阅读说明：本技术 一种阻燃型喷标油漆及其制备方法 (Flame-retardant spray paint and preparation method thereof ) 是由 吴冤 金泽明 王瑞冬 于 2020-07-14 设计创作，主要内容包括：本发明属于油漆制备技术领域,具体涉及一种阻燃型喷标油漆及其制备方法。按重量份计,所述阻燃型喷标油漆至少包括热塑性丙烯酸树脂1-10份、醋酸丁酸纤维素1-10份、颜料5-10份、阻燃剂0.2-2份、溶剂60-120份。本发明制备的阻燃型喷标油漆,阻燃性好,有很好的耐温性,在200℃可以正常使用,且具有良好的速干性、漆膜均一、色彩鲜明、耐候性好,不受气温和紫外线的影响,且阻燃型喷标油漆的附着力高；同时具有优异的分散性,长时间放置不会产生返粗和颜料沉降等问题,细度不超过3μm,软化漆膜,使用喷涂更为流畅,不易堵塞喷嘴,具有优良的稳定性。(The invention belongs to the technical field of paint preparation, and particularly relates to flame-retardant spray painting paint and a preparation method thereof. The flame-retardant spray paint at least comprises 1-10 parts by weight of thermoplastic acrylic resin, 1-10 parts by weight of cellulose acetate butyrate, 5-10 parts by weight of pigment, 0.2-2 parts by weight of flame retardant and 60-120 parts by weight of solvent. The flame-retardant spray paint prepared by the invention has good flame retardance, good temperature resistance, good quick drying property, uniform paint film, bright color, good weather resistance, no influence of air temperature and ultraviolet rays, and high adhesion; meanwhile, the paint has excellent dispersibility, cannot cause the problems of coarsening, pigment sedimentation and the like after being placed for a long time, has the fineness of not more than 3 mu m, softens a paint film, is smoother to use and spray, is not easy to block a nozzle, and has excellent stability.)

1. The flame-retardant spray paint is characterized by at least comprising 1-10 parts by weight of thermoplastic acrylic resin, 1-10 parts by weight of cellulose acetate butyrate, 5-10 parts by weight of pigment, 0.2-2 parts by weight of flame retardant and 60-120 parts by weight of solvent.

2. The flame-retardant spray paint according to claim 1, wherein the glass transition temperature of the thermoplastic acrylic resin is 40 to 60 ℃.

3. The flame-retardant spray paint according to claim 1, wherein the cellulose acetate butyrate has a butyryl group content of 35 to 45 wt%.

4. The flame-retardant spray paint according to claim 1, wherein the pigment is selected from one or more of rutile titanium dioxide color paste, carbon black, phthalocyanine blue, red iron oxide, brown iron oxide, black iron oxide, yellow iron oxide, mica iron oxide, zinc phosphate, zinc molybdate, aluminum tripolyphosphate, aluminum hydroxy silicate, and sodium metaborate.

5. The flame-retardant spray paint according to any one of claims 1 to 4, further comprising 1 to 5 parts by weight of a rosin-modified resin and 0.01 to 0.1 part by weight of a silicone antifoaming agent.

6. The flame-retardant spray paint according to claim 5, wherein the rosin-modified resin is one or more selected from rosin-modified phenolic resins, rosin-modified terpene-phenolic resins, and rosin-modified maleic acid resins.

7. The flame-retardant spray paint according to claim 5, wherein the silicone antifoaming agent is one or more selected from the group consisting of KM-71, KM-73, 73A, KM-73E, KM-75, KM-85, KM-89, KM-90, KM-98, KM-7550, KM-7752, KS-508, KS-530, KS-531, KS-538, KS-540, KS-66, KS-69, KS-7704S, X-50-1090B.

8. The flame-retardant spray paint according to claim 1, wherein the fineness of the flame-retardant spray paint is not more than 3 μm.

9. The flame-retardant spray paint according to claim 1, wherein the tack-free time of the flame-retardant spray paint is not more than 10 s.

