CN103555164B - Acrylic modified alkyd automobile finish that a kind of quick-drying salt fog resistance is good and preparation method thereof - Google Patents

Abstract

The invention provides the acrylic modified alkyd automobile finish that a kind of quick-drying salt fog resistance is good, this automobile finish is by LH-159 resin 34-36,40%HPE resin liquid 23-25, carbon black 2-3, dispersion agent 0.3-0.5, composite phosphate rust-stabilising pigment 4-7, potassium aluminum silicate 3-6, process white 16-18, anti-settling agent 1-3, low-molecular-weight epoxy resin 0.5-1, stablizer 0.5-1, siccative 0.2-0.3, aromatic solvent 6-9, modified filler 5-6, is mixed with and forms.Automobile finish of the present invention has the good feature of quick-drying, salt fog resistance.

Description

Acrylic modified alkyd automobile finish that a kind of quick-drying salt fog resistance is good and preparation method thereof

Technical field:

The present invention relates to a kind of paint, be specifically related to good acrylic modified alkyd automobile finish of a kind of quick-drying salt fog resistance and preparation method thereof.

Background technology:

Along with the development of Domestic Automotive Industry, also more and more higher to the requirement of goods vehicle vehicle bridge application.On the one hand, automotive axle is disposable application after having combined, and substrate treatment is not in place, thus requires that the coating used has the service performance of low prepared surface; On the other hand, some subassemblies (as plastic component) on automotive axle, can not high bake, and is easy to mark and carrying after rolling off the production line, and thus requires that the rate of drying of film is fast; 3rd, require that film adhesive is good, salt fog resistance is good.The vinylformic acid one high chlorination type in the past adopted, alkyd one high chlorination type or other is similar, be binary composite membrane-forming base-material.The acrylic modified alkyd automobile finish that a kind of quick-drying salt fog resistance of the present invention is good, have employed acrylic acid synthesizing modification long oil alkyd, aliphatic hydrocarbon long-chain in this resin structure and high-performance HCPE (HPE resin), have good compatibility, and plasticization effect is good.Film performance had both possessed the snappiness of long oil alkyd, water tolerance and easy working characteristic, possess again vinylformic acid to protect light, protect the characteristic of look, anti-powdering, also there is the excellent adhesive attraction and salt fog resistance etc. of HCPE simultaneously, this organic assembling, can learn from other's strong points to offset one's weaknesses in performance.

Goal of the invention:

The invention provides good acrylic modified alkyd automobile finish of a kind of quick-drying salt fog resistance and preparation method thereof, automobile finish film of the present invention had both possessed the snappiness of long oil alkyd, water tolerance and easy working characteristic, possess again vinylformic acid to protect light, protect the characteristic of look, anti-powdering, also there is the excellent adhesive attraction and salt fog resistance etc. of HCPE simultaneously, this organic assembling, can learn from other's strong points to offset one's weaknesses in performance.

The technical solution used in the present invention is as follows for achieving the above object:

The acrylic modified alkyd automobile finish that quick-drying salt fog resistance is good, it is characterized in that, it is made up of the component of following weight part:

LH-159 resin 34-36,40% high-performance HCPE liquid 23-25, pigment 2-3, dispersion agent 0.3-0.5, composite phosphate rust-stabilising pigment 4-7, potassium aluminum silicate 3-6, process white 16-18, anti-settling agent 1-3, E-51 epoxy resin 0.5-1, stablizer 0.5-1, siccative 0.2-0.3, aromatic solvent 6-9, modified filler 5-6

The preparation method of described LH-159 resin is:

(1) following component is taken by weight:

Methyl methacrylate 7-9, methacrylic acid 0.2-0.4, benzoyl peroxide 0.1-0.2, C5-9 low-carbon (LC) synthetic fatty acid 10-12, tung oil 13-15, tetramethylolmethane 6-8, MALEIC ANHYDRIDE 4-5, phthalic anhydride 5-7, dimethylbenzene 48-52,

(2) preparation of acrylic ester polymer

A, first by the methyl methacrylate of formula ratio, methacrylic acid and 80% initiator benzoyl peroxide to be made into compound A for subsequent use, remaining initiator benzoyl peroxide is dissolved in dimethylbenzene, and obtained benzoyl peroxide xylene solution B is for subsequent use;

