CN109535872B

CN109535872B - Passivation treatment product of solvent type aluminum paste

Info

Publication number: CN109535872B
Application number: CN201710614235.3A
Authority: CN
Inventors: 贺霄洁; 干佳缘; 杜瑞
Original assignee: Peter Lacke Shanghai Co ltd
Current assignee: Peter Lacke Shanghai Co ltd
Priority date: 2017-07-25
Filing date: 2017-07-25
Publication date: 2020-10-16
Anticipated expiration: 2037-07-25
Also published as: CN109535872A

Abstract

The invention discloses a passivation treatment product of solvent type aluminum paste, which is prepared from the following components in parts by weight: 40 parts of water-based acrylic resin, 0-5 parts of cosolvent, 15-20 parts of component A, 0.5-2 parts of substrate wetting agent, 0.5-2 parts of defoaming agent, 2-5 parts of rheological additive, 0-2 parts of organic amine and deionized water; the component A is prepared from the following components in parts by weight: 50-60 parts of cosolvent, 4-6 parts of metal anticorrosion auxiliary agent, 2-4 parts of organic amine, 30 parts of aluminum powder and 8 parts of wetting dispersant. The invention achieves the purposes of meeting the use requirement in a water-based paint system, prolonging the service cycle of the paint and simultaneously meeting other performance indexes under the condition of not reducing the self glossiness, metallic feeling and covering power of the aluminum powder by carrying out surface treatment on the oily aluminum powder and using different surface passivation and wrapping technologies.

Description

Passivation treatment product of solvent type aluminum paste

Technical Field

The invention relates to the technical field of coatings, in particular to a passivation treatment product of solvent type aluminum paste.

Background

In recent years, China has replaced the United states and becomes the first major automobile producing, selling and exporting country in the world. The coating of the automobile and parts thereof plays roles in decorating and protecting the automobile, and is one of links with highest energy consumption and most three wastes in the automobile manufacturing process. With the enhancement of environmental awareness, transformation and upgrade of the coating industry and the drive of legal regulations, the water-based coating which can effectively reduce coating public nuisance and has small volatile organic compound pollution is valued and applied by various coating enterprises.

The water-based paint is a paint using water as a solvent or a dispersion medium, and includes a water-soluble paint, a water-reducible paint and a water-dispersible paint.

Compared with the traditional solvent-based coating, the water-based coating has the following advantages:

firstly, water is used as a main solvent, so that a large amount of petroleum resources are saved;

secondly, the fire hazard during transportation, storage and construction is eliminated;

and thirdly, the pollution to the atmosphere is reduced. The organic solvent (accounting for the coating) in the general water-based coating is between 0 percent and 15 percent, and has obvious effect of reducing organic pollutants in the atmosphere;

fourthly, the coating tool can be cleaned by water, and the consumption of cleaning solvent is greatly reduced.

Although the water paint has many advantages and development prospects, as the aluminum powder paint widely used in automobile coating, the paint performance is seriously affected because common aluminum powder reacts with water in a water environment.

There are some methods for solving the instability of the water-based aluminum powder coating by surface treatment of aluminum powder in the market:

the water-based aluminum paste with the best quality in the market is coated with silicon dioxide, and the surface of aluminum powder is coated with a compact silicon dioxide layer, so that the effect of well isolating the reaction between the surface of metal aluminum and water can be achieved. The disadvantages are that it is expensive and affects the metallic effect of the finished paint to some extent due to the difference in refractive index between silica and paint resin.

Chinese patent application 201611257684.9 added untreated aluminum powder directly into a specific aqueous coating system to improve storage stability. However, the aluminum powder prepared by the method has no protection of any additive, can not meet the storage requirement of normal water-based paint at all, can be prepared and used immediately, and has no mass production.