10. The preparation method of the flame-retardant spray paint according to claim 5, characterized by comprising the following steps:

s1: stirring the solvent, sequentially adding the flame retardant and the organic silicon defoaming agent, and stirring;

s2: sequentially adding thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin, and stirring until the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin are completely dissolved;

s3: and adding the pigment and stirring to obtain the flame-retardant spray painting paint.

Technical Field

The invention belongs to the technical field of paint preparation, and particularly relates to flame-retardant spray painting paint and a preparation method thereof.

Background

The existing paint on the market is various in types, but along with the increase of functional requirements of people on the paint, the existing paint cannot meet the requirements of people, and the paint only realizes the protection and decoration functions at present.

The normal temperature is spouted mark paint and is a normal temperature general mark paint that matches with various types and spouts the mark machine, is the consumptive material that spouts the mark machine, spouts mark paint and generally all uses under the high temperature environment of steel mill, and the product all adopts flammable solvent on the general market for the product has great conflagration risk in the use, hardly at 500 ℃ normal use, and its manufacturing cost is higher moreover, and the production process is complicated, places for a long time and produces and return thick and pigment subsides the scheduling problem.

Disclosure of Invention

In order to solve the technical problems, the first aspect of the invention provides a flame-retardant spray painting paint which at least comprises, by weight, 1-10 parts of thermoplastic acrylic resin, 1-10 parts of cellulose acetate butyrate, 5-10 parts of pigment, 0.2-2 parts of flame retardant and 60-120 parts of solvent.

As a preferred technical scheme, the glass transition temperature of the thermoplastic acrylic resin is 40-60 ℃.

As a preferred technical scheme, the content of butyryl in the cellulose acetate butyrate is 35-45 wt%.

As a preferable technical scheme, the pigment is selected from one or more of rutile titanium dioxide color paste, carbon black, phthalocyanine blue, iron oxide red, iron oxide brown, iron oxide black, iron oxide yellow, mica iron oxide, zinc phosphate, zinc molybdate, aluminum tripolyphosphate, basic aluminum aluminosilicate and sodium metaborate.

As a preferable technical scheme, the flame-retardant spray paint further comprises 1-5 parts by weight of rosin modified resin and 0.01-0.1 part by weight of an organic silicon defoaming agent.

As a preferable technical solution, the rosin modified resin is one or more selected from rosin modified phenolic resin, rosin modified terpene phenol resin, and rosin modified maleic acid resin.

As a preferable technical scheme, the organic silicon defoaming agent is selected from one or more of KM-71, KM-73A, KM-73E, KM-75, KM-85, KM-89, KM-90, KM-98, KM-7550, KM-7752, KS-508, KS-530, KS-531, KS-538, KS-540, KS-66, KS-69 and KS-7704S, X-50-1090B.

As a preferable technical scheme, the fineness of the flame-retardant spray painting paint is not more than 3 mu m.

As a preferable technical scheme, the surface drying time of the flame-retardant spray painting paint is not more than 10 s.

The second aspect of the invention provides a preparation method of the flame-retardant spray painting paint, which comprises the following steps:

s1: stirring the solvent, sequentially adding the flame retardant and the organic silicon defoaming agent, and stirring;

s2: sequentially adding thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin, and stirring until the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin are completely dissolved;

s3: and adding the pigment and stirring to obtain the flame-retardant spray painting paint.

Has the advantages that: the main solvent of the flame-retardant spray paint prepared by the invention adopts non-flammable tetrachloroethylene and dichloromethane, so that the flame-retardant spray paint has good flame retardance and good temperature resistance, and can be normally used at 200 ℃; the performance of the flame-retardant spray paint is greatly improved through the synergistic effect among the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin, for example, the flame-retardant spray paint has the advantages of good quick drying property, uniform paint film, bright color, good weather resistance, no influence of air temperature and ultraviolet rays, and high adhesion; through the combined action of the rutile titanium dioxide color paste, the phosphate flame retardant and the organic silicon defoamer KM-98, the flame-retardant spray paint has excellent dispersibility, cannot cause the problems of thickening, pigment sedimentation and the like after being placed for a long time, has fineness of not more than 3 mu m, softens a paint film, is smoother to use and spray, is not easy to block a nozzle, and has excellent stability.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

In order to solve the technical problems, the first aspect of the invention provides flame-retardant spray painting paint which at least comprises, by weight, 1-10 parts of thermoplastic acrylic resin, 1-10 parts of cellulose acetate butyrate, 5-10 parts of pigment, 0.2-2 parts of flame retardant and 60-120 parts of solvent.

