阅读说明：本技术 一种用于快干型油墨的耐酒***性树脂乳液连接料及其制备方法 (Alcohol-resistant water-based resin emulsion binder for quick-drying ink and preparation method thereof ) 是由 张天 桂雪峰 刘凌利 孙龙凤 许正敏 方燕 许凯 于 2019-09-18 设计创作，主要内容包括：本发明提供了一种用于快干型油墨的耐酒精水性树脂乳液连接料及其制备方法。所述的耐酒精水性树脂乳液连接料采用乳化剂A与反应型非离子型表面活性剂配合作为乳化体系,以IBOMA为主要单体合成得到,保证乳液中加入酒精后的稳定性,防止破乳。所述的乳化剂A可有效降低被醇溶解可能性,同时本身可以起到保护胶体的作用,为乳胶粒提供较强的静电排斥力,起到包覆保护的作用。所述的耐酒精水性丙烯酸酯乳液树脂与乙醇混合作为油墨连接料,可大幅提高油墨干燥速率,在研磨中无需添加其他树脂既可良好分散,可直接形成分散均匀、高遮光率的稳定漆膜,且色浆稳定性很好,降低VOC含量与溶剂类原料用量,更具环保节约性,具有良好的产业化前景。(The invention provides an alcohol-resistant water-based resin emulsion binder for quick-drying ink and a preparation method thereof. The alcohol-resistant water-based resin emulsion binder is synthesized by adopting the emulsifier A and a reactive nonionic surfactant as an emulsification system and adopting IBOMA as a main monomer, so that the stability of the emulsion after the alcohol is added is ensured, and demulsification is prevented. The emulsifier A can effectively reduce the possibility of being dissolved by alcohol, and can play a role in protecting colloid, provide strong electrostatic repulsion force for emulsion particles and play a role in coating protection. The alcohol-resistant water-based acrylate emulsion resin is mixed with ethanol to be used as an ink binder, so that the drying rate of the ink can be greatly improved, the ink can be well dispersed without adding other resins during grinding, a stable paint film with uniform dispersion and high light shading rate can be directly formed, the stability of the color paste is good, the VOC content and the using amount of solvent raw materials are reduced, the environment friendliness and the economy are realized, and the industrialization prospect is good.)

1. The emulsifier A is characterized by being prepared by the following method:

and (3) forming amic acid by the amino group of the long-chain primary amine and the anhydride of the ring-opened benzene-horse resin, adding a sulfonylation amination reagent to perform sulfonylation amination reaction with the amic acid to eliminate the residual hydrogen of the amino group, and adding alkali to neutralize the carboxylic acid and the residual sulfonic acid to obtain the emulsifier A.

2. Emulsifier a according to claim 1, characterized in that:

the molecular weight of the benzene-maleic resin is M_w＝1000～3000g/mol；

The molecular weight of a polyvinyl alcohol part in the acrylic acid end-capped polyvinyl alcohol is 400-4000 g/mol;

the sulphonamide reagent is at least one of dodecyl benzene sulfonic acid, octa-alkyl sulfonic acid and propane sultone;

the alkali is at least one of NaOH or KOH;

the long-chain primary amine is primary amine containing 8-12 carbon atoms;

the long-chain primary amine and the benzene maleic resin are mixed according to the mass ratio of 1: 1.1.

3. A preparation method of alcohol-resistant water-based resin emulsion binder for quick-drying ink is characterized by comprising the following steps:

IBOMA is taken as a main monomer, acrylic acid or acrylate monomers are taken as comonomers, the emulsifier A and the emulsifier B in any one of claims 1 or 2 are taken as an emulsifier system, and the emulsifier B is acrylic acid terminated polyvinyl alcohol; adding 1-5 parts by mass of an emulsifier A and 1-5 parts by mass of an emulsifier B, wherein the mass percentage is calculated relative to the total mass of the IBOMA and the comonomer, and the mass ratio of the emulsifier A to the emulsifier B is ensured to be 1: 3-3: 1, adding the IBOMA, the comonomer and water, and pre-emulsifying to obtain a pre-emulsion; firstly, taking part of the pre-emulsion, slowly adding an initiator, and reacting to obtain a prepolymer of the water-based resin; and heating to 75-85 ℃, simultaneously dripping the rest of pre-emulsion and initiator into the prepolymer of the water-based resin, and carrying out emulsion heat preservation reaction after finishing dripping to obtain the alcohol-resistant water-based resin emulsion binder of the quick-drying ink.