And (3) passivating the aqueous aluminum paste by adopting an auxiliary agent: however, since this technique is not yet very mature, there still occurs a problem that adhesion is problematic when it is used in some aqueous resin systems, or aluminum powder is liable to react with water to generate gas. For example, application No. 201310450458.2, the water removal technology of adding the moisture-proof auxiliary agent is adopted, so that the oxidation problem in the storage process of the aluminum powder can be reduced to a certain extent. However, the aluminum powder modified by the technology can only prolong the storage time of the aluminum powder and cannot be directly used in the water-based paint. For another example, as application No. 201310253564.1, an assistant containing phosphate ester and hydroxyl acrylate phosphate ester is used for wrapping, so that the assistant has strong anchoring and adsorption effects on aluminum powder, but an initiator used in the preparation process of the assistant has strong oxidation effect, and partial residues can cause accelerated oxidation of the aluminum powder, so that the assistant cannot be applied to a part of water-based paint systems.

Disclosure of Invention

The invention provides a solvent type aluminum paste passivation treatment product, which meets the use requirement in a water-based paint system, prolongs the service cycle of paint and simultaneously meets other performance indexes under the condition of not reducing the self glossiness, metallic feeling and covering power of aluminum powder by performing surface treatment on oily aluminum powder and using a surface passivation and wrapping technology different from the prior art.

The technical scheme of the invention is as follows:

a passivation treatment product of solvent type aluminum paste is prepared from the following components in parts by weight:

the component A is prepared from the following components in parts by weight:

in the component A, the metal anticorrosion auxiliary agent can be separated out on the surface of the aluminum powder under the condition that the pH value is adjusted to be slightly alkaline, and the effect of effectively isolating the direct contact between the aluminum powder and water is achieved. In addition, the inventor also finds that the addition proportion, the addition mode and the pH value adjusting end point of the metal anticorrosion auxiliary agent in the formula all influence the effective protection time of the aluminum powder after the final aluminum powder treatment and the compatibility of the aluminum powder with the whole resin system.

In a preferred embodiment, the metal anticorrosion auxiliary agent is selected from one or more of aminocarboxylate, aliphatic metal phosphosilicate and aromatic metal phosphosilicate.

In a preferred embodiment, the co-solvent is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether or ethylene glycol ethyl ether.

The aluminum powder is a non-wrapping type aluminum powder which is sold in the market and is suitable for common solvent-based paint, and the solid content is 65%.

The wetting dispersant is selected from one or more of polyether modified polyester, polyether derivative and polyacrylic acid derivative.

In a preferred embodiment, the hydroxyl value of the aqueous acrylic resin is 0%.

In a preferred embodiment, the organic amine is selected from one or more of triethanolamine, dimethylaminoethanol or 2-amino-2-methyl-1-propanol.

In a preferred embodiment, the substrate wetting agent is one or more of silicone surfactants.

In a preferred embodiment, the defoaming agent is selected from one or more of simethicone, polyether modified silicon and specially modified polysiloxane.

In a preferred embodiment, the rheological aid is selected from one or more of polyurethanes or associated alkali swelling types.

A preparation method of a passivation treatment product of the solvent type aluminum paste comprises the following steps:

preparation of component A:

putting the cosolvent into a container, adding the metal anticorrosion auxiliary agent under slow stirring, uniformly dispersing, adding organic amine to adjust the pH value to 9, adding aluminum powder, stirring at 500rpm for 30min, standing at room temperature of 20-25 ℃ for 16h, adding the wetting dispersant, and stirring at 500rpm for 20 min;

the preparation of the passivation treatment product of the solvent type aluminum paste comprises the following steps:

putting the water-based acrylic resin into a container, adding the cosolvent and the component A while stirring, stirring at medium speed for 30min, adding the substrate wetting agent and the defoaming agent, dispersing at medium speed for 30min, adding the rheological additive and the deionized water to adjust the viscosity, and simultaneously adding the organic amine to adjust the pH value to 8Stirring quickly for 15min, and standing at room temperature of 20-25 ℃ for 16 hours; adjusting the pH value to 8 by using organic amine again, and adjusting the viscosity by using a rheological additive or deionized water; filtering with 80 mesh sieve, and packaging. The viscosity of the obtained product is as follows: 60s (DIN 4#/20 ℃), solid content: 25%, density: 1.02g/cm³。

A construction method of a passivation treatment product of the solvent type aluminum paste comprises the following steps:

adding deionized water into the solvent type aluminum paste passivation treatment product according to the requirement, adjusting the viscosity of the solvent type aluminum paste passivation treatment product to be sprayable, spraying the solvent type aluminum paste passivation treatment product onto a glass substrate by using a 1-1.5mm caliber air spray gun or a rotary cup spray gun, wherein the film thickness is 10-15 mu m, leveling is carried out at the temperature of 20-25 ℃ for 5-10min, and baking is carried out at the temperature of 80-85 ℃ for 30 min.

