阅读说明：本技术 一种用于水性印铁涂料的改性羟基丙烯酸乳液及其制备方法 (A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing ) 是由 柴广 雷木生 游仁国 于 2019-08-23 设计创作，主要内容包括：本发明提供了一种用于水性印铁涂料的改性羟基丙烯酸乳液,上述用于水性印铁涂料的改性羟基丙烯酸乳液为核壳结构,在乳胶粒的核层和壳层引入不同含量的羟基,其中核层的羟基活性高于壳层,同时使羟基大多数富集在壳层；壳层通过接枝反应引入有环氧树脂,同时在壳层还引入有交联单体,所述乳化剂接枝在聚合物分子上；采用以下方法所制备：(1)单体预乳化液的制备；(2)种子乳液的制备；(3)核壳结构乳液的制备；(4)过滤后即得到用于水性印铁涂料的改性羟基丙烯酸乳液。本发明提供的水性印铁涂料其固化速度、附着性、耐蒸煮、耐溶剂等较常规水性羟基丙烯酸乳液都有了极大的提高。(The present invention provides a kind of modified hydroxyl acrylic emulsions for aqueous coatings for tin plate printing, the above-mentioned modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing is core-shell structure, the hydroxyl of different content is introduced in the stratum nucleare and shell of emulsion particle, wherein the hydroxyl activity of stratum nucleare is higher than shell, while most of making hydroxyl and being enriched in shell；Shell has epoxy resin by graft reaction introducing, while also introducing crosslinking monomer in shell, and the emulsifier is grafted on polymer molecule；Using prepared by following methods: (1) preparation of monomer pre-emulsion；(2) preparation of seed emulsion；(3) preparation of core-shell emulsion；(4) the modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing is obtained after filtering.Its curing rate of aqueous coatings for tin plate printing provided by the invention, adhesion, resistance to boiling, solvent resistant etc. are all greatly improved compared with standard aqueous hydroxyl acrylic emulsion.)

1. a kind of modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing, it is characterised in that: above-mentioned to be applied for aqueous tin graphed sheet The modified hydroxyl acrylic emulsion of material is core-shell structure, introduces the hydroxyl of different content in the stratum nucleare and shell of emulsion particle, wherein The hydroxyl activity of stratum nucleare is higher than shell, while most of making hydroxyl and being enriched in shell；Shell has epoxy by graft reaction introducing Resin, while crosslinking monomer is also introduced in shell, the emulsifier is grafted on polymer molecule；

The modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing is using prepared by following methods: (1) the pre- cream of monomer Change the preparation of liquid: sequentially adding 8~12 parts of deionized waters, 0.2~0.4 part of compound emulsifying agent into emulsion tank, stirring is to filling Divide dissolution, 15~20 parts of acrylate monomers, 3~5 parts of functional acrylic monomers are then added, obtain white after high-speed stirred Monomer pre-emulsion 1.；

8~12 parts of deionized waters, 0.2~0.4 part of compound emulsifying agent are sequentially added into emulsion tank, stirring is dissolved to abundant, Then 15~20 parts of acrylate monomers, 3~5 parts of functional acrylic monomers, 1~2 part of epoxy resin, 1~2 part of crosslinking is added 2. monomer obtains the monomer pre-emulsion of white after high-speed stirred；

(2) 20~40 parts of deionized waters, 0.2~0.4 part of composite emulsifying the preparation of seed emulsion: are sequentially added into reaction kettle Agent, 0.04~0.06 part of pH buffer are stirred to abundant dissolution, and 0.01~0.03 part of initiator is added when being warming up to 45~50 DEG C, It is continuously heating to 70~80 DEG C and 3%~8% monomer pre-emulsion is added 1., to obtain blue light translucent by 20~30min of heat preservation Seed emulsion；