B, add dimethylbenzene in a kettle., be warming up to 120 DEG C, start to drip compound A, and at the uniform velocity heat up with the speed of 1 DEG C/6 minutes, the highlyest be warming up to 125 DEG C, intensification limit, limit drips compound A, and control time for adding is 2.5-3.5h, at 125 DEG C of insulation 1.5h after dripping off, drip initiator benzoyl peroxide xylene solution B again, drip off in 2h, be at the uniform velocity warming up to 130 DEG C simultaneously and maintain more than 2 hours, prepare acrylic ester polymer;

(3) acrylic acid modified long oil alkyd

By low-carbon (LC) synthetic fatty acid, tung oil adds reactor, tetramethylolmethane is added under stirring, be warming up to 220-240 DEG C, insulation alcoholysis 1-2h, then 180-200 DEG C is cooled to, stop stirring, add MALEIC ANHYDRIDE, after its fusing, open and stir, add phthalic anhydride and backflow dimethylbenzene, be warming up to 190-210 DEG C, after refuxing esterification 2-3h, be cooled to 125-135 DEG C again, add acrylic ester polymer, add backflow, prevent temperature from raising, insulation backflow 2.5-3.5h, when transformation efficiency reaches more than 97%, cooling, filter, discharging obtains the LH-159 resin of solids content 50%-52%,

Described modified filler is prepared by following method and obtains: a. takes off the raw material of row weight part: kaolin 100-150, calcium carbonate 120-130, zeolite 10-12, nano-sized carbon 1-2, tungstic oxide 1-2, lanthanum trioxide 2-3, Peppermint essential oil 2-3, Sodium peroxoborate 1-2, aluminum oxide 2-3, precipitator method barium sulfate 30-34, tea-polyphenol 3-4, triethyl citrate 1-2, titanate coupling agent TMC-TTS4-6, jade powder 1-2;

B, kaolin, calcium carbonate, zeolite are calcined 4-5h at 450-480 DEG C, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, add the hydrochloric acid soln of 12-15%, adjustment pH value is 4-5, ageing 10-15 hour, and repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, dry and obtain filler powder;

C, above-mentioned gained powder to be mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, to obtain final product.

The acrylic modified alkyd automobile finish that described quick-drying salt fog resistance is good, is characterized in that: described pigment is selected from one or more in carbon black, titanium dioxide, chrome yellow, molybdenum red, ferric oxide series, phthalein mountain valley with clumps of trees and bamboo series, toluidine maroon, talcum powder, calcium carbonate, barium sulfate, silicon-dioxide.

The production method of the acrylic modified alkyd automobile finish that described quick-drying salt fog resistance is good, is characterized in that, comprise the following steps:

(1) by formula rate, high-performance HCPE xylene soluble is filtered, add LH-159 resin, dispersion agent, pigment, the filler of 20-30% formula ratio more successively, with 2000-2600r/min rotating speed after high speed dispersion 1-1.5 hour, then filter with 80 eye mesh screens;

(2) material filtered enters sand mill and is ground to fineness control≤30u discharging, requires outlet mass temperatures≤60 DEG C;

(3) material that mesh-of-grind is qualified adds tune and converts in still, and adds the rest materials in formula, stirs evenly with the middling speed of 100-200r/min;

(4) after stirring evenly, with aromatic solvent adjustment viscosity to 90-120(S)/be coated with-4, filter with 200 order vibratory screening apparatuss, pack.

The theoretical foundation of invention:

(1) determination of acrylic acid modified long oil alkyd (hereinafter referred to as LH-159 resin):

In LH-159 resin, what the present invention adopted is that esterification prepares acrylic acid modified long oil alkyd.First the acrylic resin of anamorphic zone carboxyl, then adds this functional acrylic resins to prepare LH-159 resin in Synolac preparation process; Secondly, general acrylic acid modified alkyd resin and HCPE compatibility bad, painting can not be used for, the present invention selects C5-9 low-carbon (LC) synthetic fatty acid, tung oil as the properties-correcting agent of tetramethylolmethane-phthalic anhydride system, and usage quantity can be enough large, this aliphatic hydrocarbon long-chain, not only to system, there is plastification, and provide the fine compatibility of system and the wettability to color stuffing, conjugated double bond in tung oil, in the esterification process in later stage, also there is polymerization to a certain extent with double bond residual in acrylate resin.Make, in this resin segment, to give the good intermiscibility of this resin, pigment wettability, sticking power, hydrophobic nature and photostabilization.

