CN110564239A - Self-antibacterial radiation-proof primer - Google Patents
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- CN110564239A CN110564239A CN201910820181.5A CN201910820181A CN110564239A CN 110564239 A CN110564239 A CN 110564239A CN 201910820181 A CN201910820181 A CN 201910820181A CN 110564239 A CN110564239 A CN 110564239A
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention relates to a self-antibacterial radiation-proof primer which comprises the following components in parts by weight: 30.0-50.0 parts of rare earth modified acrylic acid water-based resin, 30.0-50.0 parts of graphene modified acrylic acid water-based resin, 30.0-50.0 parts of durable antibacterial acrylic acid water-based resin, 0.3-0.8 part of flatting agent, 0.3-0.8 part of wetting agent, 8.0-15.0 parts of film-forming assistant, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 20.0-50.0 parts of nano-coated filler and 15.0-40.0 parts of deionized water; the self-antibacterial radiation-proof primer prepared by the invention does not need to additionally add an antibacterial agent and a radiation-proof material, overcomes the defects of easy decomposition, easy migration, uneven dispersion and the like of the additionally added antibacterial agent and the radiation-proof material, has good functions of penetration, filling and adhesion on a base material, has the advantages of high crosslinking density, good adhesive force, good antibacterial property, good radiation-proof property and the like, and has wide application prospect.
Description
Technical Field
The invention relates to a water-based paint, in particular to a self-antibacterial radiation-proof primer, belonging to the technical field of water-based functional paints.
Background
With the development of science and technology, various electronic products including personal mobile communication devices, intelligent household appliances and other industrial electronic devices are around us. These devices provide us with a more convenient life, but at the same time also bring about stronger electromagnetic radiation. The long-term or frequent electromagnetic wave radiation environment can seriously damage the health of people. Although the pollution of electromagnetic radiation cannot be seen, the pollution is self-evident to the human body, and mainly affects the nervous system, the cardiovascular system, the immune system, the eyes and the reproductive system. Therefore, radiation protection has become a non-negligible life content for modern people.
The radiation-proof paint is a functional paint which is formed by mixing conductive particles into organic resin and can be sprayed on non-metal substrates such as composite materials, metals, engineering plastics, wood, cement surfaces and the like. It has the advantages of room temperature curing and strong adhesive force, and is a treatment mode which is most convenient for the shells of military equipment or household appliances to resist radiation.
The radiation-proof paint has the advantages of low cost, simplicity, practicability and wide application range. Advanced and developed countries abroad, particularly countries such as the United states, the Britain, the Japan and the like have already formed the industry for producing radiation-proof paint with various types and series specifications, and the products have already been applied in large scale. At the end of the last century, companies in the united states that produce barrier coatings have gone over 50, and annual sales are growing at a 50% growth rate each year. The products of the traditional radiation-proof paint are mainly classified into 4 types of silver series, copper series, nickel series and carbon series. In spite of the research conditions at home and abroad, the radiation-proof coating is developing towards low cost, nano-scale, broadband and corrosion-resistant.
At present, some radiation-proof coatings can meet the radiation-proof requirements to a certain degree, but the radiation-proof performance of the coatings is difficult to last, and the coatings are easily affected by the external environment, particularly the invasion of some bacteria, so that the coatings are damaged and decomposed, and the radiation-proof function is slowly lost. Chinese patent CN108559400A discloses a radiation-proof water-based paint, which comprises the following components in parts by weight: 45-60 parts of water-based odorless radiation-proof emulsion, 0.1-0.3 part of cellulose, 0.1-0.3 part of wetting agent, 10-20 parts of deionized water, 0.1-0.3 part of amine neutralizer, 0.2-0.6 part of defoaming agent, 0.2-0.4 part of polyphosphate, 0.3-0.8 part of flatting agent, 10-15 parts of antifreezing agent, 10-15 parts of film-forming auxiliary agent, 15.3-25 parts of pigment and filler, 5-10 parts of barium sulfate powder, 3-5 parts of diatomite and 0.3-0.5 part of thickening agent.
