CN102603991B - Environmental-friendly waterborne protective and decorative paint for inner cabin of ship - Google Patents

Abstract

The invention relates to a formula and a preparation process of environmental-friendly waterborne protective and decorative paint. The preparation process comprises the following steps of: firstly, synthesizing acrylic acid modified alcohol acid emulsion with low VOC (volatile organic compounds) content, high stability and high drying speed; then mixing the emulsion serving as a base stock and pigments and auxiliaries; and processing by the processes of grinding, dispersing and the like to form the paint. The paint has low VOC content, does not contain benzene series, is non-toxic and non-inflammable, has no pollution to the environment, is harmless for physical health of constructors, can be constructed by adopting various methods of brushing, spraying, dip-coating and the like, has high drying speed and is safe and convenient to use. The environmental-friendly waterborne protective and decorative paint has high paint film mechanical strength, strong adhesive power and good decoration and is mainly used for a steel plate and the surface of a flexible package in an inner cabin of a ship as a protective and decorative coating. The environmental-friendly waterborne protective and decorative paint can also be used for protection and decoration of a steel iron material of facility parts such as a vehicle, a bridge, a storage tank, a pipeline, and mechanical equipment.

Description

Environmentally friendly water-based protective decorative coatings for ship interiors

technical field

The invention relates to a formula and a preparation process of an environment-friendly water-based protective decorative paint. First, an acrylic-modified alkyd emulsion with low VOC content, good stability, and fast drying was synthesized, and then the emulsion was used as a base material to mix with pigments and additives, and processed into coatings through grinding and dispersing processes. The coating has low VOC content, does not contain benzene series, is non-toxic, non-flammable, has no pollution to the environment, and is harmless to the health of construction workers. It can be applied by various methods such as brushing, spraying, and dipping. It dries quickly and is safe to use. convenient. The paint film has high mechanical strength, strong adhesion, and good decoration. It is mainly used as a protective and decorative coating on steel plates and soft cladding surfaces in ship interiors. It can also be used for the protection and decoration of iron and steel materials in facilities such as vehicles, bridges, storage tanks, pipelines, and mechanical equipment.

Background technique

Inner cabin paint is widely used in shipbuilding for the decoration and protection of inner cabin steel plates and soft cladding surfaces. Due to the narrow space in the interior cabin, inconvenient painting operation, and poor ventilation, there are hidden dangers of accidents such as fire and poisoning in the paint construction of the interior cabin. At present, the most widely used interior paint in the shipbuilding industry is solvent-based alkyd paint. Since the solvent-based alkyd paint contains about 50% organic solvent, there are problems of fire hazard and pollution of the interior cabin environment during construction. Especially in the soft covering construction of the insulating layer, the covering cloth and the insulating material are porous materials, which have a large amount of paint absorption and are easy to seal the organic solvent inside the porous substrate, resulting in long-term paint odor in the cabin. It is also very harmful to the health of the personnel working and living in the cabin. Therefore, major domestic shipbuilding factories have an urgent need for environmentally friendly water-based interior paint. It is of great significance to research and develop environment-friendly water-based interior paint to eliminate hidden dangers of fire and poisoning accidents in the construction of interior paint, and to improve the living environment of interior cabins.

Traditional paints are mostly solvent-based, which contain a large amount of organic solvents, and often need to be diluted with organic solvents when used. These solvents evaporate into the atmosphere during construction and paint film drying, which is harmful to human health and pollutes the environment. Fire hazard. With the increasingly stringent environmental regulations around the world, it is the general trend to develop environmentally friendly coatings to replace solvent-based coatings. With its excellent comprehensive performance, solvent-based alkyd paint has always occupied a considerable proportion in the field of traditional coatings. With the improvement of people's awareness of environmental protection and the improvement of environmental protection regulations, the development of water-based alkyd paints that can replace solvent-based alkyd paints has always been the direction of the paint industry. This has gone through the following three stages:

The first stage is to emulsify the solventborne alkyd with an emulsifier. Due to the influence of the added emulsifier, this method has many disadvantages such as poor coating stability, poor water resistance of the paint film, and poor decoration.