(3) preparation of core-shell emulsion: initiator is obtained with 8~12 parts 0.08~0.12 part of deionized water dissolving of initiator Solution, to seed emulsion heat preservation after simultaneously be added dropwise 2/5~3/5 initiator solution and remaining monomer pre-emulsion 1., Time for adding is 1~2 hour, and reaction temperature is 80~85 DEG C, and keeps the temperature 30min；Then be added dropwise remaining initiator solution and 2., time for adding is 1~2 hour to monomer pre-emulsion, and reaction temperature is 80~85 DEG C；

(4) after completion of dropwise addition, 85~90 DEG C keep the temperature 0.5~2 hour, are then cooled to 50 DEG C hereinafter, being added 0.03~0.05 part Amine neutralizer adjusts lotion pH 7~9, and the modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing is obtained after filtering.

2. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Compound emulsifying agent compounded by nonionic emulsifier and anion emulsifier, wherein nonionic emulsifier be fatty alcohol polyoxy One of vinethene, ethoxylated dodecyl alcohol, fatty acid methyl ester APEO, allyl alkyl polyoxyethylene ether or two Kind or more mixture, wherein anion emulsifier be neopelex, lauryl sodium sulfate, dioctyl succinate The mixture of one or more of sodium sulfonate, allyl alkyl polyoxyethylene ether nekal.

3. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Electrolyte be one or more of sodium bicarbonate, ammonium hydrogen carbonate, saleratus mixture.

4. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Acrylate monomer be that n-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, styrene, methacrylic acid are different The mixture of one or more of norbornene ester, n-BMA, Tert-butyl Methacrylate.

5. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Functional acrylic monomers is methacrylic acid, acrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxypropyl Ester, hydroxy propyl methacrylate, the mixture of one or more of hy-droxybutyl.

6. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used The mixture of one or more of initiator ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.

7. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Amine neutralizer is the mixture of one or more of dimethylethanolamine, sodium hydroxide, ammonium hydroxide.

8. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Cross-linking monomer be acetoacetoxyethyl methacrylate, glycidyl methacrylate, Diacetone Acrylamide, N- hydroxyl The mixture of one or more of Methacrylamide.

9. the modified hydroxyl acrylic emulsion according to claim 1 for aqueous coatings for tin plate printing, it is characterised in that: used Epoxy resin be one or more of E51, E44, E20, E12, E06 mixture.

Technical field

The present invention relates to a kind of modified hydroxyl acrylic emulsion more particularly to a kind of modification hydroxyls for aqueous coatings for tin plate printing Base acrylic emulsion belongs to fine chemicals and preparation method thereof field.

Background technique

Aqueous coatings for tin plate printing refers to the general name for applying a kind of coating on tinplate or aluminium, also known as tin printing ink.In recent years Come the development with food industry and packaging industry, various can product rapid developments, therefore the feature of environmental protection of aqueous coatings for tin plate printing and High-performance also more and more attention has been paid to.Most common its film forming matter of aqueous coatings for tin plate printing be all by hydroxyl resin and Amino resins is formed by curing by high-temperature baking, and wherein amino resins is applied more mature, mainly there is cyanogen spy 325 and 303 etc., and The resin of hydroxyl is generally pure and mild Hydroxylated acrylic resin of solvent type polyester polyols etc., these solvent type resins in production and It can be discharged in use process a large amount of volatile organic compounds (VOC), seriously endanger environment.

Also there is aqueous hydroxy resin to be applied at present, mainly there is water-soluble poly ester polyol, water soluble hydroxy propylene Acid resin, water-based hydroxyl acrylic acid dispersion and water-based hydroxyl acrylic emulsion etc..

109485834A discloses a kind of PCM tin graphed sheet water-base resin, but has still used in resin synthesis process organic Solvent reduces viscosity, although relative solvent type resin VOC content decreases, its total VOC content is still higher.

