 0.3~1 mass parts initiator simultaneously In polymers, 82~86 DEG C of the reaction was continued 2~5h obtain water polyacrylic acid emulsion resin.

Pre-emulsified condition described in step (1) are as follows: 10~20min of pre-emulsification under 1000~2500r/min revolving speed.

Hard monomer described in step (1) is one or both of methyl methacrylate (MMA) and styrene.

Soft monomer described in step (1) is in 2- Isooctyl acrylate monomer, butyl methacrylate and butyl acrylate One kind or at least two.

Long-chain acrylic monomers described in step (1) is dodecyl acrylate, Process Conditions of Cetane Acrylate and acrylic acid 18 One of ester or at least two.

Water-soluble linear polymer described in step (1) is one in poly glycol monomethyl ether and polypropylene glycol monomethyl ether Kind or two kinds.

The molecular weight of water-soluble linear polymer described in step (1) is 400~600.

Reactive emulsifier described in step (1) and (2) is 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium, allyl One or both of oxygroup nonylphenol polyoxyethylene ether ammonium sulfate and allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate.

The allyloxy nonylphenol polyoxyethylene ether ammonium sulfate is preferably Ai Di section, Japan SE-10N.

The allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate is preferably Ai Di section, Japan SR-10.

Acid containing double bond and more carboxyls described in step (2) is one in methylene-succinic acid and maleic anhydride Kind or two kinds.

Buffer described in step (2) is one or both of sodium bicarbonate and ammonium hydrogen carbonate.

Initiator described in step (2) is one or both of ammonium persulfate and potassium peroxydisulfate.

Reaction while stirring described in step (2) be 180~250r/min of revolving speed under the conditions of be stirred to react 20min~ 45min。

The temperature of the prepolymer of water-based acrylic resin described in step (2) is 78~85 DEG C.

A kind of water polyacrylic acid emulsion resin, is prepared by above-mentioned preparation method.

Above-mentioned water polyacrylic acid emulsion resin is preparing the application in water-based ink mill base.

A kind of preparation method of water-based ink mill base specifically comprises the following steps: to take 40~55 mass parts above-mentioned aqueous poly- Acrylic acid ester emulsion resin, 0.2~0.5 mass parts pH adjusting agent, 0.2~0.4 mass parts sodium chloride solution, 2~4 mass parts Coalescing agent is uniformly mixed, and 0.2~0.4 mass parts defoaming agent, 5~30 mass parts ethyl alcohol, 20~50 mass parts water is added, in advance 10~30 mass parts high-carbon black pigments are added in grinding, grind 1~2h, obtain water-based ink mill base.

The pre-grinding is that zirconium pearl, 15~30min of pre-grinding is added.

The revolving speed of the grinding is 1500~2500r/min.

The pH adjusting agent is ammonium hydroxide, N, one of N- dimethylethanolamine and 2-amino-2-methyl-1-propanol Or at least two.

The coalescing agent is in alcohol ester 12, diethylene glycol monobutyl ether, butyl glycol ether and dipropylene One kind or at least two.

The defoaming agent is BASF ED2522 and Digao Foamex823, Digao Foamex825 and Digao One of Foamex833 or at least two.

A kind of water-based ink mill base, is prepared by above-mentioned preparation method.

Principle: the method for disperse black carbon is mostly that a large amount of small molecule dispersing agent is added at present, does not have filming performance, grinds It grinds obtained mill base to need to form a film with the collocation of other resins, and due to the presence of a large amount of small molecule dispersing agents, obtained film Appearance rough continuity is poor.Emulsion acrylic resin can form the successional film for having good mechanical strength, and obtained film Smooth.But adsorbed by carbon black poly- under the high shear forces of traditional emulsion acrylic resin during the grinding process, it leads Emulsion breaking is caused, the stability of pigment paste of preparation is bad.The present invention does following improvement to traditional emulsion acrylic resin: using third Dispersing agent of the olefin(e) acid resin emulsion as carbon black, while it being graft-polymerized with containing the function monomer of double bond and more carboxyls, and Using reactive emulsifier and the polycarboxylic function monomer of double bond be collectively incorporated into acrylic resin segment jointly a large amount of yin from Son, latex particle are coated on carbon blacksurface, so that carbon blacksurface covers charge, are promoted using ion electrostatic repulsion more Carbon black dispersion avoids lotion from flocculating.Meanwhile water-soluble polymer long-chain is accessed in acrylic molecular chain to improve dispersion The stability of carbon black further promotes emulsion resin to carbon black using the molecule of long-chain acrylic monomers access long-chain side group Dispersion effect and enhancing are to the tolerance of diluent.The water-based ink mill base of preparation both can the high pigment charcoal of the more deals of fine dispersion It is black, can also be formed be uniformly dispersed, the stabilization paint film of high shading rate.

The present invention has the following advantages and effects with respect to the prior art:

1. water polyacrylic acid emulsion resin of the invention to the dispersibility and stability of carbon black more preferably, and film-formation result Good, water-based ink mill base fineness≤10 μm of preparation meet requirement, form be uniformly dispersed, high shading rate stablizes paint Film.Without significant change, filming performance is good by the naked eye for color paste viscosity and fineness after period of storage 6 months.

2. water-and acrylate emulsion resin of the invention can effectively reduce during grinding carbon black and preparing mill base to it The use of his organic additive reduces volatile organic compounds (VOC) content and solvent raw material dosage, more environmental protection and saving, And there is better tolerance to diluent ethanol.

3. water polyacrylic acid emulsion resin of the invention overcomes traditional emulsion acrylic resin in process of lapping It is adsorbed by carbon black poly- under middle high shear forces, leads to the demulsification of lotion, the bad problem of the stability of pigment paste of preparation.

Specific embodiment

Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will It will be appreciated that following embodiments and embodiment are merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.It is not specified Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer, It is the conventional products that can be obtained by commercially available purchase.