The second stage is to introduce hydrophilic groups such as polyether segments, carboxyl groups, etc. into alkyd resin molecules, and disperse them in alkaline aqueous solution with the help of co-solvents to form water-dilutable alkyds. Most of the existing water-based alkyd paints are based on this type of resin. This method has the disadvantages of high emulsion viscosity, poor water resistance of the paint film, and high organic solvent content.

After the 1990s, people began to devote themselves to the development of a new generation of water-based alkyd resins, that is, core-shell structure, self-emulsifying emulsions. Since the emulsion does not contain an external emulsifier, it overcomes the shortcomings caused by the external emulsifier; and because the latex particles have a core-shell structure, the overall acid value of the resin is low and no external co-solvent is required, which overcomes the disadvantages of the second-generation alcohol. Some disadvantages inherent in acids. In addition, the emulsion is a microemulsion (the average particle size can be as small as 50-100nm), and a high-gloss, high-decorative finish paint can be prepared. For example, the Austrian Winova Company has developed a water-based acrylic modified alkyd topcoat (AT9400711), which is made of unsaturated fatty acids and acrylic acid mixed monomers such as methacrylic acid, polyethylene glycol (meth)acrylate, other ( Free radical polymerization of meth)acrylic acid (ester) or vinyl monomers to obtain copolymer A, and esterification of unsaturated fatty acids, polyhydric alcohols, dibasic acids, and (multiple) cyclic acids to obtain polymer B, and then make the two The latter reacts to obtain an acrylic acid-modified alkyd resin with an acid value of 25-70, and 80% of its acid value is derived from the methacrylic acid in the copolymer A. The resin can be self-emulsified by neutralizing it with alkali and stirring with water to obtain an acrylic modified alkyd emulsion. Using the emulsion as base material, acrylic modified alkyd paint can be prepared for protection and decoration of various metal surfaces. U.S. Patent No. 4,996,250 carries out radical copolymerization with methacrylic acid and other vinyl or/and (meth)acrylic acid ester monomers and dry fatty acid, synthesizes alkyd resins with an acid value of 25 to 70, wherein at least 80% of the acid Values are derived from methacrylic acid, partially or fully neutralized with alkali to form a water-reducible alkyd resin. The alkyd resin is mixed with maleated oil or fatty acid, and a polymer emulsion composed of (meth)acrylates or copolymers of butadiene and styrene is added. A new waterborne resin that can meet various requirements was synthesized. U.S. Patent No. 6,489,398 uses methacrylic acid-(meth)acrylate-vinyl monomers and unsaturated fatty acids for graft copolymerization, and then reacts with polyols to generate copolymers with an acid value of 25-70, wherein 80% of the carboxyl group source in methacrylic acid. The carboxyl groups are neutralized with ammonia to obtain a water-soluble alkyd resin. Compared with general acrylic and self-drying alkyd resins, this resin has a storage time and self-drying performance that are no less than general alkyd resins. U.S. Patent US0152830 grafts acrylic acid monomers to unsaturated fatty acids through free radical polymerization to form acrylic acid grafted fatty acids, and then reacts with alkyds with terminal hydroxyl groups to form a condensation-type acrylic acid-modified alkyd polymer. The carboxyl groups of the acrylic portion of the polymer are neutralized with the amine, making the shell portion hydrophilic while the alkyd portion remains hydrophobic. The resulting salt allows the polymer to be dispersed in water. In the core-shell structure of this polymer, the alkyd that is prone to hydrolysis acts as the core, and the acrylic acid (anti-hydrolysis) in the water phase acts as the shell, in order to obtain better hydrolytic stability. The coatings prepared by this new type of resin did not decline in various properties after being heated and stored for several weeks.

