CN100554352C - The preparation method of the nanometer aqueous automobile paint of scrape resistant - Google Patents

Abstract

The present invention relates to the preparation method of the water nano car paint that a kind of scrape resistant, anti-stone hit, belong to chemistry painting industry fabricating technology field.The present invention combines the environmental protection characteristic of the low VOC of water-borne coatings with the small-size effect of nanoparticle, the character of surface effects, prepare the water-borne coatings of scrape resistant.Water-borne coatings of the present invention has following composition and weight percent: coating film forming base-material 60～70%, nano-powder 5～15%, aqueous solvent 20～25%, auxiliary agent 0.5～1.0%; Auxiliary agent has thickening material, dispersion agent, defoamer, film coalescence aid; Adopt linking agent in addition, its consumption is benchmark with the nano-composite emulsion, and its ratio is 0.9: 1～1: 1; Linking agent is mainly the chemical substance of trimeric cyanamide system.Index is hindered in the scratch resistance of paint coatings can reach for 96～99% (representing with gloss retention).

Description

The preparation method of the nanometer aqueous automobile paint of scrape resistant

Technical field

The present invention relates to a kind of preparation method of nanometer aqueous automobile paint of scrape resistant, belong to chemistry painting industry fabricating technology field.

Background technology

Body of a motor car scribbles one deck paint film, plays protection and decorative effect, but during use, vehicle body regular meeting and hard objects contact-impact.For example automobile is subjected to the bump of stone chippings on the road in the process of moving; When scrubbing vehicle body, impurity washing away in the water to paint film; Be subjected to the scratch of objects such as metal, branch in addition, thereby influenced the attractive in appearance of body of a motor car.

Simultaneously, along with car paint towards environmental protectionization, the water-borne coatings with low VOC becomes one of main flow of following car paint.Therefore, exploitation has the important topic that water-borne coatings that excellent, damage resistant, anti-stone hit becomes the car paint scientific research personnel.

Have quantum effect and the surface effects that big specific surface area and very strong interfacial interaction produce by dried nano-powder, nano material is not only shown be different from general macroscopical performance of composites; Also may have characteristic performance and function that stock blend does not possess.Nano material is used in the coating, can improve the mechanical property of paint film, can keep the higher transparency simultaneously.

The higher car paint of development scratch resistance, traditional method is the development of new resin.According to the literature, people such as U.S. Van Der Linde once developed the higher car paint of a kind of scratch resistance, and this coating is to be filmogen with the vibrin, mixes varnish and colored paint, and its scoring resistance is 89～95%.But its manufacturing cost is higher, and the performance biography does not reach desirable requirement.

Summary of the invention

The objective of the invention is to overcome the defective of existing automotive coating, water nano car paint that a kind of scrape resistant, anti-stone hits and preparation method thereof is provided.

The nanometer aqueous automobile paint of a kind of scrape resistant of the present invention is characterized in that this water-borne coatings has following composition and weight percent:

Coating film forming base-material, 60～70%; Include urethane acrylate, epoxy acrylate, urethane and polyester, select wherein any;

Nano-powder, 5～15%; Include silicon-dioxide, titanium dioxide, barium sulfate, barite, lime carbonate and aluminum oxide, select wherein any; The particle diameter of nano-powder is 20～80nm;

Aqueous solvent, 20～25%; Be deionized water;

Auxiliary agent, 0.5～1.0%; Comprise thickening material, dispersion agent, defoamer, film coalescence aid; Select wherein more than three kinds or three kinds;

Make nano-composite emulsion by above component;

Linking agent is a benchmark with the nano-composite emulsion that makes, and the part by weight of its add-on is 0.9: 1～1: 1; Linking agent includes hexa methoxy melamine methylol, butylation trimeric cyanamide, isobutyl trimeric cyanamide, blended methylates and the butylation trimeric cyanamide; Select wherein any.

