阅读说明：本技术 不含双酚a的罐听涂料及其制备方法 (Can-coating and preparation method thereof without bisphenol-A ) 是由 宁坤 许峰 付静 童军 于 2019-08-29 设计创作，主要内容包括：本发明提供了一种不含双酚A的罐听涂料及其制备方法,所述罐听涂料由2-亚甲基-1,3-二氧环庚烷,甲基丙烯酸缩水甘油酯以及丙烯酸单体先合成一种环氧改性的聚酯树脂,再与酚醛树脂配合得到一种不含双酚A单体的罐听涂料。本发明保留了具有很高抗性的环氧-酚醛反应体系,同时不使用含有双酚A的单体,使得涂层具有很好的耐酸性,耐蒸煮性能等。由于环氧改性聚酯的主链中有大量的酯键存在,从而更好的提供了金属附着力及其可加工性能。(The present invention provides a kind of can-coating and preparation method thereof without bisphenol-A, the can-coating is by 2- methylene -1,3- cyclic heptane dioxide, glycidyl methacrylate and acrylic monomers first synthesize a kind of epoxy-modified polyester resin, then cooperate to obtain a kind of can-coating without bisphenol A monomer with phenolic resin.Present invention preserves having very resistance epoxy-phenol-formaldehyde reaction system, while the monomer containing bisphenol-A is not used, so that coating has good acid resistance, boiling resistance can be waited.Due in the main chain of epoxy-modified polyester with the presence of a large amount of ester bond, to preferably provide metal adhesion and its processability.)

1. a kind of can-coating without bisphenol-A, it is characterised in that: the coating is mainly by epoxy modified polyester resin, phenolic aldehyde Resin, catalysts and solvents composition, the phenolic resin account for the 10-25% of epoxy modified polyester resin quality, and the catalyst accounts for The 1-3% of epoxy modified polyester resin quality, the solvent account for the 30-60% of epoxy modified polyester resin quality.

2. a kind of can-coating without bisphenol-A as described in claim 1, it is characterised in that: the coating further includes coating Additive, the coating additive is in levelling agent, delustering agent, pigment wetting and dispersing agent, pigment, filler, defoaming agent One or more combination.

3. a kind of can-coating without bisphenol-A as described in claim 1, it is characterised in that: the catalyst be selected from carboxylic acid, One of sulfonic acid, tertiary amine, tertiary phosphine or more than one combinations.

4. a kind of can-coating without bisphenol-A as described in claim 1, it is characterised in that: the solvent includes aromatic hydrocarbon The a combination of one or more of class solvent, alcohols solvent, ether solvent, esters solvent and ketones solvent.

5. a kind of a kind of preparation method of the can-coating without bisphenol-A as described in claim 1, it is characterised in that: including Following steps:

S1, epoxy modified polyester resin is prepared, according to monomer molar content ratio 2- methylene 1,3-cyclic heptane dioxide 30- 60%, glycidyl methacrylate 10-30%；Acrylic monomers 10-30% is obtained by free radical polymerization；

S2, the mixed solvent that propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, aromatic hydrocarbon solvent are added into mixing kettle, are being stirred It mixes under state, epoxy modified polyester resin prepared by S1, phenolic resin is added into mixing kettle, stirs evenly, is then added Catalyst, levelling agent, high-speed stirred are uniformly mixed so as to obtain food cover inner-wall paint.

6. a kind of preparation method of the can-coating without bisphenol-A as claimed in claim 5, it is characterised in that: in the S1 Epoxy modified polyester resin number-average molecular weight be 10000-30000,50-80 DEG C of glass transition temperature.

7. a kind of preparation method of the can-coating without bisphenol-A as claimed in claim 5, it is characterised in that: in the S1 Acrylic monomers is selected from iso-bornyl acrylate, lauryl acrylate, lauryl methacrylate, methacrylic acid trifluoro second Two kinds or more any combination of ester, butyl methacrylate.

8. a kind of preparation method of the can-coating without bisphenol-A as claimed in claim 5, it is characterised in that: the S2 is mixed Propylene glycol methyl ether acetate in bonding solvent, ethylene glycol monobutyl ether, aromatic hydrocarbon solvent mass ratio be 1:1:4.