The advantage of this type of invention is that the emulsion has high mechanical stability, can be ground together with pigments and fillers, and simplifies the paint-making process. The paint construction performance and wet film leveling are better, and the paint film has higher mechanical strength. One of the disadvantages is that unsaturated fatty acids with less sources and higher prices are used as raw materials, and the resin preparation process is complicated, the source of raw materials is limited, and the production cost is high. The second is that the resin contains polyether (polyoxyethylene) groups with strong hydrophilicity, which affects the water resistance of the paint film. The third is that acrylic acid and alkyd are connected by ester bond, and the storage stability is not ideal. The fourth is that the particle size of the emulsion is relatively large (average particle size > 200 μm), and the gloss of the paint film is low.

In order to overcome the shortcomings of the existing water-based alkyd paint, the present invention develops a new type of core-shell structure acrylic modified alkyd resin emulsion, that is, first synthesize high molecular weight alkyd resin, and then use acrylic monomer and alkyd resin An acrylic acid grafted alkyd resin with an acid value of 20-40 mgKOH/g is prepared by radical polymerization, and the resin is neutralized with amine and added with water to form an acrylic modified alkyd emulsion with good storage stability. The water-based acrylic modified alkyd paint is made by mixing the emulsion with pigments and additives. It has low VOC content, does not contain formaldehyde and benzene series, has no pollution to the environment, and is harmless to the health of construction workers. Its construction performance, self-drying property, mechanical strength of the paint film, and decorative properties have all reached the level of solvent-based alkyd paints. It can replace solvent-based alkyd paint for ship interior steel and soft cladding surfaces as a protective and decorative coating.

The implementation of the invention can remarkably improve the paint coating construction environment of the inner cabin, and protect the health of construction and cabin working and living personnel. This product can also be popularized and applied to automobiles, railway vehicles and other means of transportation, facilities such as storage tanks and pipelines in the petrochemical industry, steel structures such as bridges, iron towers, and interframes, and the protection and decoration of steel materials in the manufacture and maintenance of various mechanical equipment. Notable economic benefits, but also has huge social benefits. It is of great significance to the technological progress of the paint industry and the protection of the human living environment.

Contents of the invention

The present invention solves the problems that the traditional alkyd paint has high organic solvent content, pollutes the environment, is harmful to human health and has fire hazards, and the existing water-based alkyd paint has complex preparation process, high cost, poor dryness and stable storage Sexual disadvantages.

The invention consists of two parts, the preparation of the acrylic acid modified alkyd emulsion and the preparation of the paint based on the emulsion.

Preparation of Acrylic Modified Alkyd Emulsion:

Technical route: first prepare alkyd resin, first carry out alcoholysis reaction with vegetable oil and polyalcohol, then add dibasic alcohol, dibasic acid (anhydride) and tung oilic acid and alcoholyzate for esterification, the acid value reaches 5--10mgKOH /g or the viscosity reaches 4--6s, lower the temperature to obtain alkyd resin. Then dropwise add acrylic acid monomer with an acid value (theoretical value) of 40-60mgKOH/g and other unsaturated monomers (containing an initiator), keep warm for a period of time, and after the viscosity reaches 6-9s, cool down, Self-emulsifying in an aqueous solution, that is, an emulsion with a hydrophobic alkyd resin as the core and a hydrophilic acrylic resin as the shell is produced.

Lotion recipe:

Preparation Process:

①Put the vegetable oil, trihydric alcohol and catalyst in the formula into the 1 ^# reaction vessel, start stirring, blow nitrogen, raise the temperature to 230--240°C, keep it warm for about 1.5--2h, measure the ethanol tolerance (95% ethanol, 1:9 as the end point), after passing the test, cool down to 180--190°C.

②Add the formulated amount of glycol, dibasic acid or dibasic anhydride and 3-5 parts of refluxing xylene into 1 ^# reaction vessel, and react at 210--220°C for 1 hour.