4. The method for preparing an alcohol-resistant aqueous resin emulsion vehicle for a quick-drying ink according to claim 3, characterized in that:

the comonomer is one or at least two of methyl methacrylate, methacrylic acid, butyl acrylate, isooctyl acrylate, itaconic acid and hydroxypropyl acrylate;

adding an initiator when the prepolymer of the water-based resin is added when the temperature of the pre-emulsion is increased to 72-75 ℃;

the reaction time in the prepolymer of the water-based resin obtained by the reaction is 20-50 min;

the addition amount of the IBOMA is 5-15 parts by mass;

the prepolymer of the aqueous resin obtained by the reaction is stirred for reaction;

the time of the emulsion heat preservation reaction is 2-5 h;

the emulsion heat-preservation reaction is carried out at 80-85 ℃.

5. The method for preparing an alcohol-resistant aqueous resin emulsion vehicle for a quick-drying ink according to claim 4, characterized in that:

the initiator is one or two of ammonium persulfate or potassium persulfate;

the pre-emulsification time is 10-20 min;

the rotating speed of the stirring reaction is 150-180 r/min;

the addition amount of the comonomer is 75-90 parts by mass;

the amount of the water is 80-110 parts by mass;

the pre-emulsion part is prepared by taking 1/6-1/4 of pre-emulsion in advance for reaction.

6. An alcohol-resistant water-based resin emulsion binder for quick-drying ink is characterized in that:

the preparation method of any one of claims 3 to 5.

7. The water-based ink color paste is characterized by being prepared from the following raw materials in parts by mass:

8. the preparation method of the water-based ink color paste according to claim 7, which is characterized by comprising the following steps:

(1) taking 40-60 parts by mass of the alcohol-resistant water-based resin emulsion binder of the quick-drying ink, and adding 1-5 times of ethanol for mixing;

(2) adjusting the pH value to 8, adding 2-6 parts by mass of a film forming aid, 0.2-0.4 part by mass of a defoaming agent, 20-30 parts by mass of water, 10-40 parts by mass of ethanol and zirconium beads, and pre-grinding; and then adding 15-30 parts by mass of pigment, and uniformly grinding to obtain the water-based ink paste.

9. The preparation method of the water-based ink color paste according to claim 8, wherein the method comprises the following steps:

the pH value is adjusted by one or at least two of ammonia water, N-dimethylethanolamine and 2-amino-2-methyl-1-propanol in the step (2);

the film forming additive in the step (2) is one or at least two of alcohol ester twelve, diethylene glycol monobutyl ether and dipropylene glycol butyl ether;

the defoaming agent in the step (2) is one or at least two of basf ED2500, basf ED2522 and dikamex 823, dikamex 825 and dikamex 833;

the pigment in the step (2) is a bright red pigment;

the pre-grinding time in the step (2) is at least 15 min;

the rotation speed of the grinding in the step (2) is 1500-2500 r/min;

and (3) grinding in the step (2) for 1-2 h.

10. The use of the alcohol-resistant aqueous resin emulsion binder for quick-drying ink or the aqueous ink paste according to claim 7 in aqueous ink.

Technical Field

The invention belongs to the technical field of water-based ink, and particularly relates to an alcohol-resistant water-based resin emulsion binder for quick-drying ink and a preparation method thereof.

Background

The water-based ink takes water as a solvent, and can effectively solve the problems of emission and pollution in the current packaging and printing industries due to the extremely low VOC content and excellent environmental protection performance, and can replace the traditional solvent-based ink. The binder of the water-based ink is generally water-based resin, and the research on the binder at home and abroad at present mainly comprises modified rosin water-soluble resin, polyacrylic acid water-soluble resin and emulsion type water-soluble resin, wherein the emulsion type binder is a type which develops very rapidly. Compared with the coating attached to the porous substrate, the substrate attached to the ink is generally a compact material, water cannot penetrate into the base layer quickly, and the drying speed is slow. Since the emulsion resin itself is a thermodynamically unstable system and the thermal degradation temperature of the resin itself is not high, it is difficult to accelerate solvent evaporation by heating. In order to solve the problem that the drying process of the water-based ink is slow, researchers adopt a method of adding low molecular alcohols (such as methanol, ethanol, isopropanol and the like) to increase the volatility of a solvent so as to realize fast drying of the ink. However, most of the emulsifiers adopted in the traditional resin emulsion binder synthesis process are small molecular emulsifiers, and the emulsifiers are easy to dissolve after alcohol solvents (mainly alcohol) are added, so that emulsion breaking of latex particles is not available. Common emulsifiers such as OP-10 (alkylphenol ethoxylates), sulfonate, alkylphenol ethoxylates and the like are small molecular emulsifiers and are easily dissolved in ethanol.

Therefore, research on preparing the resin emulsion with alcohol resistance has important practical significance on the development of the quick-drying ink, wherein the important point is to improve the stability of the emulsifier and prepare an emulsifier system which can stably exist in an alcohol solvent system.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide the emulsifier A, the emulsifier is a macromolecular surfactant, the possibility of being dissolved by alcohol can be effectively reduced, and meanwhile, the emulsifier A can play a role of protecting colloid, provides strong electrostatic repulsion force for emulsion particles and plays a role of coating protection.