Chinese patent CN106609083A discloses an electromagnetic radiation resistant aqueous graphene metal antirust primer, which is prepared from the following raw materials: acrylate emulsion, waste polystyrene foam, graphene, tea alkaloid, triglycerol monostearate, polyester fiber, nano barium ferrite magnetic powder, dandelion powder, bagasse, vinyl triethoxysilane, pigment and a proper amount of deionized water. It has the advantage of resisting electromagnetic radiation. However, the radiation protection performance is provided by adding the radiation protection agent externally, and the radiation protection agent externally added is physically mixed, so that the defects of nonuniform mixing, easy separation and the like exist.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a self-antibacterial radiation-proof primer without additionally adding an antibacterial agent and a radiation-proof material.
The invention effectively overcomes the defects of extra radiation-proof material, heavy rendering layer of radiation-proof paint, low radiation-proof capability and the like, the rare earth ions and the graphene have good radiation-proof performance, and in order to achieve a lasting radiation-proof effect, the rare earth ions and the graphene are connected with the high-molecular water-based resin through chemical bonds, and the water-based resin with good radiation-proof function is used as a main base material of the paint and can stably exist in the water-based paint.
In order to solve the problems that the radiation protection performance of the coating is damaged by bacterial corrosion and the performance of the coating is influenced by an external antibacterial agent, the invention adds the water-based resin with good antibacterial function, and the adopted water-based resin with the antibacterial function is a good antibacterial agent without the need of an external antibacterial agent.
In order to solve the problems of poor adhesion between the primer and the base material, filling property and the like, the nano coating filler is added.
the invention relates to a self-antibacterial radiation-proof primer which comprises the following components in parts by weight: 30.0-50.0 parts of rare earth modified acrylic acid water-based resin, 30.0-50.0 parts of graphene modified acrylic acid water-based resin, 30.0-50.0 parts of durable antibacterial acrylic acid water-based resin, 0.3-0.8 part of flatting agent, 0.3-0.8 part of wetting agent, 8.0-15.0 parts of film-forming assistant, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 20.0-50.0 parts of nano-coated filler and 15.0-40.0 parts of deionized water.
The rare earth modified acrylic waterborne resin is composed of an acrylic soft monomer, an acrylic hard monomer, hydroxyethyl acrylate, polyisocyanate, a hydroxyl Schiff base monomer, a rare earth solution, a sodium ethoxide ethanol solution, absolute ethanol, acrylic acid, azodiisobutyronitrile, an emulsifier, a neutralizer and deionized water.
The durable antibacterial water-based acrylic resin is prepared by reacting an acrylate monomer, a Schiff base acrylate monomer, acrylic acid, a cross-linking agent monomer and a neutralizing agent.
the graphene modified waterborne acrylic resin is composed of an acrylate monomer, oligomer polyether polyol, dimethylolpropionic acid, diisocyanate, special graphene, a hydroxy acrylic monomer, ammonium persulfate, dibutyltin dilaurate, a neutralizer and deionized water.
The nano-coating filler comprises the following components in parts by weight: 20.0-40.0 parts of barium sulfate, 10.0-20.0 parts of gas phase silica, 8.0-16.0 parts of coupling agent, 10.0-20.0 parts of hydroxyethyl methacrylate phosphate, 5.0-10.0 parts of polyvinyl alcohol, 0.3-1.0 part of ammonium persulfate, 2.0-8.0 parts of sodium polyacrylate, 6.0-14.0 parts of white graphene and 20.0-40.0 parts of deionized water.
The preparation method of the nano-coating filler comprises the following preparation steps:
a) weighing the components according to a formula ratio, sequentially adding the coupling agent, hydroxyethyl methacrylate phosphate, sodium polyacrylate and polyvinyl alcohol into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) Adding deionized water into a reaction kettle, preparing 5% aqueous solution from ammonium persulfate, adding 1/2 aqueous solution of ammonium persulfate, stirring at the speed of 100r/min, heating to 75-80 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding barium sulfate, meteorological silica and white graphene under the condition of high-speed stirring, and reacting for 1.5-2.0 h under the condition of high-speed stirring;
c) And simultaneously, controlling the dripping time to be 2.0-3.0 h for the rest of the dropwise added mixed solution I and the rest of the ammonium persulfate aqueous solution, stirring at a high speed at 78-82 ℃ for reacting for 1.5h after finishing dripping, cooling to room temperature, and stirring at a high speed for 0.5h to obtain the nano-coated filler.