③Add the formula amount of tungoleic acid, reflux at 230-240°C for 2-3h, measure the acid value and viscosity. As you approach the finish line, measure every half hour. When the viscosity reaches 4--6s or the acid value reaches 5--8mgKOH/g, stop heating, cool down to 120--130°C, put it into 2 ^# reaction vessel, and pump out the refluxing xylene at the same time.

④Mix the unsaturated monomer and initiator in the formula amount, enter the high-level dripping tank, and drop it into the 2 ^# reaction vessel under the protection of nitrogen. The dropping time is about 3 hours, and the temperature is kept at 100--130 ℃ for about 3 hours. , when the viscosity reaches 6-9s, cool down to 70--80°C.

⑤ Add the softened water and neutralizer in the formula amount to 3 ^# reaction container, start stirring, transfer the material in 2 ^# reaction container to 3 ^# reaction container, stir and emulsify at low speed for 1--3 hours, and obtain a solid content of 30 -50% acrylic modified alkyd emulsion.

The above-mentioned vegetable oil can be linseed oil, soybean oil or a mixture thereof, and the optimal amount is 40-60 parts; the trihydric alcohol can be glycerin, trimethylolpropane or a mixture thereof, and the optimal amount is 5-10 parts; the catalyst is hydrogen Lithium oxide or calcium hydroxide; Dibasic alcohol can be butylene glycol, neopentyl glycol or its mixture, and optimum dosage is 5-10 parts; Dibasic acid (anhydride) can be hexahydrophthalic anhydride, isophthalic acid, One or more in fumaric acid, (methyl) Nadic acid anhydride, preferably isophthalic acid consumption is 6-20 parts, preferably 10-20 parts; (Methyl) Nadic acid anhydride consumption is 5- 10 parts; unsaturated monomers include one or more of (meth)acrylic acid, methyl methacrylate, butyl (meth)acrylate, styrene, dibutyl maleate, and vinyl tertiary carbonate. The initiator is benzoyl peroxide, the optimal dosage is 0.6-1.2 parts; the neutralizer is one of ammonia water, AMP-95, N-ethylmorpholine, N, N dimethylethanolamine, and triethylamine or several. Demineralized water is deionized water or distilled water, the dosage is 120-180 parts, the content of water-soluble substances is required to be less than 100ppm, and the conductivity is less than 20μs/cm.

Preparation of paint

Coating Formulation:

Preparation Process

①Add the demineralized water, additives, and neutralizers in the formula amount into the slurry mixing container, and stir evenly with an adjustable high-speed disperser (the same below).

② Add 60% of the formula of acrylic modified alkyd emulsion and stir well.

③ Add the pigments and fillers in the prescribed amount, and stir evenly.

④Add 1/3 of the thickener in the formula and stir well.

⑤Use a sand mill to grind until the fineness is below 30 μm to obtain the color paste.

⑥Add the obtained color paste, the remaining 40% of the recipe amount of acrylic modified alkyd emulsion, and the recipe amount of drier into the paint mixing container, and stir evenly.

⑦ Add 2/3 thickener of the remaining formula, stir evenly, and filter to obtain the finished product.

The above-mentioned demineralized water is deionized water or distilled water, wherein the total amount of water-soluble substances is less than 100ppm, and the conductivity is less than 20 μs/cm.

The neutralizing agent is one or more of ammonia water, triethylamine, dimethylethanolamine, N-ethylmorpholine, and 2-amino-2-methyl-1-propanol.

The auxiliary agent is one or more of wetting agent, leveling agent, defoamer, preservative, and antifungal agent. The wetting agent is polyether-modified acetylenic alcohol, such as SURFYNOL GA and SURFYNOL TG of American Gas Chemical Company; the leveling agent can be selected from fluorine-containing surfactant or polyether-modified silicone additive, such as the German BYK company Byk348, 307 or EFKA-3570 from Efka Company in the Netherlands, SFL-50 from AJA Company in the United States; the defoamer is mineral oil, polyether, silicone resin and their composites, such as SN1311, 1340, NXZ from NOPCO Company, BYK’s BYK024; preservatives can be KATHON LXE from Oriental-Rohm and Haas, PG520 from SK Korea; antifungal agents can be SKANE M-8 from Oriental-Rohm and Haas, MA from SK Korea -twenty one;