Compared with the prior art, the invention has the following beneficial effects:

the passivation treatment product of the solvent type aluminum paste disclosed by the invention has the advantages that through surface treatment of oily aluminum powder, and by using a surface passivation and wrapping technology different from the prior art, the use requirement in a water-based paint system is met under the condition that the glossiness, the metallic feeling and the covering power of the aluminum powder are not reduced, the service cycle of the paint is prolonged, and other performance indexes are met.

The product is used as a low-cost substitute of the water-based aluminum powder coated by silicon dioxide, and has the effect of effectively reducing the cost of the water-based aluminum paint.

Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.

Drawings

FIGS. 1a and 1b are views of an experimental apparatus for flatulence in example 2 of the present invention;

FIG. 2 is a graph showing the results of the flatulence test in example 2 of the present invention.

Detailed Description

The invention provides a passivation treatment product of solvent type aluminum paste.

In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.

Example 1

Passivation samples # 1, # 2, # 3 of solvent-based aluminum pastes were prepared according to the formulation of table 1 below and according to the following preparation method:

preparation of component A:

putting the cosolvent into a container, adding the metal anticorrosion auxiliary agent under slow stirring, uniformly dispersing, adding organic amine to adjust the pH value to 9, adding aluminum powder, stirring at 500rpm for 30min, standing at room temperature of 20-25 ℃ for 16h, adding the wetting dispersant, and stirring at 500rpm for 20 min.

putting the water-based acrylic resin into a container, adding the cosolvent and the component A while stirring, stirring at medium speed for 30min, adding the substrate wetting agent and the defoaming agent, dispersing at medium speed for 30min, adding the rheological additive and the deionized water to adjust the viscosity, adding the organic amine to adjust the pH value to 8, stirring at medium speed for 15min, and standing at room temperature of 20-25 ℃ for 16 hours; adjusting the pH value to 8 by using organic amine again, and adjusting the viscosity by using a rheological additive or deionized water; filtering with 80 mesh sieve, and packaging.

TABLE 1

Samples # 1-3 demonstrate the effect of different amounts of metal corrosion inhibitor additives on the appearance of finished paint films made from the treated aluminum pastes. It can be seen that 8 parts by weight of the metal corrosion inhibitor additive can cause abnormal particles in the aluminum powder paint, and the aluminum powder paint cannot be adopted. Therefore, the subsequent examples assume a suitable weight range of 4 to 6 parts by weight of the metal corrosion inhibitor additive.

Example 2

This example first produced various compositions A (Experimental Nos. A1-A13) using different amounts of the metal corrosion inhibitors listed in Table 2, adjusting the pH, and allowing to stand for different periods of time. Component a was prepared in the same manner as in example 1.

TABLE 2

The above-mentioned components A in various states were prepared into components B in different states (component A test numbers A1# -A13# correspond to component B test numbers B1# -B13#, respectively) according to the preparation methods of examples, as shown in Table 3.

TABLE 3

Experiment number	B1#	B2#	B4#	B5#	B6#	B7#	B8#	B9#	B10#	B11#	B12#	B13#
													Water-based acrylic resin	40	40	40	40	40	40	40	40	40	40	40	40
Ethylene glycol butyl ether	5	5	5	5	5	5	5	5	5	5	5	5
													Component A	20	20	20	20	20	20	20	20	20	20	20	20
Organosilicon substrate wetting agent	1	1	1	1	1	1	1	1	1	1	1	1
													Polyether modified silicon type defoaming agent	1	1	1	1	1	1	1	1	1	1	1	1
Rheological assistant for polyurethanes	5	5	5	5	5	5	5	5	5	5	5	5
													Triethanolamine	1	1	1.5	1.5	1	1	1.5	1.5	1	1	1.5	1.5
Deionized water	27	27	26.5	26.5	27	27	26.5	26.5	27	27	26.5	26.5
													Appearance of the product	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste	Good taste
Adhesion force	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified	Qualified

Table 2 demonstrates that the above examples of the invention, stringent 1-13, meet the requirements for both appearance and adhesion.