In one embodiment, the flame-retardant spray painting paint at least comprises 6 parts by weight of thermoplastic acrylic resin, 5 parts by weight of cellulose acetate butyrate, 8 parts by weight of pigment, 1 part by weight of flame retardant and 90 parts by weight of solvent.

Thermoplastic acrylic resin

In one embodiment, the thermoplastic acrylic resin has a glass transition temperature of 40 to 60 ℃; preferably, the glass transition temperature of the thermoplastic acrylic resin is 50 ℃.

In the present invention, the glass transition temperature refers to the transition temperature of amorphous polymer (including amorphous part in crystalline polymer) from glassy state to high elastic state or from the latter to the former, and is the lowest temperature of free movement of amorphous polymer macromolecular segment, usually expressed by Tg, and is an important characteristic parameter of the material, and many characteristics of the material are changed sharply around the glass transition temperature.

In one embodiment, the thermoplastic acrylic resin is selected from one or more of BR-113, BR-116, BR-73, BR-85, MB-2952, MB-2660, BR-106; preferably, the thermoplastic acrylic resin is BR-106, has a glass transition temperature of 50 ℃ and is purchased from Mitsubishi corporation.

Cellulose acetate butyrate

In one embodiment, the cellulose acetate butyrate has a butyryl content of from 35 to 45 weight percent; preferably, the butyryl group content of the cellulose acetate butyrate is 38 wt%.

In the invention, the method for testing the content of the butyryl group in the cellulose acetate butyrate is carried out by the method of ASTM D817-96, and the method comprises the steps of distilling a sample twice after saponification, and finally carrying out chemical titration to obtain the content of the butyryl group.

In one embodiment, the cellulose acetate butyrate is selected from one or more of CAB-381-0.5, CAB-381-2, CAB-381-0.1, CAB-381-20, CAB-551-0.2, CAB-551-0.01, CAB-381-2BP, CAP-482-0.5, CAB-553-0.4, CAB-531-1; preferably, the cellulose acetate butyrate is CAB-381-0.1, and the cellulose acetate butyrate has a butyryl group content of 38 wt% and is purchased from Istman chemical company.

Pigment (I)

In one embodiment, the pigment is selected from one or more of rutile titanium dioxide mill base, carbon black, phthalocyanine blue, red iron oxide, brown iron oxide, black iron oxide, yellow iron oxide, micaceous iron oxide, zinc phosphate, zinc molybdate, aluminum tripolyphosphate, aluminum hydroxy aluminosilicate, and sodium metaborate; preferably, the pigment is rutile titanium dioxide color paste with the model number of U4002, and is purchased from Shanghai pigment-loving chemical technology Co.

Flame retardant

In one embodiment, the flame retardant is a phosphate flame retardant.

In the present invention, the phosphate-based flame retardant includes, but is not limited to, trixylenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trihexyl phosphate, cresyldiphenyl phosphate, hexyldiphenylphosphate, octyldiphenylphosphate, diphenyl-2-ethylcresylphosphate, tri (isopropylphenyl) phosphate, resorcinol diphenylphosphate, polyphosphate esters (bisphenol a diphosphate, hydroquinone diphosphate, resorcinol diphosphate, trisphenol triphosphate, bisphenol a bis (xylylphosphate), phenylene bis (diphenylphosphate), phenylene bis (xylylphosphate).

In a preferred embodiment, the flame retardant is tri (xylene) phosphate (CAS number 25155-23-1).