The pigment can be one or more of iron oxide red, iron oxide black, iron oxide yellow, zirconium-aluminum coated rutile titanium dioxide, BGS phthalocyanine blue (P.B.15:3), carbon black; the filler can be precipitated sulfuric acid Barium, talc or a mixture thereof; the thickener is an alkali-soluble acrylic emulsion thickener or a polyether polyurethane thickener, such as Beijing Dongfang-Rohm and Haas TT935 thickener, Hemings 420 thickener Thickener, R-278 thickener, the 830W thickener of French COATEX company, consumption preferably 0.5-1.0 part; Emulsions with zinc alkanoate as active ingredients, such as the VXW drier of Austrian Vinova Company.

Unsaturated carboxylate, the composition is amine (or ammonium) salt of unsaturated carboxylic acid, (meth)acrylic acid ester and ethylenically unsaturated monomer copolymer. Its preparation process is as follows:

①Add 25-35 parts of propylene glycol methyl ether into the 1 ^# reaction vessel, start stirring, blow nitrogen, raise the temperature to 110--120°C, and keep a slight boiling state;

② Mix 30-50 parts of unsaturated carboxylic acid monomer, 20-30 parts of (meth)acrylate monomer and 20-30 parts of vinyl monomer with 2-3 parts of initiator, enter the high-level dripping tank, and Under the protection of nitrogen, add it dropwise to 1 ^# reaction container, the dropwise addition time is about 3-4h, after the addition is completed, keep it at 110-120°C for 1-2h.

③ Cool down to 60-70℃, add 20-25 parts of neutralizer. Gradually add water and stir to obtain an unsaturated carboxylate with a solid content of 35-40%.

Wherein the unsaturated carboxylic acid is one or more in acrylic acid, methacrylic acid, maleic anhydride; (meth)acrylic acid ester can be (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, ( One or more of butyl methacrylate; vinyl monomer can be one or more of styrene, dibutyl maleic anhydride, vinyl acetate, tertiary vinyl acetate; initiator It is benzoyl peroxide; the neutralizing agent is N,N dimethylethanolamine or 2-amino-2-methyl-1-propanol.

Beneficial effects of the present invention:

The water-based acrylic modified alkyd resin of the present invention replaces phthalic anhydride with isophthalic acid and tetrahydrophthalic anhydride, introduces dihydric alcohol in the esterification stage, the molecular weight of the resin tends to be uniform, the molecular regularity is greatly improved, and the crystallinity tendency is significantly increased. It not only significantly improves the problem of poor storage stability caused by the imminent hydrolysis effect of phthalic anhydride in traditional water-based alkyd resins, but also significantly improves the drying speed of the paint film. After the cabin is constructed, it can be surface-dried quickly, which greatly reduces the chance of the paint film being contaminated by dust, and significantly improves the construction efficiency and the decorativeness of the paint film.

Compared with traditional solvent-based alkyd paints and existing water-based alkyd paints, the environmentally friendly water-based paint for ship interior cabins of the present invention has the following advantages: ①It is safe and convenient to use. The coating uses water as the dispersion medium, does not contain co-solvent, has low VOC content (≤150g/L), and has little odor, which improves the construction environment and avoids fire hazards. ②Good decoration. The base material of the paint is self-emulsifying acrylic acid modified alkyd emulsion, the emulsion particle size is small (the average particle size is only 50-70nm), the film-forming property is good, and the top paint with high gloss and high decoration can be prepared. ③The performance of the paint film is good. The base material of this coating is acrylic modified alkyd emulsion with core-shell structure, the core is alkyd resin, and the shell is acrylic resin, which not only retains the good self-drying property, excellent adhesion and flexibility of alkyd resin, It also has the excellent weather resistance of acrylic resin. ④ Good storage stability. The use of isophthalic acid instead of phthalic anhydride improves the hydrolysis resistance of the resin; the introduction of methyl nadic anhydride increases the grafting rate of acrylic resin on the alkyd resin chain, and the mechanical storage stability and thermal stability of the resin are significantly improved. , It is convenient for paint grinding, which greatly prolongs the storage period of paint. ⑤ Broad application prospects. All the indicators of this coating have reached or exceeded the level of solvent-based alkyd coatings, and can completely replace solvent-based alkyd coatings. It has a good effect on the decoration and protection of steel components. Replacing solvent-based alkyd paint with water-based alkyd paint can save energy, protect the environment, and have important social and huge economic benefits.