(2) determination of paint formula is become:

Acrylic modified alkyd automobile finish, require that salt fog resistance is good, strong adhesion, dryness is fast, be easy to construction, determine the solids ratios 1.8: 1 of LH-159 and HPE resin, this ratio not only ensure that construction requirement, and ensure that the mechanical property that film is good and salt fog resistance.

In automobile finish of the present invention, apply special rust-stabilising pigment-composite phosphate rust-stabilising pigment, it has dual antirust function---namely chelating protection and physics antirust, physics is antirust is the general character that general rust-stabilising pigment has, it leans on the inertia of rust-stabilising pigment self and impermeability to come antirust, and this special pigment is except having above-mentioned functions, can also and polymer and steel structure chelated surface, make polymeric membrane finer and close, impervious better, thus reduction water, oxygen, the seepage force of low-molecular material confrontation paint film, improve erosion resistance and the oil-proofness of paint film, strengthen the sticking power of paint film, water tolerance and oil-proofness.The application of potassium aluminum silicate, shows the unexistent surface effects of conventional fillers and comprehensive physicochemical property.In lacquering of the present invention, add siccative, cross-linking density is strengthened further.

In automobile finish production technique of the present invention, LH-159 resin is the critical material of painting, the temperature of resins synthesis controls, the control of reinforced at the uniform velocity property is the key point of resin property quality, effectively controls to make the molecular weight distribution of synthetic resins narrower, thus obtains desirable paint film; In sand milling operation, high-performance sand grinder grinding 2-3 road, fineness can reach 30 below μ; Filter progress carries out last purification to product, to provide gratifying visual appearance.

Advantage of the present invention:

1, the present invention adopts acrylic ester polymer modification long oil alkyd, solves the compatibility with HPE resin and the plastification of film; Solve the problem that the dryness of film is slow, and the contradiction that low prepared surface ground not easily adheres to.

2, acrylic modified alkyd automobile finish of the present invention, salt spray resistance is excellent, shows through user's life-time service: the resistance to neutral salt spray of paint film reaches 150h and not containing heavy metal, low Hazardous, belongs to environmentally friendly machine.

Embodiment

One, the preparation LH-159 resin raw material of embodiment 1 acrylic acid modified alkyd resin (LH-159 resin raw material)

1.1 material compositions

Methyl methacrylate (MMA), methacrylic acid (AA), benzoyl peroxide (B, P, O), C5-9 low-carbon (LC) synthetic fatty acid), tung oil, tetramethylolmethane, MALEIC ANHYDRIDE, phthalic anhydride, dimethylbenzene (XYL) is industrial goods.

The material component weight percent of 1.2LH-159 resin

1.3LH-159 resin manufacturing processes:

(1) preparation of acrylic ester polymer

A, first by the methyl methacrylate of formula ratio, methacrylic acid and 80% initiator benzoyl peroxide to be made into compound A for subsequent use, remaining initiator benzoyl peroxide is dissolved in dimethylbenzene, and obtained benzoyl peroxide xylene solution B is for subsequent use;

B, add dimethylbenzene in a kettle., be warming up to 120 DEG C, start to drip compound A, and at the uniform velocity heat up with the speed of 1 DEG C/6 minutes, the highlyest be warming up to 125 DEG C, intensification limit, limit drips compound A, and control time for adding is 2.5-3.5h, at 125 DEG C of insulation 1.5h after dripping off, drip initiator benzoyl peroxide xylene solution B again, drip off in 2h, be at the uniform velocity warming up to 130 DEG C simultaneously and maintain more than 2 hours, prepare acrylic ester polymer; (2) acrylic acid modified alkyd resin is prepared

