RU2602553C1 - Non-fouling enamel prohydroph - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to paint materials and is intended for producing hydrophobic non-fouling coatings, is used in ship building and for protection of metal articles and structures used in atmospheric conditions. Described is non-fouling enamel consisting of amine type curing agent and semi-finished enamel, which is a suspension of pigments and filler in a solution of epoxy film-forming agent, synthesised from aromatically conjugated hydroxyphenylene and containing technical carbon and aerosil, wherein enamel semi-finished product further contains a liquid fluorinated modifier, solid fine fluorinated modifier in following ratio of ingredients in enamel semi-finished product, wt%: technical carbon 1.5-2.5, aerosil 2.5-3.5, liquid fluorinated modifier 2.5-4.5, solid fine fluorinated modifier 3.5-5.0, solution of epoxy film-forming agent to 100, wherein solution of epoxy film-forming agent contains pigments and filler materials in form of fluorinated fine fluoroplastic 2.5-4.5 wt% and perfluoropolyester liquid 3.5-5.0 wt%, and curing agent used is gamma-aminopropyltriethoxysilane AGM-9.

EFFECT: obtaining a composition of an enamel semi-finished product, which reduces possibility of attachment of fouling, reduction of specific wear of coating and high contact angle of wetting.

1 cl, 1 tbl

Description

The invention relates to the paint and varnish industry, in particular to paint and varnish materials, and can be used to obtain hydrophobic antifouling coatings used in shipbuilding, as well as for the protection of metal products and structures operated in atmospheric conditions.

Known anti-fouling coatings, RU No. 2502765 C2, C09D 5/16, 12/27/2013; RU No. 2479608 C2, C09D 5/16, 04/20/2013; RU No. 2478114 C1, C09D 5/14, C09D 5/16, 03/27/2013; RU No. 2476469 C2, C09D 5/16, 02.27.2013; RU No. 2439110 C2, C09D 5/16, 01/10/2012; RU No. 2433154 C1, C09D 5/14, C09D 5/16, 10/10/2011; RU No. 21115680 C1, C09D 5/16, C09D 5/08, 07.20.1998.

Known methods for producing anti-fouling enamels, RU No. 2441045 C1, C09D 5/16, 01/27/2012; RU No. 2394864 C1, C09D 5/16, 07/20/2010; RU No. 2057203 C1, C23C 28/02, 05.27.1996.

Known chemically resistant epoxy enamel related to the composition of paints and varnishes intended for the protection and decorative finish of reinforced concrete structures and structures made of ferrous and non-ferrous metals exposed to open and industrial atmospheres, as well as chemically aggressive environments, RU No. 2530075 C1, C09D 163/02 10/10/2014.

Known polymer composite material of cold curing based on epoxy resins, containing Aerosil, RU No. 2386653 C2, C09D 5/34, 04/20/2010.

Known PTFE coating material for coatings, including additional aerosil, RU No. 2532192 C1, C09D 127/16, 10.27.2014.

Known epoxy composition comprising epoxy resin, amine hardener and modifier, RU No. 2230086 C1, C09D 5/08, C09D 163/02, C09D 163/10, 06/10/2004; RU No. 2230081 C1, C09D 163/02, 06/10/2004.

Known weather-resistant paint composition based on polystyrene film-forming, RU No. 2214436 C1, C09D 183/04, 10/20/2003; RU No. 2155785 C1, C09D 125/06, 09/10/2000.

Known two-component enamel ARGOF-EP from the hardener and the base, which is a suspension of pigments and fillers in a solution of epoxidized aromatically conjugated hydroxyphenylene, http://www.biz-ural.ru/ru/products/?produkt=20, 03/06/2015.

Known compositions and methods for their preparation are individual.

Known enamel for coating, consisting of an amine type hardener and a prefabricated enamel, which is a suspension of pigments and fillers in a solution of epoxy film-forming, synthesized from aromatically conjugated hydroxyphenylene and containing carbon, technical and aerosil, RU No. 2307143 C2, C09D 163/00, 27.09. 2007.

This technical solution is made as the closest analogue of the present invention.

In the closest analogue, the contact wetting angle of the coating is low, which indicates that the coating is not hydrophobic.

When enamel of the closest analogue is used, fouling agents are attached rather quickly to the surface of the vessel, which leads to an increase in resistance to the movement of the vessel, an increase in fuel consumption to maintain the required speed, or a decrease in speed with constant shaft power.

The composition of the closest analogue based on epoxy film-forming contains a significant amount of ingredients, in addition to technical carbon and aerosil, it includes: yellow lead crown, microtalc, kaolin, micromica, xylene, toluene.

The present invention is based on the solution of the problem, which allows to increase the protective properties of enamel, reduce the formulation, provide the coating with hydrophobic properties and increase its service life.