Solvent(s)

In one embodiment, the solvent is selected from one or more of chlorinated hydrocarbons, aliphatic alcohols, alcohol ether solvents; preferably, the solvent is a mixture of chlorinated hydrocarbon, aliphatic alcohol and alcohol ether solvent.

In one embodiment, the mass ratio of the chlorinated hydrocarbon, the fatty alcohol and the alcohol ether solvent is (22-60): 1: 1; preferably, the mass ratio of the chlorohydrocarbon to the aliphatic alcohol to the alcohol ether solvent is 28: 1: 1.

in one embodiment, the chlorinated hydrocarbon is selected from tetrachloroethylene, 1, 2-dichloroethane, 1,1 dichloroethane, 2-chloro-2-methylpropane, 3-chloropropene, 1, 1-dichloroethylene, monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, 1, 1-dichloroethane, 1,1, 1-trichloroethane, 1,1, 2-trichloroethane, one or more of 1,1,1, 2-tetrachloroethane, 1,1,2, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, chloropentane, dichloropentane, 1-chlorohexane, 1-chloro-2-ethylhexane; preferably, the chlorinated hydrocarbon is a mixture of tetrachloroethylene and dichloromethane.

In a preferred embodiment, the mass ratio of tetrachloroethylene to dichloromethane is (1.2-1.4): 1; more preferably, the mass ratio of tetrachloroethylene to dichloromethane is 1.3: 1.

in one embodiment, the fatty alcohol is a C1-C5 fatty alcohol.

In one embodiment, the C1-C5 fatty alcohol includes, but is not limited to, one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, n-butanol, n-pentanol, 2-butanol, 2-pentanol; preferably, the fatty alcohol of C1-C5 is isopropanol.

In the invention, the alcohol ether solvent is an oxygen-containing solvent, and mainly is low-carbon alcohol ether of ethylene glycol and propylene glycol. The composition has both ether bond and hydroxyl. The former has lipophilicity and can dissolve hydrophobic compounds, and the latter has hydrophilicity and can dissolve water-soluble compounds. The alcohol ether solvent is mixed with other solvents in solvent paint for use, and is characterized in that the leveling property of a coating film can be maintained after most of the solvents are volatilized. The alcohol ether solvent has good compatibility with water, and is widely used in water paint as a cosolvent for coupling.

In one embodiment, the alcohol ether solvent is selected from one or more of propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether; preferably, the alcohol ether solvent is propylene glycol methyl ether.

In one embodiment, the flame-retardant spray paint further comprises 1-5 parts by weight of rosin modified resin and 0.01-0.1 part by weight of organic silicon defoamer.

In a preferred embodiment, the flame-retardant spray paint further comprises 3 parts by weight of rosin modified resin and 0.05 part by weight of silicone defoamer.

Rosin modified resin

In one embodiment, the rosin-modified resin is selected from one or more of rosin-modified phenolic resins, rosin-modified terpene phenol resins, rosin-modified maleic acid resins; preferably, the rosin modified resin is a rosin modified maleic acid resin.

In a preferred embodiment, the rosin-modified maleic acid resin is Japanese crude maleic acid resin No.8, purchased from Japanese crude chemical.

Organic silicon defoaming agent

In one embodiment, the silicone defoamer is selected from one or more of KM-71, KM-73A, KM-73E, KM-75, KM-85, KM-89, KM-90, KM-98, KM-7550, KM-7752, KS-508, KS-530, KS-531, KS-538, KS-540, KS-66, KS-69, KS-7704S, X-50-1090B; preferably, the silicone defoamer is KM-98, purchased from shin-Etsu corporation of Japan.