The self-antibacterial radiation-proof primer prepared by the invention has the following advantages:
1) The self-antibacterial radiation-proof primer prepared by the invention does not need to be additionally added with an antibacterial agent and a radiation-proof material, and overcomes the defects of easy decomposition, easy migration, uneven dispersion and the like of the additionally added antibacterial agent and radiation-proof material.
2) the self-antibacterial radiation-proof primer prepared by the invention overcomes the problems of easy falling off of the primer, insufficient adhesion to a base material and the like, and the nano-coating filler introduced by the invention has good penetration, filling and bonding functions on the base material.
3) The anti-radiation coating has the advantages of high crosslinking density, good adhesive force, good antibacterial performance, good anti-radiation performance and the like, and has wide application prospect.
Detailed Description
The invention is further described with reference to the following examples in the preparation of self-antimicrobial radiation-protective primers.
Example 1
The nano-coating filler A comprises the following steps:
a) Weighing 12.0 parts of coupling agent, 15.0 parts of hydroxyethyl methacrylate phosphate, 5.0 parts of sodium polyacrylate and 6.0 parts of polyvinyl alcohol in sequence according to the formula ratio, adding the mixture into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) adding 30.0 parts of deionized water into a reaction kettle, preparing a 5% aqueous solution from 0.6 part of ammonium persulfate, adding 1/2 of an ammonium persulfate aqueous solution, stirring at the speed of 100r/min, heating to 76 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding 30.0 parts of barium sulfate, 15.0 parts of meteorological silica and 8.0 parts of white graphene under the condition of high-speed stirring, and reacting for 1.5-2.0 h under the condition of high-speed stirring;
c) And simultaneously, controlling the dripping time to be 2.5h, after finishing dripping, carrying out high-speed stirring reaction at 80 ℃ for 1.5h, cooling to room temperature, and carrying out high-speed stirring for 0.5h to obtain the nano-coated filler A.
Example 2
the nano-coating filler B comprises the following steps:
a) Weighing 8.0 parts of coupling agent, 20.0 parts of hydroxyethyl methacrylate phosphate, 6.0 parts of sodium polyacrylate and 6.0 parts of polyvinyl alcohol in sequence according to the formula ratio, adding the mixture into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) Adding 26.0 parts of deionized water into a reaction kettle, preparing a 5% aqueous solution from 0.5 part of ammonium persulfate, adding 1/2 of an ammonium persulfate aqueous solution, stirring at the speed of 100r/min, heating to 80 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding 20.0 parts of barium sulfate, 15.0 parts of meteorological silica and 12.0 parts of white graphene under the condition of high-speed stirring, and reacting for 1.5-2.0 h under the condition of high-speed stirring;
c) And simultaneously, controlling the dripping time to be 2.0h, after the dripping is finished, carrying out high-speed stirring reaction at 82 ℃ for 1.5h, cooling to room temperature, and carrying out high-speed stirring for 0.5h to obtain the nano-coated filler B.
example 3
The nano-coating filler C comprises the following steps:
a) weighing 10.0 parts of coupling agent, 14.0 parts of hydroxyethyl methacrylate phosphate, 4.0 parts of sodium polyacrylate and 8.0 parts of polyvinyl alcohol in sequence according to the formula ratio, adding into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) Adding 32.0 parts of deionized water into a reaction kettle, preparing 5% aqueous solution from 0.5 part of ammonium persulfate, adding 1/2 of aqueous solution of ammonium persulfate, stirring at the speed of 100r/min, heating to 80 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding 32.0 parts of barium sulfate, 18.0 parts of meteorological silica and 10.0 parts of white graphene under the condition of high-speed stirring, and reacting for 1.5h under high-speed stirring;
c) and simultaneously, controlling the dripping time to be 2.5h, after finishing dripping, carrying out high-speed stirring reaction at 80 ℃ for 1.5h, cooling to room temperature, and carrying out high-speed stirring for 0.5h to obtain the nano-coated filler C.
