阅读说明：本技术 环氧防腐底漆及其制备方法和具有底漆层的制品 (Epoxy anti-corrosion primer, preparation method thereof and product with primer layer ) 是由 夏震球 于 2020-05-19 设计创作，主要内容包括：本发明公开了一种环氧防腐底漆及其制备方法和具有底漆层的制品,该环氧防腐底漆包括组分A和组分B；以环氧防腐底漆的总重量为基准,组分A的原料包括：15～19％固体环氧树脂、9～15％液体环氧树脂、2～4％环氧活性稀释剂、48.5～60.5％填料、0.5～0.6％催化剂、7～9％溶剂；液体环氧树脂中含有占液体环氧树脂的总重量50～80％的螯合改性液体环氧树脂；以环氧防腐底漆的总重量为基准,组分B的原料包括：4～6％固化剂,固化剂包括酰胺基胺、聚醚胺和改性胺。本发明环氧防腐底漆固含量高、涂装VOCs排放量低,附着力强,适用于低表面处理的可带锈装涂,通用性强,所形成漆膜具有优异的物理机械性能和防腐性能。(The invention discloses an epoxy anticorrosive primer, a preparation method thereof and a product with a primer layer, wherein the epoxy anticorrosive primer comprises a component A and a component B; based on the total weight of the epoxy anticorrosive primer, the component A comprises the following raw materials: 15-19% of solid epoxy resin, 9-15% of liquid epoxy resin, 2-4% of epoxy active diluent, 48.5-60.5% of filler, 0.5-0.6% of catalyst and 7-9% of solvent; the liquid epoxy resin contains chelate modified liquid epoxy resin which accounts for 50-80% of the total weight of the liquid epoxy resin; based on the total weight of the epoxy anticorrosive primer, the component B comprises the following raw materials: 4-6% of a curing agent, wherein the curing agent comprises amidoamine, polyether amine and modified amine. The epoxy anti-corrosion primer disclosed by the invention is high in solid content, low in VOCs (volatile organic compounds) discharge amount during coating, strong in adhesive force, suitable for rusty coating with low surface treatment, strong in universality, and excellent in physical and mechanical properties and anti-corrosion properties of a formed paint film.)

1. The epoxy anticorrosive primer is characterized by comprising a component A and a component B;

based on the total weight of the epoxy anticorrosive primer, the preparation raw materials of the component A comprise: 15-19% of solid epoxy resin, 9-15% of liquid epoxy resin, 2-4% of epoxy active diluent, 48.5-60.5% of filler, 0.5-0.6% of catalyst and 7-9% of solvent; the liquid epoxy resin contains chelate modified liquid epoxy resin which accounts for 50-80% of the total weight of the liquid epoxy resin;

based on the total weight of the epoxy anticorrosive primer, the preparation raw materials of the component B comprise: 4-6% of a curing agent, wherein the curing agent comprises amidoamine, polyether amine and modified amine.

2. The epoxy anticorrosive primer according to claim 1, wherein the mass ratio of the component A to the component B is (9-30): 1.

3. the epoxy anticorrosion primer according to claim 1, wherein the catalyst is at least one of aliphatic acrylic resin and tertiary amine catalyst.

4. The epoxy corrosion resistant primer according to claim 1, wherein the solvent comprises an alcohol solvent, an aromatic hydrocarbon solvent, and a ketone solvent.

5. The epoxy anticorrosive primer according to claim 1, wherein the filler comprises 21.5-25.5% of barium sulfate, 11-15% of talcum powder and 16-20% of feldspar powder based on the total weight of the epoxy anticorrosive primer.

6. The epoxy anticorrosion primer according to any one of claims 1 to 5, wherein the raw materials for preparing component A further comprise an auxiliary agent, and the auxiliary agent comprises at least one of an adhesion promoter, an anti-settling agent and an anti-sagging agent.

7. The epoxy anticorrosive primer according to claim 6, wherein the auxiliary comprises 0.4-0.6% of adhesion promoter, 1.5-2.0% of anti-settling agent and 0.3-0.6% of anti-sagging agent, based on the total weight of the epoxy anticorrosive primer.

8. The epoxy anticorrosive primer according to any one of claims 1 to 5, wherein the raw materials for preparing the component A further comprise 3.2-7.2% of pigment based on the total weight of the epoxy anticorrosive primer.

9. The method for preparing the epoxy anticorrosive primer according to any one of claims 1 to 8, characterized by comprising the steps of preparing a component A and preparing a component B; wherein the content of the first and second substances,

the preparation of the component A comprises the following steps:

s1, mixing and stirring the solid epoxy resin, the liquid epoxy resin, the epoxy active diluent, the filler, the catalyst and part of the solvent uniformly to obtain slurry;

s2, grinding the slurry to obtain grinding slurry;

s3, curing the grinding slurry, adjusting the viscosity to 40-60poise by using the residual solvent, and filtering;

the preparation of the component B comprises the following steps: and mixing and stirring the preparation raw materials of the component B uniformly, and then filtering.