Detailed ways

Several emulsion synthesis examples are listed below, but the present invention is not limited to these examples. The emulsion preparation formula is shown in Table 1.

Table 1 Emulsion Synthesis Example

The emulsion synthesis process conditions are shown in Table 2.

Table 2 Emulsion synthesis process conditions

project Temperature (°C) Time (h) Alcoholysis 230-250 1.5-2 Esterification 220-230 3-4 Free radical polymerization plus monomer 100-130 3-4 Free radical polymerization insulation 100-130 1-2 self-emulsifying 40-60 1-2

The properties of the emulsion are shown in Table 3.

Table 3 Emulsion properties

It can be seen from the above examples that the storage stability of the water-based resin of the present invention is significantly improved, the drying time is significantly shortened, and the water resistance is also significantly improved.

The coating preparation method is illustrated below, but the present invention is not limited to the following examples, and the formula is shown in Table 4:

Table 4 Formulation example

Note: The self-made 1 ^# -3 ^# and 9 ^# emulsions in the above formula are the emulsions obtained in the emulsion synthesis examples 1-3 and comparative example 9 respectively.

The AC-261 emulsion in comparative example 2 is the acrylic emulsion of Beijing Dongfang-Rohm and Haas Company.

The AY-396 emulsion in Comparative Example 3 is an acrylic-modified alkyd emulsion from Vinova Company in Austria.

Coating properties are shown in Table 5

Table 5. Coating Properties

Claims (5)

1. the acrylic modified alkyd nanoemulsions of a nucleocapsid structure, it is synthetic by following prescription:

The preparation method of the acrylic modified alkyd nanoemulsions of wherein said nucleocapsid structure is:

1. vegetables oil, trivalent alcohol and the catalyzer with formula ratio adds 1 ^#Reaction vessel starts stirring, and logical nitrogen is warmed up to 230--240 ℃, and insulation 1.5--2h surveys the ethanol tolerance, and with 95% ethanol, 1:9 is terminal point, qualified after, cool to 180--190 ℃;

2. formula ratio dibasic alcohol, diprotic acid or dibasic acid anhydride and 3-5 part backflow dimethylbenzene are added 1 ^#Reaction vessel, 210--220 ℃ of reaction 1h;

3. add the formula ratio eleostearic acid, 230--240 ℃ of back flow reaction 2--3h surveys acid number, viscosity, during near terminal point, surveys once every half an hour, when viscosity reaches 4--6s or acid number and reaches 5--8mgKOH/g, stops heating, cools to 120--130 ℃, puts into 2 ^#Reaction vessel extracts backflow dimethylbenzene simultaneously;

4. formula ratio unsaturated monomer and initiator are mixed, enter the high-order groove that drips, under nitrogen protection, be added drop-wise to 2 ^#In the reaction vessel, drip time 3h, 100--130 ℃ of insulation reaction 3h when viscosity reaches 6-9s, cools to 70--80 ℃;

5. formula ratio softening water, neutralizing agent are joined 3 ^#In the reaction vessel, open stirring, with 2 ^#Material in the reaction vessel transfers to 3 ^#In the reaction vessel, stirring at low speed emulsification 1--3h, obtaining solids content is the acrylic modified alkyd emulsion of 30-50%;

Described vegetables oil is oleum lini, soya-bean oil or its mixture; Described trivalent alcohol is glycerine, TriMethylolPropane(TMP) or its mixture; Described dibasic alcohol is butyleneglycol, neopentyl glycol or its mixture; Described diprotic acid or binary acid anhydride are one or more in HHPA, m-phthalic acid, fumaric acid, (methyl) carbic anhydride; Described unsaturated monomer is one or more in (methyl) vinylformic acid, methyl methacrylate, (methyl) butyl acrylate.