Since these water-soluble resins that limit of synthesis technology all contain a certain amount of cosolvent, environmental protection is wanted It is not applicable for seeking higher aqueous coatings for tin plate printing.And water-based hydroxyl acrylic emulsion does not contain any from emulsion polymerization Organic solvent has the excellent feature of environmental protection, is increasingly taken seriously, but water-based hydroxyl acrylic emulsion also has its deficiency Place, for example will lead to the paint film adhesion after solidifying, solvent resistance, boiling resistance using emulsifier in synthesis process and be deteriorated, this It is unevenly distributed that also result in curing efficiency low due to hydroxyl outside.

109929067 A of CN discloses a kind of hydroxyl acrylic emulsion with core-shell structure, passes through two layers of nucleocapsid of control The size and introducing caprolactone modification acrylate monomer of molecular weight, improve the patience and gloss of paint film, but this method does not have Have and make a search for specific application, and overall cost is higher.

To sum up, the water-based hydroxyl acrylic emulsion for aqueous coatings for tin plate printing of prior art report, comprehensive performance is simultaneously It is unsatisfactory, especially curing rate, solvent resistance and in terms of more traditional water-soluble resin there is also Very big gap, therefore develop very significant for the high-performance hydroxyl acrylic emulsion of aqueous coatings for tin plate printing.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of modified hydroxyl propylene yogurts for aqueous coatings for tin plate printing Liquid, aqueous coatings for tin plate printing its curing rate being formulated with it, adhesion, resistance to boiling, solvent resistant etc. are compared with standard aqueous hydroxyl Acrylic emulsion is all greatly improved.

The present invention realizes that above-mentioned purpose technical solution is as follows: a kind of modified hydroxyl propylene yogurt for aqueous coatings for tin plate printing Liquid, the above-mentioned modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing are core-shell structure, are drawn in the stratum nucleare and shell of emulsion particle Enter the hydroxyl of different content, wherein the hydroxyl activity of stratum nucleare is higher than shell, while most of making hydroxyl and being enriched in shell；Shell is logical Crossing graft reaction introducing has epoxy resin, while also introducing crosslinking monomer in shell, and the emulsifier is grafted on polymer point On son；

The modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing is using prepared by following methods: (1) monomer The preparation of pre-emulsion: sequentially adding 8~12 parts of deionized waters, 0.2~0.4 part of compound emulsifying agent into emulsion tank, stirring To abundant dissolution, 15~20 parts of acrylate monomers, 3~5 parts of functional acrylic monomers are then added, are obtained after high-speed stirred The monomer pre-emulsion of white is 1.；

8~12 parts of deionized waters, 0.2~0.4 part of compound emulsifying agent are sequentially added into emulsion tank, are stirred to sufficiently molten Then 15~20 parts of acrylate monomers, 3~5 parts of functional acrylic monomers, 1~2 part of epoxy resin, 1~2 part are added in solution 2. cross-linking monomer obtains the monomer pre-emulsion of white after high-speed stirred；

(2) 20~40 parts of deionized waters, 0.2~0.4 part compound the preparation of seed emulsion: are sequentially added into reaction kettle Emulsifier, 0.04~0.06 part of pH buffer are stirred to abundant dissolution, are added 0.01~0.03 part when being warming up to 45~50 DEG C and are drawn Agent is sent out, 70~80 DEG C is continuously heating to and 3%~8% monomer pre-emulsion is added 1., to obtain blue light semi-transparent by 20~30min of heat preservation Bright seed emulsion；

(3) preparation of core-shell emulsion: the initiator with 8~12 parts 0.08~0.12 part of deionized water dissolving is drawn Agent solution is sent out, 2/5~3/5 initiator solution and remaining monomer pre-emulsion is added dropwise after keeping the temperature to seed emulsion simultaneously 1. time for adding is 1~2 hour, reaction temperature is 80~85 DEG C, and keeps the temperature 30min；Then remaining initiator solution is added dropwise 2. with monomer pre-emulsion, time for adding is 1~2 hour, and reaction temperature is 80~85 DEG C；

(4) after completion of dropwise addition, 85~90 DEG C keep the temperature 0.5~2 hour, be then cooled to 50 DEG C hereinafter, be added 0.03~ 0.05 part of amine neutralizer adjusts lotion pH 7~9, and the modified hydroxyl propylene yogurt for aqueous coatings for tin plate printing is obtained after filtering Liquid.