10. An article having a primer layer comprising a substrate and a primer layer adhered to at least a portion of a surface of the substrate, the primer layer formed from the epoxy corrosion resistant primer of any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of coatings, in particular to an epoxy anticorrosive primer, a preparation method thereof and a product with a primer layer.

Background

In recent years, the problem of environmental pollution is increasingly severe, along with the issuance of a series of laws and regulations relating to environmental protection and air pollution control, governments also make a VOCs emission reduction plan one after another, and environmental-friendly coatings with low VOCs are vigorously promoted in the coating and painting industry.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the epoxy anticorrosive primer, the preparation method thereof and the product with the primer layer, wherein the epoxy anticorrosive primer has high solid content and strong adhesive force, and a paint film formed by coating has excellent physical and mechanical properties and anticorrosive property.

The technical scheme adopted by the invention is as follows:

in a first aspect of the present invention, there is provided an epoxy anti-corrosive primer comprising a component a and a component B;

based on the total weight of the epoxy anticorrosive primer, the preparation raw materials of the component A comprise: 15-19% of solid epoxy resin, 9-15% of liquid epoxy resin, 2-4% of epoxy active diluent, 48.5-60.5% of filler, 0.5-0.6% of catalyst and 7-9% of solvent; the liquid epoxy resin contains chelate modified liquid epoxy resin which accounts for 50-80% of the total weight of the liquid epoxy resin;

based on the total weight of the epoxy anticorrosive primer, the preparation raw materials of the component B comprise: 4-6% of a curing agent, wherein the curing agent comprises amidoamine, polyether amine and modified amine.

The chelate-modified liquid epoxy resin is an epoxy resin having 1 or more functional groups having a chelating effect. The group having a chelating effect may specifically be an acid group such as a carboxyl group, a phosphonic acid group, a sulfonic acid group, a phosphoric acid group, a sulfuric acid group, a nitric acid group, a boric acid group, or a functional group other than an acid group such as an alcoholic hydroxyl group, a phenolic hydroxyl group, a nitrile group, a thiol group, and an amino group. The chelate-modified liquid epoxy resin may be a commercially available product such as EP-49-10N from ADEKA, or a chelate-modified liquid epoxy resin from other companies. The liquid epoxy resin can adopt liquid epoxy resin E-51 or other commercially available liquid epoxy resins; the solid epoxy resin can be solid epoxy resin E-44 or other commercially available solid epoxy resins.

The amidoamine and the modified amine can also be directly prepared from commercial products, such as American air chemical amidoamine curing agent Ancamide 2443 and American air chemical modified amine curing agent Ancamide 2766. Wherein, the viscosity of the amido amine curing agent Ancamide 2443 is 30mPa.s/25 ℃, the amine value is 530mg KOH/g, the active hydrogen equivalent is 86, the amido amine curing agent Ancamide has good oil resistance, good adhesion to rusty metal and excellent moisture resistance and corrosion resistance. The viscosity of the modified amine curing agent Ancamide 2766 is 1000-3000mPa.s/25 ℃, the amine value is 255-295mg KOH/g, and the active hydrogen equivalent is 120, so that the modified amine curing agent Ancamide has excellent adhesion and elasticity, good flexibility and strength, and excellent weather resistance and aging resistance. In addition, other commercially available amidoamine curing agents and modified amine curing agents may also be used.

According to some embodiments of the invention, the mass ratio of the component A to the component B is (9-30): 1. preferably, the mass ratio of the component A to the component B is (15-20): 1.

the epoxy reactive diluent can specifically adopt at least one of butyl glycidyl ether and ethylene glycol diglycidyl ether, or adopt other commercially available epoxy reactive diluents.

According to some embodiments of the invention, the catalyst is at least one of an aliphatic acrylic resin, a tertiary amine catalyst (e.g., Ancamine K54 from U.S. gas); aliphatic acrylic resins are preferably used. The aliphatic acrylic resin is used as a catalyst, so that the reaction can be accelerated, the low-temperature hardening speed is improved, meanwhile, the whitening property of a paint film is reduced, and the water resistance and the hardness of the paint film are enhanced.

According to some embodiments of the invention, the solvent comprises an alcohol solvent, an aromatic hydrocarbon solvent and a ketone solvent. The solvent comprising alcohols, aromatic hydrocarbons and ketones is adopted by combining the selection of other raw materials, so that the dissolving power is strong, the volatilization speed is high, and the cost is low.