Example 4
Nano-coating filler D, comprising the following steps:
a) weighing 16.0 parts of coupling agent, 18.0 parts of hydroxyethyl methacrylate phosphate, 7.0 parts of sodium polyacrylate and 8.0 parts of polyvinyl alcohol in sequence according to the formula ratio, adding the mixture into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) Adding 38.0 parts of deionized water into a reaction kettle, preparing a 5% aqueous solution from 0.9 part of ammonium persulfate, adding 1/2 of an ammonium persulfate aqueous solution, stirring at the speed of 100r/min, heating to 80 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding 40.0 parts of barium sulfate, 18.0 parts of meteorological silica and 13.0 parts of white graphene under the condition of high-speed stirring, and stirring at a high speed for reacting for 2.0 h;
c) And simultaneously, controlling the dripping time to be 3.0h, after the dripping is finished, carrying out high-speed stirring reaction at 82 ℃ for 1.5h, cooling to room temperature, and carrying out high-speed stirring for 0.5h to obtain the nano-coated filler D.
Example 5
a preparation method of self-antibacterial radiation-proof primer comprises the following steps:
40.0 parts of rare earth modified acrylic acid water-based resin, 40.0 parts of graphene modified acrylic acid water-based resin, 35.0 parts of durable antibacterial acrylic acid water-based resin, 0.5 part of flatting agent, 0.5 part of wetting agent, 12.0 parts of film-forming assistant, 0.6 part of dispersing agent, 0.5 part of defoaming agent, 35.0 parts of nano-coated filler A and 20.0 parts of deionized water.
Example 6
a preparation method of self-antibacterial radiation-proof primer comprises the following steps:
50.0 parts of rare earth modified acrylic acid water-based resin, 30.0 parts of graphene modified acrylic acid water-based resin, 40.0 parts of durable antibacterial acrylic acid water-based resin, 0.5 part of flatting agent, 0.6 part of wetting agent, 12.0 parts of film-forming assistant, 0.8 part of dispersing agent, 0.5 part of defoaming agent, 40.0 parts of nano-coated filler B and 25.0 parts of deionized water.
Example 7
A preparation method of self-antibacterial radiation-proof primer comprises the following steps:
35.0 parts of rare earth modified acrylic acid water-based resin, 40.0 parts of graphene modified acrylic acid water-based resin, 45.0 parts of durable antibacterial acrylic acid water-based resin, 0.4 part of flatting agent, 0.6 part of wetting agent, 12.0 parts of film-forming assistant, 0.8 part of dispersing agent, 0.6 part of defoaming agent, 45.0 parts of nano-coated filler C and 28.0 parts of deionized water.
Example 8
a preparation method of self-antibacterial radiation-proof primer comprises the following steps:
42.0 parts of rare earth modified acrylic acid water-based resin, 38.0 parts of graphene modified acrylic acid water-based resin, 46.0 parts of durable antibacterial acrylic acid water-based resin, 0.7 part of flatting agent, 0.7 part of wetting agent, 14.0 parts of film-forming assistant, 0.8 part of dispersing agent, 0.7 part of defoaming agent, 50.0 parts of nano-coated filler D and 35.0 parts of deionized water.
examples of the present invention were examined in comparison with conventional primers (comparative examples) according to the relevant standards, namely "determination of water resistance of paint films" (GB/T1733-1993), "test of marking of paint films of colored and varnishes" (GB/T9286-1998), "determination of flexibility of paint films" (GB/T1731-1993), "determination of resistance to neutral salt spray of colored and varnishes" (GB/T1771-2007), "determination of impact resistance of paint films" (GB/T1732-1993), resistance to acids (GB/T1763-1979), resistance to bases (GB/1763-1979), HG/T3950-2007 "antibacterial paint" and the like, and the results of the tests are shown in Table 1.
table 1: technical indexes of performance of the embodiment of the invention and the conventional primer (comparative example)
table 1 shows that the self-antibacterial radiation-proof primer of the present invention has better properties of adhesion, acid and alkali resistance, antibacterial property, filling property, etc. than conventional primer coatings; after 3 years of aging is simulated, the antibacterial rate of the self-antibacterial radiation-proof primer is basically unchanged, which shows that the self-antibacterial radiation-proof primer has lasting antibacterial performance.