Samples # 1-13 above were used to evaluate the effect of aluminum paste pH and the time of standing before aluminum paste was added to the paint on the flatulence of the finished paint film and the finished paint. The less gas generated in a certain time in the flatulence test indicates that the better the passivation treatment effect.

FIG. 1 shows the apparatus for carrying out the flatulence test in this example. The method of the flatulence test is as follows: 200 g of the coating are placed in an erlenmeyer flask and left to stand in a water bath at 40 ℃. The gas generated after the reaction of the aluminum powder surface and water enters the inverted burette and the liquid (usually water) therein is discharged, and the reading is displayed. During testing, compared with the paint without the added aluminum powder, the data obtained after the co-solvent and water are heated and the gas generation amount caused by volatilization is removed is valid data.

FIG. 2 is a graph showing the results of the flatulence test of each sample in this example. The experimental data of fig. 2 show that, during passivation treatment of the aluminum paste for preparing the component a, setting of the pH value has a certain influence on the passivation effect, and the results are good when the pH is 8-9. The standing time after the addition of the auxiliary agent during the passivation of the aluminum paste plays a decisive role in the final effect, and 16h is a more reasonable time. The addition amount of the metal anti-corrosion additive is between 13 and 20 percent relative to the supplied mass of the aluminum powder.

Example 3

This example uses an aqueous aluminum powder dispersion as a control.

Preparation of aluminum powder dispersion A1:

mixing 30 g of oily aluminum powder (selected from German Eckart, particle size of 13 mu m, silver round) and 50 g of ethylene glycol butyl ether, soaking for half an hour, adding 6 parts of metal anti-corrosion auxiliary agent aromatic metal phosphosilicate under moderate-speed stirring, adding 8 g of polyether derivative type wetting dispersant after stirring for half an hour, adjusting the pH value to 9 by using triethanolamine, continuing stirring for half an hour, and standing for 16 hours at normal temperature.

Preparation of aqueous aluminum powder dispersion A2:

using 30 g of SiO₂Coated aqueous aluminum powder (selected from Eckart, Germany, particle size 13 μm, silver round) as a control, was mixed with 50 g butyl cellosolve, soaked for half an hour, stirred at moderate speedAdding 8 g of polyether derivative type wetting dispersant, adjusting the pH value to 9, stirring for half an hour, and standing.

Coating examples are prepared as shown in Table 4 below, C4-C6 are used as comparative samples of waterborne aluminum powder to C1-C3 metal corrosion inhibitor assistant passivated aluminum powder.

TABLE 4

Components	C1	C2	C3	C4	C5	C6
							NeoCryl XK-205	40	—	—	40	—	—
RESYDROLAN 6481W	—	40	—	—	40	—
							Picassian PU-406	—	—	50	—	—	50
Deionized water	27.5	29.2	20.4	27.5	29.2	20.4
							Ethylene glycol butyl ether	5	5	3	5	5	3
Organosilicon substrate wetting agent	0.5	1	1	0.5	1	1
							Polyether modified silicon type defoaming agent	0.5	0.3	0.3	0.5	0.3	0.3
Rheological assistant for polyurethanes	5	3.5	4	5	3.5	4
							Aluminum powder dispersion A1	20	20	20	—	—	—
Aqueous aluminum powder dispersion A2	—	—	—	20	20	20
							Triethanolamine	1.5	1	1.3	1.5	1	1.3

Wherein NeoCryl XK-205 is a water-based acrylic resin from Tesmann, RESYDROL AN 6481W is a water-based polyester resin from Zhanxin, and Picassian PU-406 is a water-based polyurethane resin from Stahl.

The coating materials in the samples of the examples and the comparative samples are sprayed on test boards with the film thickness of 14-16 mu m through air spraying equipment, the test boards are leveled for 5 minutes at room temperature, then are baked for 30 minutes in an oven at 80 ℃, and are aged for 4 hours in the oven at 80 ℃ for testing.