According to some embodiments of the invention, the filler comprises 21.5-25.5% of barium sulfate, 11-15% of talcum powder and 16-20% of feldspar powder based on the total weight of the epoxy anticorrosive primer.

According to some embodiments of the present invention, the raw material for preparing component a further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of an adhesion promoter, an anti-settling agent and an anti-sagging agent.

According to some embodiments of the invention, the auxiliary agent comprises 0.4-0.6% of adhesion promoter, 1.5-2.0% of anti-settling agent and 0.3-0.6% of anti-sagging agent based on the total weight of the epoxy anticorrosive primer.

According to some embodiments of the invention, the raw materials for preparing the component a further comprise 3.2-7.2% of pigment based on the total weight of the epoxy anticorrosive primer.

In addition, auxiliaries may also be added to the raw materials for the preparation of component B. For example, the raw material for preparing the component B may further include 0.3 to 0.6% of a first additive, and the first additive may include a defoaming agent, based on the total weight of the epoxy anticorrosive primer.

In a second aspect of the invention, a method for preparing any one of the epoxy anticorrosive primers provided by the first aspect of the invention is provided, which comprises the preparation of component a and the preparation of component B; wherein the content of the first and second substances,

the preparation of the component A comprises the following steps:

s1, mixing and stirring the solid epoxy resin, the liquid epoxy resin, the epoxy active diluent, the filler, the catalyst and part of the solvent uniformly to obtain slurry;

s2, grinding the slurry to obtain grinding slurry;

s3, curing the grinding slurry, adjusting the viscosity to 40-60poise by using the residual solvent, and filtering;

the preparation of the component B comprises the following steps: and mixing and stirring the preparation raw materials of the component B uniformly, and then filtering.

In the preparation process of the component A, in the step S1, the materials can be sequentially added and uniformly stirred at the rotating speed of 1000-1200 rpm, and the stirring time is generally 20-40 min; the amount of the solvent added in the step S1 is generally 97 to 99% of the total weight of the solvent. In step S2, the grinding temperature is generally controlled to be 53-57 ℃, and the slurry can be ground to the fineness of less than 60 μm. In step S3, the curing time is generally 7-9 h, and the viscosity after viscosity adjustment is 40-60Poise (Poise) at 23 ℃; after the viscosity adjustment, the mixture is filtered by a 120-mesh screen.

In the preparation process of the component B, the preparation raw material of the component B can be uniformly stirred at the rotating speed of 400-500 rpm, and the stirring time is generally 20-40 min; after being homogenized, the mixture is filtered by a 150-mesh screen.

In a second aspect of the invention, there is provided an article having a primer layer comprising a substrate and a primer layer adhered to at least a portion of a surface of the substrate, the primer layer being formed from any of the epoxy corrosion resistant primers provided in the first aspect of the invention. The substrate can be specifically a coating substrate such as a ship shell, a ship outer clamping plate, a ballast water tank and the like, and the epoxy anticorrosive primer can be coated on the surface to be coated of the substrate in the coating process.

The embodiment of the invention has the beneficial effects that:

the embodiment of the invention provides an epoxy anticorrosive primer, which is prepared by mixing solid epoxy resin, liquid epoxy resin and chelate-modified liquid epoxy resin according to a specific ratio and matching with a curing agent comprising amidoamine, polyetheramine and modified amine. The liquid epoxy resin has small molecular weight, good permeability and high crosslinking density, and can improve the compactness of a paint film; the solid epoxy resin has good flexibility after film forming, the solid epoxy resin and the solid epoxy resin are mixed according to a specific proportion, the mechanical property of a paint film formed by coating the primer can be improved, and the paint film is tough, wear-resistant and excellent in bending property; by adopting the chelate-modified liquid epoxy resin with functional groups with a chelating effect, the functional groups with the chelating effect in the epoxy resin can form a chelate bond with metal ions in the rust and have a strong effect on the rust, so that the primer has excellent adhesive force and is suitable for the rusty coating with low surface treatment; in addition, the curing agent comprising amidoamine, polyether amine and modified amine has excellent wettability and permeability to the substrate, and the coating formed by the crosslinking reaction of the curing agent and the epoxy resin has excellent physical and mechanical properties and corrosion resistance. The epoxy anti-corrosion primer formed by the method has high solid content, low VOCs discharge amount in coating and strong adhesive force, is suitable for low surface treatment of products such as ships and the like, can be coated with rust, can be particularly used for ship shells, superstructures, outer splints, ballast water tanks and other parts, has strong universality, and has excellent physical and mechanical properties and anti-corrosion properties.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.

(I) preparing epoxy anticorrosive primer

The preparation method of the epoxy anticorrosive primer comprises the preparation of a component A (main agent) and a component B (curing agent).