The test results of the radiation protection performance test were carried out on the samples 2mm thick prepared from example 5, example 6, example 7 and example 8 of the present invention and the conventional additive radiation protection paint (comparative example), and are shown in Table 2.
table 2: results of radiation protection assay
As can be seen from Table 2, the shielding performance of the conventional additive radiation-proof paint is reduced with the passage of time, and the self-antibacterial radiation-proof primer disclosed by the embodiment of the invention still has good shielding property after being aged for a long time because the radiation-proof ions are fixed on the film-forming substance and are hardly lost, and the radiation-proof performance is efficient and durable.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. a self-antibacterial radiation-proof primer is characterized by comprising the following components in parts by weight: 30.0-50.0 parts of rare earth modified acrylic acid water-based resin, 30.0-50.0 parts of graphene modified acrylic acid water-based resin, 30.0-50.0 parts of durable antibacterial acrylic acid water-based resin, 0.3-0.8 part of flatting agent, 0.3-0.8 part of wetting agent, 8.0-15.0 parts of film-forming assistant, 0.4-1.0 part of dispersing agent, 0.3-0.8 part of defoaming agent, 20.0-50.0 parts of nano-coated filler and 15.0-40.0 parts of deionized water;
the nano-coating filler comprises the following components in parts by weight: 20.0-40.0 parts of barium sulfate, 10.0-20.0 parts of gas phase silica, 8.0-16.0 parts of coupling agent, 10.0-20.0 parts of hydroxyethyl methacrylate phosphate, 5.0-10.0 parts of polyvinyl alcohol, 0.3-1.0 part of ammonium persulfate, 2.0-8.0 parts of sodium polyacrylate, 6.0-14.0 parts of white graphene and 20.0-40.0 parts of deionized water.
2. A self-antimicrobial radiation protective primer according to claim 1 wherein: the rare earth modified acrylic waterborne resin is composed of an acrylic soft monomer, an acrylic hard monomer, hydroxyethyl acrylate, polyisocyanate, a hydroxyl Schiff base monomer, a rare earth solution, a sodium ethoxide ethanol solution, absolute ethanol, acrylic acid, azodiisobutyronitrile, an emulsifier, a neutralizer and deionized water.
3. A self-antimicrobial radiation protective primer according to claim 1 wherein: the durable antibacterial water-based acrylic resin is prepared by reacting an acrylate monomer, a Schiff base acrylate monomer, acrylic acid, a cross-linking agent monomer and a neutralizing agent.
4. a self-antimicrobial radiation protective primer according to claim 1 wherein: the graphene modified waterborne acrylic resin is composed of an acrylate monomer, oligomer polyether polyol, dimethylolpropionic acid, diisocyanate, special graphene, a hydroxy acrylic monomer, ammonium persulfate, dibutyltin dilaurate, a neutralizer and deionized water.
5. A self-antimicrobial radiation protective primer according to claim 1 wherein: the preparation process of the nano-coating filler comprises the following steps:
a) Weighing the components according to a formula ratio, sequentially adding the coupling agent, hydroxyethyl methacrylate phosphate, sodium polyacrylate and polyvinyl alcohol into a metering tank G1, and uniformly stirring to obtain a mixed solution I;
b) adding deionized water into a reaction kettle, preparing 5% aqueous solution from ammonium persulfate, adding 1/2 aqueous solution of ammonium persulfate, stirring at the speed of 100r/min, heating to 75-80 ℃, slowly adding 1/2 of the mixed solution I, reacting for 0.5h, adding barium sulfate, meteorological silica and white graphene under the condition of high-speed stirring, and reacting for 1.5-2.0 h under the condition of high-speed stirring;
c) And simultaneously, controlling the dripping time to be 2.0-3.0 h for the rest of the dropwise added mixed solution I and the rest of the ammonium persulfate aqueous solution, stirring at a high speed at 78-82 ℃ for reacting for 1.5h after finishing dripping, cooling to room temperature, and stirring at a high speed for 0.5h to obtain the nano-coated filler.
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Application publication date: 20191213 |