The preparation method of the nanometer aqueous automobile paint of a kind of scrape resistant of the present invention is characterized in that having following technological process and step:

A. by the ready raw material of above-mentioned formula rate, at first nano-powder is put into container, add dispersion agent, part defoamer and certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards;

B. above-mentioned nano-powder dispersion liquid slurry is incorporated in the resinous polymer of coating film forming base-material, the defoamer that adds film coalescence aid and remainder subsequently mixes, and disperses 30 minutes with homogenizer again, makes nano-composite emulsion;

C. then linking agent is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.9: 1～1: 1; Under 25～30 ℃ of temperature, mix, and add remaining solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Advantage of the present invention is: its VOC content of the raw material of employing is low, meets the environmental requirement of car paint, and is water-borne coatings, and is easy to use; The car paint that the inventive method makes has good scratch resistance, anti-stone hits performance; Its scratch resistance or scoring resistance are represented with protecting the light rate, can be reached 96～99%.

Embodiment

After now specific embodiments of the invention being described in.

Embodiment 1

The compositing formula of Xuan Ding car paint at first, wherein: coating film forming base-material urethane acrylate consumption is 70%, and the nano-powder amount of titanium is 8%, and the solvent deionized water consumption is 21%, and auxiliary dosage is 1%.

The titanium dioxide that is averaged particle diameter 40nm is put in the container, name is gone into dispersion agent TENLO 70, defoamer polydimethylsiloxane subsequently, and the certain amount of solvent deionized water carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards; This nano-powder dispersion liquid slurry is incorporated in the coating film forming base-material urethane acrylate, the defoamer polydimethylsiloxane that adds film coalescence aid Texanol alcohol ester and part remainder subsequently mixes, disperseed again 30 minutes with homogenizer, make nano-composite emulsion; Then linking agent hexa methoxy melamine methylol is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.01: 1; Under 28 ℃ of temperature, mix, and add remaining partial solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Made coating evenly is sprayed on the tinplate, and being coated with thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets the precoating plate Sample A, gives over to benchmark test.

Embodiment 2

Selected system component prescription is substantially with above-mentioned embodiment 1 in the present embodiment.But nano-powder adopts the titanium dioxide of 60nm, and its consumption is 12wt%, and the consumption of film forming base-material urethane acrylate is 66wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step.

Final prepared coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets the precoating plate sample B, gives over to benchmark test.

Embodiment 3

The compositing formula of at first selected good car paint, wherein: coating film forming base-material urethane acrylate consumption is 70%, and nano-powder silicon-dioxide consumption is 8%, the solvent deionized water consumption is 21%, auxiliary dosage is 1%.

The silicon-dioxide that is averaged particle diameter 40nm is put in the container, add dispersion agent TENLO 70, defoamer polydimethylsiloxane, certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards; This nano-powder dispersion liquid slurry is incorporated in the coating film forming base-material urethane acrylate, the defoamer polydimethylsiloxane that adds film coalescence aid Texanol alcohol ester and part remainder subsequently mixes, disperseed again 30 minutes with homogenizer, make nano-composite emulsion; Then linking agent butylation melamine is added in the above-mentioned nano-composite emulsion that makes; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.91: 1; Under 28 ℃ of temperature, mix, and add surplus partial solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Made coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample C, gives over to benchmark test.

Embodiment 4

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the silicon-dioxide of 40nm, and its consumption is 12wt%, and the film forming base-material adopts epoxy acrylate, and its consumption is 66wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide, and the linking agent of adding and the part by weight of emulsion are 0.91: 1.

Finally make nanometer aqueous automobile paint.Obtained coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample D, gives over to benchmark test.

Embodiment 5

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barium sulfate of 50nm, and its consumption is 8%, and the film forming base-material adopts epoxy acrylate, and its consumption is 70wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, is 0.91: 1 but linking agent adopts isobutyl trimeric cyanamide, the linking agent of adding and the part by weight of emulsion.

Finally make nanometer aqueous automobile paint.Obtained coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample E, gives over to benchmark test.

Embodiment 6

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barite of 40nm, and its consumption is 10wt%, and the film forming base-material adopts epoxy acrylate, and its consumption is 68wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts the butylation trimeric cyanamide.

Finally make nanometer aqueous automobile paint.Make precoating plate sample F by above-mentioned with quadrat method, give over to benchmark test.

Embodiment 7

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barite of 60nm, and its consumption is 15wt%, and the film forming base-material adopts urethane, and its consumption is 63wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide.

Finally make nanometer aqueous automobile paint.Make precoating plate sample G by above-mentioned with quadrat method, give over to benchmark test.