The inventor finds that the chlorinated hydrocarbon, the fatty alcohol and the alcohol ether solvent are used as the solvents, and the phosphate flame retardant is added, so that the flame retardant is good in flame retardance and good in temperature resistance, can be normally used at 200 ℃, is particularly suitable for spraying, and is not easy to block a nozzle. The reason the inventor believes is probably that the tri (xylene) phosphate not only has excellent flame retardancy, but also has a plasticizing effect and can interact with thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin to soften a paint film. In addition, the prepared flame-retardant spray paint has the advantages of good quick drying property, uniform paint film, bright color, good weather resistance, no influence of air temperature and ultraviolet rays and high adhesion force by adopting the synergistic effect of thermoplastic acrylic resin BR-106 with the glass transition temperature of 50 ℃, cellulose acetate butyrate CAB-381-0.1 with the butyryl content of 38 wt% and rosin modified maleic resin. The reason the inventor guesses may be that the cellulose acetate butyrate CAB-381-0.1 with the butyryl content of 38 wt% can inhibit sagging and shrinkage cavities so as to reduce surface defects, can effectively inhibit plasticizer migration due to interaction with the tri (xylene) phosphate, has good compatibility with the cellulose acetate butyrate and rosin modified resin and the thermoplastic acrylic resin BR-106 with the glass transition temperature of 50 ℃, and further improves the adhesion and weather resistance of the flame retardant type spray marking paint. The inventor unexpectedly discovers in the further research process that the problems of thickening, pigment sedimentation and the like cannot be caused by long-time placement of the flame-retardant spray painting paint due to the interaction of the cellulose acetate butyrate CAB-381-0.1 with the butyryl content of 38 wt% and the rutile titanium dioxide color paste U4002 and the organic silicon defoamer KM-98, the fineness is not more than 3 mu m, the reason guessed by the inventor is probably that the cellulose acetate butyrate CAB-381-0.1 with the butyryl content of 38 wt% promotes the oriented arrangement of rutile titanium dioxide in resin, the dispersibility of the organic silicon defoamer KM-98 is improved, the fineness of the system is not more than 3 mu m, and the spraying is smooth.

In one embodiment, the flame retardant spray paint has a fineness of no more than 3 μm.

In the invention, the fineness detection method is GB/T1724-1979.

In one embodiment, the tack-free time of the flame retardant spray paint does not exceed 10 seconds.

In the invention, the detection method of the surface drying time is GB/T1728-1979.

The second aspect of the invention provides a preparation method of the flame-retardant spray painting paint, which comprises the following steps:

s1: stirring the solvent, sequentially adding the flame retardant and the organic silicon defoaming agent, and stirring;

s2: sequentially adding thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin, and stirring until the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin are completely dissolved;

s3: and adding the pigment and stirring to obtain the flame-retardant spray painting paint.

In one embodiment, the preparation method of the flame retardant spray paint comprises the following steps:

s1: the chlorinated hydrocarbon, the fatty alcohol and the alcohol ether solvent are stirred uniformly in sequence, and the stirring speed is 300-500 rpm; sequentially adding the flame retardant and the organic silicon defoamer, and uniformly stirring at the stirring speed of 1000-1400 rpm;

s2: sequentially adding thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin, and stirring until the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin are completely dissolved, wherein the stirring speed is 1000-1400 rpm;

s3: and adding the pigment, and stirring for 0.5-2h at the stirring speed of 1000-1400rpm to obtain the flame-retardant spray painting paint.

In a preferred embodiment, the preparation method of the flame-retardant spray painting paint comprises the following steps:

s1: uniformly stirring the chlorohydrocarbon, the fatty alcohol and the alcohol ether solvent in turn at the stirring speed of 400 rpm; sequentially adding the flame retardant and the organic silicon defoamer, and uniformly stirring at the stirring speed of 1200 rpm;

s2: sequentially adding thermoplastic acrylic resin, cellulose acetate butyrate and rosin modified resin, and stirring until the thermoplastic acrylic resin, the cellulose acetate butyrate and the rosin modified resin are completely dissolved, wherein the stirring speed is 1200 rpm;

s3: and adding the pigment, and stirring for 1h at the stirring speed of 1200rpm to obtain the flame-retardant spray painting paint.

The third aspect of the invention provides an application of the flame-retardant spray painting paint, which is applied to spraying in a steel mill at the temperature of 200 ℃.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the starting materials used are all commercially available, unless otherwise specified.