Technical field

The invention belongs to technical field of coatings, and in particular to a kind of can-coating and preparation method thereof without bisphenol-A.

Background technique

With the gradual improvement of people's living standard, more and more people start to pursue the life of high quality, to food Safety problem is especially paid attention to, therefore food safety also just becomes in the nature of things with worldwide challenge and public health concern Topic.

The metal can of China's food listens inner coating mainly or using epoxy resin and organosol resin at present, is used for It protects metal can not by the corrosion of content, had both been avoided that in metal can that heavy metal transformation increased the shelf-life to food in this way.Its In, two kinds of most commonly seen materials are epoxy-phenolic resin and vinyl organosol resin, they are in flexibility, adhesive force There is certain advantage with inoxidizability etc., is therefore widely used in the material of film in food metal can.Epoxy- Phenolic resin is mainly synthesized by bisphenol-A (BPA) and bisphenol-A-diglycidyl ether (BADGE) reaction.Vinyl is organic molten Gum resin then needs to add bisphenol-A-diglycidyl ether (BADGE) and bisphenol-f-diglycidyl ether in process of production (BFDGE) to remove the hydrochloric acid as caused by curing reaction, coating is avoided to be decomposed.Wherein bisphenol-A is similar to estrogen, can be with Cause the hormonal reaction of human body.On October 18th, 2008, federal government of Canada announced, determined to arrange bisphenol-A (BPA) Enter in noxious material list, it means that this chemicals for being widely used in food packaging will be forbidden making in Canada soon With, therefore develop existing good function and the product without structure of bisphenol A becomes more meaningful.

Summary of the invention

The present invention provides a kind of can-coating and preparation method thereof without bisphenol-A.

The purpose of the present invention is achieved through the following technical solutions:

A kind of can-coating without bisphenol-A, the coating mainly by epoxy modified polyester resin, phenolic resin, catalyst and Solvent composition, the phenolic resin account for the 10-25% of epoxy modified polyester resin quality, and the catalyst accounts for epoxy-modified polyester The 1-3% of resin quality, the solvent account for the 30-60% of epoxy modified polyester resin quality.

Preferably, the coating further includes coating additive, and the coating additive is selected from levelling agent, delustering agent, pigment Wetting and one of dispersing agent, pigment, filler, defoaming agent or more than one combinations.

Preferably, the catalyst is selected from one of carboxylic acid, sulfonic acid, tertiary amine, tertiary phosphine or more than one combinations.

Preferably, the solvent includes aromatic hydrocarbon solvent, alcohols solvent, ether solvent, esters solvent and ketones solvent One or more kinds of combinations.

Preferably, a kind of preparation method of the can-coating without bisphenol-A described in a kind of meaning, includes the following steps:

S1, epoxy modified polyester resin is prepared, according to monomer molar content ratio 2- methylene 1,3-cyclic heptane dioxide 30- 60%, glycidyl methacrylate 10-30%；Acrylic monomers 10-30% is obtained by free radical polymerization；

S2, the mixed solvent that propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, aromatic hydrocarbon solvent are added into mixing kettle, are being stirred It mixes under state, epoxy modified polyester resin prepared by S1, phenolic resin is added into mixing kettle, stirs evenly, is then added Catalyst, levelling agent, high-speed stirred are uniformly mixed so as to obtain food cover inner-wall paint.

Preferably, epoxy modified polyester resin number-average molecular weight is 10000-30000, glass transition temperature in the S1 50-80℃。

Preferably, acrylic monomers is selected from iso-bornyl acrylate, lauryl acrylate, methacrylic acid in the S1 Two kinds or more any combination of lauryl, trifluoroethyl methacrylate, butyl methacrylate.

Preferably, the quality of the S2 in the mixed solvent propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, aromatic hydrocarbon solvent Than for 1:1:4.

The beneficial effects of the present invention are embodied in: present invention preserves having very resistance epoxy-phenol-formaldehyde reaction system, together When without using the monomer containing bisphenol-A so that coating has good acid resistance, boiling resistance can be waited.Due to epoxy-modified poly- With the presence of a large amount of ester bond in the main chain of ester, to preferably provide metal adhesion and its processability.

Specific embodiment

Below by way of specific embodiment, the present invention will be further elaborated.