The second purpose of the invention is to provide a preparation method of the alcohol-resistant water-based resin emulsion binder of the quick-drying ink; the emulsifier A is matched with a reactive nonionic surfactant (marked as emulsifier B) to be used as an emulsifier, and IBOMA (isobornyl methacrylate) is used as a main monomer of the alcohol-resistant resin emulsion to synthesize the resin emulsion binder for the quick-drying ink.

The third purpose of the invention is to provide the alcohol-resistant water-based resin emulsion binder of the quick-drying ink prepared by the preparation method, wherein the resin emulsion binder can resist the erosion of low-molecular alcohol solvent (such as alcohol), has good stability in preparing color paste and can be directly formed into a film.

The fourth purpose of the invention is to provide an alcohol erosion resistant resin emulsion.

The fifth purpose of the invention is to provide a synthetic method of the alcohol erosion resistant resin emulsion.

The purpose of the invention is realized by the following technical scheme:

an emulsifier A is prepared by the following method: and (2) forming amic acid by the amino group of the long-chain primary amine and the anhydride of ring-opening styrene-maleic resin (SMA), adding a sulfonylation reagent to perform sulfonylation reaction with the amic acid to eliminate the residual hydrogen of the amino group, and then adding alkali to neutralize the carboxylic acid and the residual sulfonic acid to obtain the emulsifier A.

The molecular weight of the styrene-maleic resin (SMA) is preferably M_w＝1000～3000g/mol。

The molecular weight of the polyvinyl alcohol moiety in the acrylic acid-terminated polyvinyl alcohol is preferably 400 to 4000 g/mol.

The sulphonamide reagent is preferably at least one of dodecylbenzene sulphonic acid, decaalkylbenzene sulphonic acid, octaalkyl sulphonic acid and propane sultone.

The alkali is preferably at least one of NaOH or KOH.

The long-chain primary amine is preferably primary amine containing 8-12 carbon atoms; more preferably at least one of octaalkylamine, decaalkylamine and dodecylamine.

The long-chain primary amine and the benzene horse resin are preferably matched according to the mass ratio of 1:1.1, and the long-chain primary amine is slightly excessive to ensure complete ring opening.

A preparation method of alcohol-resistant water-based resin emulsion binder for quick-drying ink comprises the following steps:

IBOMA is used as a main monomer, acrylic acid or acrylate monomer is used as a comonomer, the emulsifier A and the emulsifier B are used as an emulsifier system, and the emulsifier B is acrylic acid-terminated polyvinyl alcohol (PEG); adding 1-5 parts by mass of an emulsifier A and 1-5 parts by mass of an emulsifier B, wherein the mass percentage is calculated relative to the total mass of the IBOMA and the comonomer, and the mass ratio of the emulsifier A to the emulsifier B is ensured to be 1: 3-3: 1, adding the IBOMA, the comonomer and water, and pre-emulsifying to obtain a pre-emulsion; firstly, taking part of the pre-emulsion, slowly adding an initiator, and reacting to obtain a prepolymer of the water-based resin; and heating to 75-85 ℃, simultaneously dripping the rest of pre-emulsion and initiator into the prepolymer of the water-based resin to ensure that the polymerization reaction is carried out stably, the obtained emulsion is uniform and reduces gel, and carrying out the emulsion heat preservation reaction after finishing dripping to obtain the alcohol-resistant water-based resin emulsion binder of the quick-drying ink.

The comonomer is preferably one or at least two of Methyl Methacrylate (MMA), methacrylic acid (MAA), Butyl Acrylate (BA), isooctyl acrylate (EHA), itaconic acid (ITA) and hydroxypropyl acrylate (HPA).

The initiator is preferably one or two of ammonium persulfate or potassium persulfate.

The pre-emulsification time is preferably 10-20 min.

The reaction time of the prepolymer of the water-based resin obtained by the reaction is preferably 20-50 min, and the addition speed of the initiator can influence the size and uniformity of the particle size of the latex particles of the seed emulsion.

The prepolymer which is reacted to give the aqueous resin is preferably stirred.

The rotation speed of the stirring reaction is preferably 150-180 r/min, the rotation speed is too low, the stirring is not uniform, the normal distribution of the sizes of the latex particles is increased, and the gel is increased; too high a rotational speed can reduce the molecular weight of the polymer, which can negatively affect the stability in the grinding stage; the stirring is preferably effected by means of a stirrer.

The addition amount of the IBOMA is preferably 5-15 parts by mass; if IBOMA is added too little, it will affect the stability after addition of alcohol, and if too much, the cost will be too high.

The addition amount of the comonomer is preferably 75-90 parts by mass.

The amount of the water is preferably 80 to 110 parts by mass.