The technical result of the present invention is to reduce the possibility of attachment of fouling due to the proposed composition of the prefabricated enamel due to the additional introduction of perfluoropolyether liquid and finely dispersed fluoroplastic into the prefabricated enamel, due to the use of gamma aminopropyltriethoxysilane AGM-9 as a hardener; in reducing the specific wear of the coating by weight and in increasing the contact angle of wetting of the coating due to the use of a solution of epoxy film-forming with fillers in the form of semi-finished enamel in the form of fluorinated finely divided fluoroplastic and perfluoropolyether liquid.

According to the invention, this problem is solved due to the fact that antifouling enamel consists of an amine type hardener and a prefabricated enamel.

Prefabricated enamel is a suspension of pigments and fillers in a solution of epoxy film-forming.

The epoxy film-forming solution is synthesized from aromatically conjugated hydroxyphenylene.

The enamel prefabricated product contains technical carbon, aerosil and additionally a liquid fluorinated modifier, a solid finely divided fluorinated modifier and a solution of epoxy film-forming.

Prefabricated enamel has the following ratio of ingredients, wt. %: technical carbon 1.5-2.5, aerosil, 2.5-3.5, liquid fluorinated modifier 2.5-4.5, solid finely dispersed fluorinated modifier 3.5-5.0, epoxy film-forming solution up to 100 .

The solution of the epoxy film-forming contains pigments and fillers in the form of fluorinated finely divided fluoroplastic 2.5-4.5 wt. % and perfluoropolyether liquid 3.5-5.0 wt. %

As hardener use gamma-aminopropyltriethoxysilane AGM-9.

The applicant has not identified sources containing information about technical solutions identical to the present invention, which allows us to conclude that it meets the criterion of "novelty."

Due to the implementation of the distinguishing features of the invention (in conjunction with the features indicated in the restrictive part of the formula), important new properties of the object are achieved.

The composition of the prefabricated enamel based on epoxy film-forming, the additional introduction of perfluoropolyether liquid and finely dispersed fluoroplastic into the prefabricated enamel, the use of gamma-aminopropyltriethoxysilane AGM-9 as a hardener increase the protective properties of enamel, reduce the possibility of attachment of coatings and reduce the growth of coatings.

The prescription composition of the semi-finished enamel in the form of carbon technical, aerosil, perfluoropolyether fluid and finely divided fluoroplastic is optimal.

The use of an epoxy film-forming solution with fillers in the form of a perfluoropolyether liquid and finely divided fluoroplastic increases the contact angle of the coating and the effectiveness of anti-fouling, gives the coating hydrophobic properties and increases the service life of the coating.

The applicant is not aware of any publications that would contain information on the influence of the distinguishing features of the invention on the achieved technical result. In this regard, according to the applicant, it can be concluded that the claimed technical solution meets the criterion of "inventive step".

Antifouling enamel Progidrof is a two-pack system consisting of component A (semi-finished enamel) and component B (amine type hardener AGM-9 - gamma-aminopropyltriethoxysilane).

Prefabricated enamel is a suspension of pigments and fillers in a solution of epoxy film-forming.

The epoxy film-forming solution is synthesized from aromatically conjugated hydroxyphenylene.

The enamel prefabricated product contains technical carbon, aerosil, liquid fluorinated modifier, solid finely dispersed fluorinated modifier and a solution of epoxy film-forming.

Prefabricated enamel has the following ratio of ingredients, wt. %: technical carbon 1.5-2.5, aerosil, 2.5-3.5, liquid fluorinated modifier 2.5-4.5, solid finely dispersed fluorinated modifier 3.5-5.0, epoxy film-forming solution up to 100 .

The solution of the epoxy film-forming contains pigments and fillers in the form of fluorinated finely divided fluoroplastic 2.5-4.5 wt. % and perfluoropolyether liquid 3.5-5.0 wt. %

As hardener use gamma-aminopropyltriethoxysilane AGM-9.

The process of obtaining a film-forming is carried out in several stages:

1. Synthesis of oligomer

The oligomer is synthesized by oxidative polycondensation of hydroquinone in a reactor.

For the manufacture of an epoxy film-forming, preheated resorcinol is loaded into the reactor. After loading resorcinol into the reactor, heating is turned on and the contents of the reactor are heated. When the temperature in the reactor reaches 130 ° C, sulfuric acid is introduced into the reactor.

When the temperature in the reactor reaches 240 ° C, it is maintained in the range of 240-250 ° C for at least 3 hours.

The reaction product is a thermoplastic aromatically conjugated oligomers of red-brown hydroquinone with a number average molecular weight of 340 cu A distinctive feature of these oligomers is aromatic conjugation, which is the strongest chemical bond, and insolubility in polar solvents.

2. Epoxidation of the oligomer

The oligomer is charged into the reactor and heated to a temperature of 120-130 ° C, then ethyl cellosolph is added in an amount of 80% by weight of the oligomer. Next, the contents of the reactor are stirred for 60 minutes and cooled.