2. the acrylic modified alkyd nanoemulsions of nucleocapsid structure according to claim 1 is characterized in that, described initiator is benzoyl peroxide; Described neutralizing agent is ammoniacal liquor, AMP-95, N-ethylmorpholine, N, and one or more in N-dimethylethanolamine, the triethylamine, described softening water are deionized water or distilled water; Described catalyzer is lithium hydroxide or calcium hydroxide.

3. the cabin is characterized in that with environment-friendly type aqueous protected decoration coating this system component is in the boats and ships of making as base-material with the acrylic modified alkyd nanoemulsions of the nucleocapsid structure of claim 1:

Described salt unsaturated carboxylic acid prepares by the following method:

1. 1 ^#Add 25-35 part propylene glycol monomethyl ether in the reaction vessel, start stirring, logical nitrogen is warmed up to 110--120 ℃, keeps slight boiling condition;

2. one or more in 30-50 part vinylformic acid, methacrylic acid, the MALEIC ANHYDRIDE, 20-30 part (methyl) acrylate monomer and 20-30 part vinyl monomer and 2-3 part initiator are mixed, and enter the high-order groove that drips, and under nitrogen protection, are added drop-wise to 1 ^#In the reaction vessel, drip time 3-4h, add the back in 110-120 ℃ of insulation reaction 1-2h;

3. cool to 60-70 ℃, add 20-25 part neutralizing agent; Add water gradually and stir, obtain the salt unsaturated carboxylic acid that solid content is 35-40%;

Described pigment is one or more in iron oxide black, red iron oxide, iron oxide yellow, titanium dioxide, phthalocyanine blue, the carbon black; Described filler is process white, talcum powder or its mixture; Described siccative is that cobalt naphthenate, zirconium naphthenate, zinc naphthenate, calcium naphthenate are the emulsion of effective ingredient; Described thickening material is caustic solubility ACRYLIC EMULSION class or polyether-polyurethane class thickening material; Described auxiliary agent is one or more in wetting agent, flow agent, defoamer, sanitas, the mould inhibitor; Described neutralizing agent is one or more in ammoniacal liquor, triethylamine, dimethylethanolamine, N ethyl morpholine, the 2-amino-2-methyl-1-propanol; Described softening water is deionized water or distilled water.

4. the cabin is with environment-friendly type aqueous protected decoration coating in the boats and ships according to claim 3, and its preparation method is:

1. in joining the slurry container, add softening water, auxiliary agent, the neutralizing agent of formula ratio, stir with the adjustable high-speed dispersion machine;

2. add the acrylic modified alkyd emulsion of 60% formula ratio, stir;

3. add pigment, the filler of formula ratio, stir;

4. add the thickening material of formula ratio 1/3, stir;

5. be ground to fineness with sand mill and reach below the 30 μ m, get mill base;

6. in the paint container, add the mill base that obtains, the acrylic modified alkyd emulsion of residue 40% formula ratio, the siccative of formula ratio, stir;

7. add residue formula ratio 2/3 thickening material, stir, filter, get finished product.

In the boats and ships according to claim 4 the cabin with environment-friendly type aqueous protected decoration coating, it is characterized in that described (methyl) acrylate is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate; Vinyl monomer is vinylbenzene, vinyl acetate or its mixture; Initiator is benzoyl peroxide; Neutralizing agent is N, N dimethylethanolamine or 2-amino-2-methyl-1-propanol.