Compound emulsifying agent used is compounded by nonionic emulsifier and anion emulsifier, wherein nonionic emulsifier For fatty alcohol polyoxyethylene ether, ethoxylated dodecyl alcohol, fatty acid methyl ester APEO, allyl alkyl polyoxyethylene ether One or more of mixture, wherein anion emulsifier be neopelex, lauryl sodium sulfate, The mixing of one or more of dioctyl sodium sulfosuccinate, allyl alkyl polyoxyethylene ether nekal Object.

Electrolyte used is the mixture of one or more of sodium bicarbonate, ammonium hydrogen carbonate, saleratus.

Acrylate monomer used be n-butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, styrene, The mixing of one or more of isobornyl methacrylate, n-BMA, Tert-butyl Methacrylate Object.

Functionality acrylic monomers used is methacrylic acid, acrylic acid, hydroxy-ethyl acrylate, hydroxyethyl methacrylate second Ester, hydroxypropyl acrylate, hydroxy propyl methacrylate, the mixture of one or more of hy-droxybutyl.

The mixture of one or more of initiator ammonium persulfate used, potassium peroxydisulfate, sodium peroxydisulfate.

Amine neutralizer used is the mixture of one or more of dimethylethanolamine, sodium hydroxide, ammonium hydroxide.

Cross-linking monomer used is acetoacetoxyethyl methacrylate, glycidyl methacrylate, diacetone The mixture of one or more of acrylamide, N hydroxymethyl acrylamide.

Epoxy resin used is the mixture of one or more of E51, E44, E20, E12, E06.

Compared with prior art, the beneficial effects of the present invention are:

(1) it during emulsion polymerization in such a way that two steps are added dropwise, is introduced in the stratum nucleare and shell of emulsion particle different Functional group.The hydroxyl that different content is specifically introduced in stratum nucleare and shell, makes hydroxyl be enriched in shell, more as much as possible In the generation of cross-linking reaction, curing efficiency is improved.

(2) epoxy resin is introduced by graft reaction in shell, the epoxy group, hydroxyl, ehter bond on epoxy resin assign Give the fabulous substrate adhesion of new resin and faster solidification rate.

(3) in shell introducing crosslinked monomer, making it, further cross-linking reaction reaction improves crosslink density in the curing process, Substantially increase solvent resistance, the boiling resistance of paint film.

(4) polymerizable reactive emulsifier is used during emulsion polymerization, emulsifier is finally grafted on polymer On molecule, reduce the presence of free emulsifier small molecule, improves conventional emulsifier to the shadow of paint film adhesion and patience It rings.

(5) acrylate monomers are screened, the hydroxyl activity of stratum nucleare is made to be higher than shell, it in this way can be to avoid out The phenomenon that existing outer layer solidification and internal layer are without sufficiently solidifying, can make outer layer rapid curing also and can guarantee that internal layer sufficiently solidifies.

(6) epoxy resin is screened, uses the epoxy resin of macromolecule as far as possible, adhesion can be improved in this way Also it can guarantee the flexibility of paint film.

In conclusion prepared by a kind of modified hydroxyl acrylic emulsion for aqueous coatings for tin plate printing provided by the invention Any organic solvent is not used in journey, environmentally friendly, the aqueous coatings for tin plate printing curing rate prepared with it is fast, and adhesion is good, And solvent resistance, boiling resistance, corrosion resistance are very excellent, and comprehensive performance is better than traditional hydroxypropyl lotion, and and water-soluble Resin is very close, has wide commercial application prospect.

Specific embodiment

Detailed specific description done to the present invention combined with specific embodiments below, but protection scope of the present invention not office It is limited to following embodiment.