After cooling the reactor, an ED-20 epoxy resin is added to the reactor and stirred for one hour at a temperature of 80 + 5 ° С, then an accelerator (NaOH) is added and stirring is continued.

At the end of mixing, a further rise in temperature in the reactor to 120-130 ° C.

In the process of heating, samples are taken to determine the mass fraction of epoxy groups. The process is considered complete when the content of the mass fraction of epoxy groups reaches 8-11%.

Upon receipt of positive analysis results on the content of the mass fraction of epoxy groups, the reactor is cooled to 140-130 ° C and solvents are added at certain temperatures:

- ethyl cellosolve at 140-130 ° C;

- xylene at 110-80 ° C;

- acetone at 50-40 ° C.

The process continues until a homogeneous mixture is obtained.

The starting components for the film-forming: hydroquinone, epoxy resin ED-20, acetone, xylene, ethyl cellosolve, sodium hydroxide, sulfuric acid.

The initial components for the preparation of prefabricated enamel: pigments, liquid fluorinated modifier, solid fluorinated modifier.

Technical pigments and aerosil are used as pigments.

Technical carbon is a finely dispersed, partially microcrystalline carbon whose practically spherical primary particles are combined into large aggregates that form chains or clusters.

Aerosil is colloidal silicon dioxide (SiO2), a very light micronized powder with pronounced adsorption properties (technical name is pyrogenic silicon dioxide).

As a solid fluorinated modifier, finely dispersed fluoroplastic is used. Finely dispersed fluoroplastic is a combination of fluorine with carbon in the form of a white finely divided powder with a particle size of 1 μm, the technical name is polytetrafluoroethylene.

Perfluoropolyether fluid is used as a fluorinated liquid modifier. Perfluoropolyether liquid is a colorless oily liquid containing functional groups CF ₂ and having a molecular weight of 2800-4000.

The formulation of antifouling enamel Progidrof presented in table 1.

The ratio of ingredients (min and max) are optimal - investigated and confirmed upon receipt of enamel.

From table 1 it is seen that in the composition of antifouling enamel Progidrof the number of ingredients compared to the closest analogue is reduced.

Obtaining antifouling enamel Progidrof is as follows.

Prepare prefabricated enamel:

- add to the epoxy film-forming mixture of solvents to obtain the desired viscosity;

- prepare the pigment paste in a high-speed mixer;

- mix epoxy film-forming and pigment paste;

- carry out the dispersion of the resulting composition to obtain a homogeneous mixture with a given value of milling;

- carry out sampling of the semi-finished enamel;

- carry out the analysis and testing of semi-finished enamel according to technical characteristics;

- pour the semi-finished enamel into the container.

Prepare antifouling enamel Progidrof:

- add the hardener AGM-9 to the semi-finished enamel;

- mix the semi-finished enamel and hardener AGM-9;

- maintain the mixture for 45 minutes;

- apply the obtained enamel to the surface with a brush, roller or spray.

Properties of antifouling enamel Progidrof in comparison with the closest analogue are presented in table 2.

From table 2 it is seen that the specific wear by weight in the proposed composition is significantly reduced and the contact angle before testing, and also after exposure to salt fog and 3% NaCl solution is higher than in the closest analogue.

The technical and economic effect of the invention of the antifouling enamel Progidrof is achieved due to the fact that the solution of the epoxy film-forming synthesized from aromatically conjugated hydroxyphenylene contains pigments and fillers in the form of fluorinated finely divided fluoroplastic and perfluoropolyether liquid, which increases the efficiency of protection against fouling and the service life of the coating sea water.

The proposed antifouling enamel Progidrof used ingredients that are widely used in the paint and varnish industry, and studies of the quantitative composition and testing of prototypes of FSUE TsNII KM Prometey determine, in the applicant's opinion, compliance with its criterion of "industrial applicability".

Using the proposed antifouling enamel Progidrof allows you to:

- increase the protective properties of enamel;

- reduce the recipe;

- provide the coating with hydrophobic properties;

- increase the service life of the coating.

Claims (1)

Antifouling enamel, consisting of an amine type hardener and a prefabricated enamel, which is a suspension of pigments and fillers in an epoxy film-forming solution synthesized from aromatically conjugated hydroxyphenylene and containing carbon technical and aerosil, characterized in that the prefabricated enamel additionally contains a fluorinated, fluorinated, modifier, solid, modifier, solid modifier in the following ratio of ingredients in the enamel semi-finished product, wt. %:
carbon technical 1.5-2.5 aerosil 2.5-3.5 liquid fluorinated modifier 2.5-4.5 solid finely divided fluorinated modifier 3,5-5,0 epoxy film-forming solution up to 100
wherein the solution of the epoxy film-forming contains pigments and fillers in the form of fluorinated finely divided fluoroplastic 2.5-4.5 wt. % and perfluoropolyether liquid 3.5-5.0 wt. %, and as a hardener use gamma-aminopropyltriethoxysilane AGM-9.