The test results are given in table 5 below.

TABLE 5

As can be seen from the above tests:

1. the storage property test result shows that the aluminum powder passivated by the metal anticorrosion auxiliary agent has good stability in the water-based paint;

2. through comprehensive analysis of tests, aluminum powder passivated by metal anticorrosion auxiliary agent is used for SiO in water paint and on the market₂The coated aqueous aluminum powder has similar properties.

In conclusion, the passivating aluminum powder coating prepared by the method has the characteristics of simple construction mode, low cost and excellent performance, can replace low-end and medium-end waterborne aluminum powder in the market to a certain extent, partially solves the problem of high price of the waterborne aluminum powder in the current market, and can promote the whole industry to develop to the waterborne and environment-friendly properties.

In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.

Claims

1. A passivation treatment product of solvent type aluminum paste is characterized by being prepared from the following components in parts by weight:

the water-based acrylic resin (40) is,

0-5 parts of a cosolvent,

the components A are 15-20 parts by weight,

0.5-2 parts of substrate wetting agent,

0.5 to 2 portions of defoaming agent,

2-5 parts of a rheological additive,

0-2 parts of organic amine, namely,

supplementing the formula with deionized water;

the component A is prepared from the following components in parts by weight:

50-60 parts of a cosolvent,

4-6 parts of a metal anti-corrosion additive,

2-4 parts of organic amine,

the aluminum powder 30 is mixed with the aluminum powder,

a wetting dispersant 8;

wherein the metal anticorrosion auxiliary agent is aminocarboxylate.

2. The passivation product of solvent-borne aluminum pastes according to claim 1, wherein the co-solvent is selected from one or more of ethylene glycol butyl ether, diethylene glycol butyl ether or ethylene glycol ethyl ether.

3. The passivation product of a solvent-borne aluminum paste according to claim 1, wherein the aluminum powder is a commercially available non-encapsulated aluminum powder suitable for use in a conventional solvent-borne coating, and has a solids content of 65%.

4. The passivation product of solvent-based aluminum paste according to claim 1, wherein the wetting dispersant is one or more selected from polyether derivatives and polyacrylic acid derivatives.

5. The passivation product of a solvent-borne aluminum paste according to claim 1, wherein the hydroxyl number of the water-borne acrylic resin is 0%.

6. The passivation product of solvent-based aluminum paste according to claim 1, wherein the organic amine is one or more selected from triethanolamine, dimethylaminoethanol, or 2-amino-2-methyl-1-propanol.

7. The passivation product of a solvent-borne aluminum paste according to claim 1, wherein the substrate wetting agent is a silicone surfactant;

the defoaming agent is selected from one or more of dimethyl silicone oil and polyether modified silicon;

the rheological additive is selected from one or more of polyurethanes or associated alkali swelling types.

8. A method for preparing a passivation treatment product of the solvent-based aluminum paste according to any one of claims 1 to 7, comprising the steps of:

preparation of component A:

putting the water-based acrylic resin into a container, adding the cosolvent and the component A while stirring, stirring at medium speed for 30min, adding the substrate wetting agent and the defoaming agent, dispersing at medium speed for 30min, adding the rheological additive and the deionized water to adjust the viscosity, adding the organic amine to adjust the pH value to 8, stirring at medium speed for 15min, and standing at room temperature of 20-25 ℃ for 16 hours; adjusting the pH value to 8-9 by using organic amine again, and adjusting the viscosity by using a rheological additive or deionized water; filtering with 80 mesh sieve, and packaging.

9. A method for constructing a passivation product of the solvent-based aluminum paste according to any one of claims 1 to 7, comprising the steps of:

deionized water is added into the passivation treatment product of the solvent type aluminum paste according to the requirement, the spraying viscosity is adjusted to be spraying viscosity, an air spray gun with the caliber of 1-1.5mm or a rotary cup spray gun is used for spraying the passivation treatment product on a glass substrate, the film thickness is 10-15 mu m, the passivation treatment product is leveled for 5-10min at the temperature of 20-25 ℃, and the passivation treatment product is baked for 30min at the temperature of 80-85 ℃.