Embodiment 8

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the aluminum oxide of 40nm, and its consumption is 11wt%, and the film forming base-material adopts polyester, and its consumption is 67wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts the hexa methoxy melamine methylol, and the linking agent of adding and the part by weight of emulsion are 1: 1.

Finally make nanometer aqueous automobile paint.Made coating is made precoating plate sample H by above-mentioned with quadrat method.

Embodiment 9

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the lime carbonate of 50nm, and its consumption is 11wt%, and the film forming base-material adopts polyester, and its consumption is 67wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide, and the linking agent of adding and the part by weight of emulsion are 0.91: 1.

Finally make nanometer aqueous automobile paint.Made coating is made precoating plate sample I by above-mentioned with quadrat method.

Benchmark test

1. do scratch resistance

On the Clear coating of sample board, be coated with Bon Ami abrasive material thin layer (this abrasive material is by the supply of Faultloss Starch/BonAmi company), put exceedingly beautiful felt fingerstall subsequently, prop up the contact sample board, come and go 10 times wiping examination, to test its scratch situation.Scratch resistance is that promptly gloss guarantor percentage is represented by the regional relative not relative ratios of the glossiness at 20 ° of visual angles in scratch zone of the scratch of measuring paint sheet.

2. wet scratch resistance

Adopt above-mentioned similar program, just substitute Bon Ami abrasive material with wet oxidation aluminium slurry.This aluminum oxide slurry is made up of AMP 95% aqueous solution and 7 parts of aluminum oxide (120# grit) of 294 parts of deionized waters, 21 parts of ASE-60 thickening materials, 25 parts of amino methyl propyl alcohol.

Test result sees the following form 1.

The performance evaluation result of each coating model of table 1

Test event Conventional ??A ??B ??C ??D ??E ??F ??G ??H ??I Do scratch resistance (gloss retention %) ??82％ ??97％ ??93％ ??94％ ??92％ ??93％ ??93％ ??90％ ??88％ ??89％ Wet scratch resistance (gloss retention %) ??71％ ??83％ ??79％ ??81％ ??78％ ??79％ ??80％ ??77％ ??75％ ??76％ 20 ° of gloss ??85 ??98 ??94 ??95 ??94 ??94 ??95 ??93 ??92 ??92

By experimental result as seen, compare, hit performance through the scoring resistance of nano-material modified aqueous clear coating coating and anti-stone and be significantly increased with the conventional paint coatings that does not add the nano powder body.

Claims (2)

1. the nanometer aqueous automobile paint of a scrape resistant is characterized in that this water-borne coatings has following composition and weight percent:

Coating film forming base-material, 60～70%; Include urethane acrylate, epoxy acrylate, urethane and polyester, select wherein any;

Nano-powder, 5～15%; Include silicon-dioxide, titanium dioxide, barium sulfate, barite, lime carbonate and aluminum oxide, select wherein any; The particle diameter of nano-powder is 20～80nm;

Aqueous solvent, 20～25%; Be deionized water;

Auxiliary agent, 0.5～1.0%; Comprise thickening material, dispersion agent, defoamer, film coalescence aid; Select wherein more than three kinds or three kinds;

Make nano-composite emulsion by above component;

Linking agent is a benchmark with the nano-composite emulsion that makes, and the part by weight of its add-on is 0.9: 1～1: 1;

Linking agent includes hexa methoxy melamine methylol, butylation trimeric cyanamide, isobutyl trimeric cyanamide, blended methylates and the butylation trimeric cyanamide; Select wherein any.

2. the preparation method of the nanometer aqueous automobile paint of the described a kind of scrape resistant of claim 1 is characterized in that having following technological process and step:

A. by the ready raw material of above-mentioned formula rate, at first nano-powder is put into container, add dispersion agent, part defoamer and certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards;

B. above-mentioned nano-powder dispersion liquid slurry is incorporated in the resinous polymer of coating film forming base-material, the defoamer that adds film coalescence aid and remainder subsequently mixes, and disperses 30 minutes with homogenizer again, makes nano-composite emulsion;

C. then linking agent is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.9: 1～1: 1; Under 25～30 ℃ of temperature, mix, and add remaining solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.