Wherein, the preparation of the component A comprises the following steps:

s1, taking a container with a certain volume, sequentially adding solid epoxy resin, liquid epoxy resin, an epoxy reactive diluent, an auxiliary agent (comprising an anti-settling agent, an anti-sagging agent and an adhesion promoter), a pigment, a filler and a part of solvent (accounting for 98% of the total solvent weight) into the container according to the preparation raw material proportion in Table 1 at the rotating speed of 1000-1200 rpm, and fully stirring for 30min to fully and uniformly mix the raw materials to prepare a slurry;

and S2, pumping the slurry prepared in the step S1 into a horizontal sand mill by a pump, controlling the grinding temperature to be 53-57 ℃, and grinding until the fineness is less than 60 mu m to obtain the grinding slurry.

S3, curing the grinding slurry prepared in the step S2 for 8 hours, and adjusting the viscosity to be within a specified range (40-60Poise, 23 ℃) by using the residual 2% solvent;

s4, filtering by using a 120-mesh screen and packaging.

The preparation of the component B comprises the following steps: taking a container with a certain volume, sequentially adding the raw materials into the container according to the preparation raw material ratio in the table 1, and fully stirring for 30min at the rotating speed of 400-500 rpm; filtering with 150 mesh sieve, and packaging.

The epoxy anticorrosive primer is prepared by respectively taking the raw materials according to the preparation raw material ratios of the examples 1-4 in the table 1 and preparing the epoxy anticorrosive primer according to the method, and when the epoxy anticorrosive primer is used, the component A and the component B are uniformly mixed according to the ratio in the table 1.

TABLE 1 preparation of epoxy anticorrosion primer for each example

(II) Performance testing

The epoxy anticorrosive primer prepared in examples 1 to 8 was used as a ship ballast tank paint, and according to the requirements of the ship ballast tank paint (GB/T6823-2008), coating and plate making were performed, and performance tests were performed, respectively, and the obtained results are shown in Table 2. The performance tests were carried out as follows:

1) the adhesion is carried out according to GB5210-2006 adhesion test by pulling open method of colored paint and varnish;

2) the preparation of the sample is carried out according to GB1765-79, paint film preparation method for measuring humidity and heat resistance, salt mist resistance and weather resistance (manual acceleration);

3) the paint film evaluation is carried out according to GB1766-2008 'rating method for color paint and varnish coating aging';

4) the moisture and heat resistance of the paint film is carried out according to GB13893-2008 'continuous condensation method for measuring the moisture and heat resistance of colored paint and varnish';

5) the rust grade and the rust removal grade of the steel surface before GB/T8293-1998 coating;

6) evaluation of the roughness grade of the steel surface before GB/T13288-1998 coating (comparative sample block method).

TABLE 2 Performance test results of epoxy anticorrosive primer prepared in each example as paint for ballast tank of ship

The epoxy anticorrosive primer prepared in examples 1 to 8 was used as a marine anticorrosive paint, and coated to prepare a plate according to the requirements of the marine anticorrosive paint (GB/T6748-2008), and performance tests were performed, respectively, and the results are shown in table 3. The performance tests were carried out as follows:

1) the adhesion is carried out according to GB5210-2006 adhesion test by pulling open method of colored paint and varnish;

2) the flexibility is carried out according to GB1731-1993 paint film flexibility determination method;

3) the salt spray resistance is carried out according to GB1771-2007 determination of neutral salt spray resistance of colored paint and varnish;

4) the salt water resistance is carried out according to GB/T10834 salt water resistance determination method of marine paint and hot salt water soaking method.

TABLE 3 Performance test results of epoxy anticorrosive primer prepared in each example as marine anticorrosive paint

The epoxy anticorrosive primer prepared in examples 1 to 8 was used as an anticorrosive paint, and a plate was prepared by coating on a rusted hot rolled plate substrate, and the results of performance tests were respectively performed, and are shown in table 4. The performance tests were carried out as follows:

1) the adhesion is carried out according to GB9268-1998 test for marking the paint film of the colored paint and the varnish;

2) the salt spray resistance is determined in accordance with GB1771-2007 determination of neutral salt spray resistance of paints and varnishes.

TABLE 4 Performance test results of epoxy anticorrosion primers prepared in each example on rusty substrates

As can be seen from tables 1 to 4, the epoxy anticorrosive primer disclosed by the invention is high in solid content, low in VOCs (volatile organic compounds) discharge amount during coating, strong in adhesive force and thick in coating property, a one-time film-forming dry film can reach more than 250 microns, does not sag or have pinholes, can be suitable for low-surface treatment of products such as ships and the like, can be coated with rust, can be specifically used for ship shells, superstructures, outer splints, ballast water tanks and other parts, is strong in universality, and has excellent physical and mechanical properties and anticorrosive properties.