Low-carbon (LC) synthetic fatty acid, tung oil are added reactor, add tetramethylolmethane under stirring, be warming up to 240 DEG C, insulation alcoholysis 1.5-2h, be cooled to 200 DEG C, stop stirring, add MALEIC ANHYDRIDE, after its fusing, open and stir, add phthalic anhydride and backflow dimethylbenzene, be warming up to 200 DEG C, refuxing esterification, after esterification 3h, be cooled to 130 DEG C, add acrylic ester polymer, add backflow, prevent temperature from raising, general insulation backflow 3h, when transformation efficiency reaches more than 97%, cooling, filter, LH-159 resin that discharging obtains solids content 50%-52%.

1.4LH-159 resin detected result

Project

Index

Assay

Color (number, Fe-Co method)≤	13	13
			Solids content %	51±2	51.2
Viscosity (being coated with-4), s	60-100	71
			Acid value mgKOH/g≤	12	9.6

The preparation of embodiment 2, lacquering black matte acrylic modified alkyd automobile finish

Main raw material(s)

2.1 material compositions

LH-159 resin, high-performance HCPE (HPE resin) prepared by embodiment 1, middle colour carbon black 3#, composite phosphate rust-stabilising pigment, potassium aluminum silicate, process white, modified filler, various auxiliary agent and aromatic solvent are industrial goods.

2.2 black matte acrylic modified alkyd automobile finishs each component weight (kg) are:

LH-159 resin 35,40%HPE resin liquid 24, carbon black 3, dispersion agent 0.4, composite phosphate rust-stabilising pigment 45, potassium aluminum silicate 4, process white 17, anti-settling agent 2, low-molecular-weight epoxy resin 0.6, UV light absorber 9440.6, siccative 0.2, aromatic solvent 8, modified filler 5

2.3 black matte acrylic modified alkyd automobile finish preparation technologies are:

(1) high-performance HCPE (HPE resin) is filtered by xylene soluble, then add part LH-159 resin and dispersion agent, pigment, filler high speed dispersion (2000-2600r/min) after 1 hour, filter with 80 eye mesh screens;

(2) material filtered enters sand mill circular grinding, outlet mass temperatures≤60 DEG C, fineness control≤30u.

(3) material that mesh-of-grind is qualified adds tune and converts in still, and adds remaining material, balance formula, and middling speed (100-200r/min) stirs evenly;

(4) after stirring evenly, with aromatic solvent adjustment viscosity to 90-120(S)/be coated with-4, filter with 200 order vibratory screening apparatuss, pack.

Wherein, modified filler is prepared by following method and obtains:

A, take off the raw material of row weight part: kaolin 120, calcium carbonate 125, zeolite 11, nano-sized carbon 1.5, tungstic oxide 1.5, lanthanum trioxide 2.5, Peppermint essential oil 2.5, Sodium peroxoborate 1.5, aluminum oxide 2.5, precipitator method barium sulfate 33, tea-polyphenol 3.5, triethyl citrate 1.5, titanate coupling agent TMC-TTS5, jade powder 1.5;

B, kaolin, calcium carbonate, zeolite are calcined 4-5h at 450-480 DEG C, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, add the hydrochloric acid soln of 12-15%, adjustment pH value is 4-5, ageing 10-15 hour, and repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, dry and obtain filler powder;

C, above-mentioned gained powder to be mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, to obtain final product.

2.4 black matte acrylic modified alkyd automobile finish detected results

Claims (3)

1. a drip-dry acrylic modified alkyd automobile finish, it is characterized in that, it is made up of the component of following weight part: LH-159 resin 34-36,40% HCPE liquid 23-25, pigment 2-3, dispersion agent 0.3-0.5, composite phosphate rust-stabilising pigment 4-7, potassium aluminum silicate 3-6, process white 16-18, anti-settling agent 1-3, E-51 epoxy resin 0.5-1, stablizer 0.5-1, siccative 0.2-0.3, aromatic solvent 6-9, modified filler 5-6;

The preparation method of described LH-159 resin is:

(1) following component is taken by weight: methyl methacrylate 7-9, methacrylic acid 0.2-0.4, benzoyl peroxide 0.1-0.2, C5-9 low-carbon (LC) synthetic fatty acid 10-12, tung oil 13-15, tetramethylolmethane 6-8, MALEIC ANHYDRIDE 4-5, phthalic anhydride 5-7, dimethylbenzene 48-52;

(2) preparation of acrylic ester polymer

A, first by the methyl methacrylate of formula ratio, methacrylic acid and 80% initiator benzoyl peroxide to be made into compound A for subsequent use, remaining initiator benzoyl peroxide is dissolved in dimethylbenzene, and obtained benzoyl peroxide xylene solution B is for subsequent use;

B, add dimethylbenzene in a kettle., be warming up to 120 DEG C, start to drip compound A, and at the uniform velocity heat up with the speed of 1 DEG C/6 minutes, be warming up to 125 DEG C, intensification limit, limit drips compound A, and control time for adding is 2.5-3.5h, at 125 DEG C of insulation 1.5h after dripping off, drip initiator benzoyl peroxide xylene solution B again, drip off in 2h, be at the uniform velocity warming up to 130 DEG C simultaneously and maintain more than 2 hours, prepare acrylic ester polymer;

(3) acrylic acid modified long oil alkyd is by low-carbon (LC) synthetic fatty acid, tung oil adds reactor, tetramethylolmethane is added under stirring, be warming up to 220-240 DEG C, insulation alcoholysis 1-2h, then 180-200 DEG C is cooled to, stop stirring, add MALEIC ANHYDRIDE, after its fusing, open and stir, add phthalic anhydride and backflow dimethylbenzene, be warming up to 190-210 DEG C, after refuxing esterification 2-3h, be cooled to 125-135 DEG C again, add acrylic ester polymer, add backflow, prevent temperature from raising, insulation backflow 2.5-3.5h, when transformation efficiency reaches more than 97%, cooling, filter, discharging obtains the LH-159 resin of solids content 50%-52%,

Described modified filler is prepared by following method and obtains:

A, take off the raw material of row weight part: kaolin 100-150, calcium carbonate 120-130, zeolite 10-12, nano-sized carbon 1-2, tungstic oxide 1-2, lanthanum trioxide 2-3, Peppermint essential oil 2-3, Sodium peroxoborate 1-2, aluminum oxide 2-3, process white 30-34, tea-polyphenol 3-4, triethyl citrate 1-2, titanate coupling agent TMC-TTS4-6, jade powder 1-2;

B, kaolin, calcium carbonate, zeolite are calcined 4-5h at 450-480 DEG C, be cooled to room temperature, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, add the hydrochloric acid soln of 12-15%, adjust ph is 4-5, ageing 10-15 hour, and repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, dry and obtain filler powder;

C, above-mentioned gained powder to be mixed with other remaining component, and even with the high speed dispersion of 8000-10000 rev/min, to obtain final product.

2. drip-dry acrylic modified alkyd automobile finish according to claim 1, is characterized in that: described pigment is selected from one or more in carbon black, titanium dioxide, chrome yellow, molybdenum red, ferric oxide series, phthalein mountain valley with clumps of trees and bamboo series, toluidine maroon, talcum powder, calcium carbonate, barium sulfate, silicon-dioxide.

3. the production method of drip-dry acrylic modified alkyd automobile finish according to claim 1, is characterized in that, comprise the following steps:

(1) by formula rate, HCPE xylene soluble is filtered, add LH-159 resin, dispersion agent, pigment, the modified filler of 20-30% formula ratio more successively, with 2000-2600r/min rotating speed after high speed dispersion 1-1.5 hour, then filter with 80 eye mesh screens;

(2) material filtered enters sand mill and is ground to fineness control≤30 μm of dischargings, requires outlet mass temperatures≤60 DEG C;

(3) material that mesh-of-grind is qualified adds tune and converts in still, and adds the rest materials in formula, stirs evenly with the middling speed of 100-200r/min;

(4), after stirring evenly, be coated with-4 with aromatic solvent adjustment viscosity to 90-120S/, filter with 200 order vibratory screening apparatuss, pack.