The operation of adding the initiator during the prepolymer of the water-based resin is preferably that the initiator is added when the temperature of the pre-emulsion rises to 72-75 ℃, the half-life of the low-temperature initiator is too long to influence the reaction process, and the initiation rate of the high-temperature initiator is too fast to cause implosion or uneven seed in the synthesis stage of the seed emulsion, so that the normal distribution of the size of the latex particles of the final emulsion is too large, and the probability of the occurrence of gel particles is greatly increased.

The pre-emulsion part is preferably pre-emulsion 1/6-1/4 in the pre-emulsion part for reaction.

The time of the emulsion heat-preservation reaction is preferably 2-5 h, so that the participating monomers in the emulsion have sufficient time to react, and the monomer residue is reduced.

The emulsion heat-preservation reaction is preferably carried out at 80-85 ℃, the emulsion is subjected to heat preservation in the temperature range after the dripping is finished, and the emulsion continues to react, and the temperature higher than 85 ℃ does not reduce the heat preservation time and can damage the stability of the emulsion.

An alcohol-resistant water-based resin emulsion binder for quick-drying ink is prepared by the preparation method.

The water-based ink paste is prepared from the following raw materials in parts by mass:

the preparation method of the water-based ink color paste comprises the following steps:

(1) taking 40-60 parts by mass of the alcohol-resistant water-based resin emulsion binder of the quick-drying ink, and adding 1-5 times of ethanol for mixing;

(2) adjusting the pH value to about 8, adding 2-6 parts by mass of a film forming additive, 0.2-0.4 part by mass of a defoaming agent, 20-30 parts by mass of water, 10-40 parts by mass of ethanol and zirconium beads, and pre-grinding; and then adding 15-30 parts by mass of pigment, and uniformly grinding to obtain the water-based ink paste.

The pH value of the adjustment in the step (2) is preferably adjusted by one or at least two of ammonia water, N-dimethylethanolamine and 2-amino-2-methyl-1-propanol.

The film forming auxiliary agent in the step (2) is preferably one or at least two of alcohol ester twelve, diethylene glycol monobutyl ether and dipropylene glycol butyl ether.

The antifoaming agent described in step (2) is preferably one or at least two of basf ED2500, basf ED2522 and difo Foamex823, difo Foamex825, and difo Foamex 833.

The pigment described in step (2) is preferably a bright red pigment.

The pre-grinding time in the step (2) is preferably at least 15 min; more preferably 15 to 30 min.

The rotation speed of the grinding in the step (2) is preferably 1500-2500 r/min; the color paste can be sufficiently ground in the rotating speed range, and the grinding stability is not influenced.

The grinding time in the step (2) is preferably 1-2 h, and if the time is too short, the grinding is insufficient.

The alcohol-resistant water-based resin emulsion binder for the quick-drying ink or the water-based ink paste is applied to the water-based ink.

The synthetic macromolecular surfactant designed by the invention can effectively reduce the possibility of being dissolved by alcohol, and simultaneously can play a role of protecting colloid, provides stronger electrostatic repulsion force for latex particles and plays a role of coating protection; meanwhile, a reactive nonionic surfactant is introduced, and the polymerization reaction process participates in monomer polymerization to obtain an emulsifier chemically bonded with the resin matrix, so that the possibility of dissolving by alcohol can be avoided or reduced. The two emulsifier systems are used as the emulsifier system in proportion, and the water-based resin obtained by polymerization can be expected to resist ethanol erosion and keep emulsion stable.

Compared with the prior art, the invention has the following advantages and effects:

(1) the invention provides a preparation method of an alcohol-resistant water-based resin emulsion binder for quick-drying ink. Specifically, the combination of an anionic macromolecular surfactant (emulsifier A) and a reactive nonionic surfactant (emulsifier B) is used as an emulsifier system, isobornyl methacrylate is used as a main monomer, and multiple acrylic monomers are used as comonomers to polymerize to form stable resin emulsion. The stability of the emulsion after adding alcohol is ensured and the emulsion breaking is prevented by utilizing the anionic high molecular characteristic of the emulsifier A and the solvent resistance of the emulsifier B after being chemically bonded to the latex particles.

(2) The alcohol-resistant water-based acrylate emulsion resin prepared by the invention is mixed with ethanol to be used as an ink binder, so that the drying rate of the ink can be greatly improved, the use of other dispersing agents in the process of grinding and preparing color paste is reduced, the VOC content and the use amount of solvent raw materials are reduced, and the environment-friendly property and the economical property are realized.

(3) The alcohol-resistant water-based acrylate emulsion resin and the high-content pigment (such as scarlet pigment) prepared by the invention do not need to be added with other resins during grinding, can be well dispersed, can also directly form a stable paint film with uniform dispersion and high shading rate, and has good color paste stability.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.