CN109777235A - Automobile external coating sour epoxy hot setting type coating varnish and preparation method thereof - Google Patents
Automobile external coating sour epoxy hot setting type coating varnish and preparation method thereof Download PDFInfo
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Abstract
Automobile external coating sour epoxy hot setting type coating varnish and preparation method thereof, the varnish mainly consist of the following components: thermosetting acrylic resin that thermosetting acrylic resin that total acid number is 120-140, epoxide number are 2.0-4.0, anti-sag resin, the saturated polyester containing hexahydrophthalic anhydride monomer, amino resins, ammonium bromide class catalyst, catalyst sealer, levelling agent, polyacrylate defoaming agent, ultraviolet absorbing agent, hindered amine light stabilizer, anti-sag auxiliary agent, alcohols solvent, diluent containing fumed silica.The invention also includes the preparation methods of the varnish.Varnish of the invention has the characteristics that high construction contains admittedly, appearance is good and high acidproof, has stronger competitiveness on the market.
Description
Technical field
The present invention relates to a kind of automobile external coating sour epoxy hot setting type coating varnishes and preparation method thereof.
Background technique
In the prior art, automobile acrylic acid-amino coating varnish curing mechanism are as follows:
Remarks: R group is-C4H9Or-CH3
The solidification process as shown in above-mentioned reaction equation, because of system reason, there is small molecule release in when solidification, and there are volume receipts
Contracting, shielding is poor, so that matched finishing coat planarization is poor, will cause product appearance unsightly, is not easy to be readily accepted by customers.
Acrylic acid-amino varnish construction contains situation admittedly in the prior art:
The automobile acrylic acid of the prior art-amino coating varnish Primary resins are made of acrylic acid and amino resins, by
In resin reason itself, crosslink density is not high enough, to guarantee that physicochemical property and weather resistance, resin molecular weight need to remain higher
Level, the weight average molecular weight Mw of general acrylic resin are 6000-12000, and amino Mw is 600-4500, and molecular weight height is bound to
It causes viscosity to increase, is diluted to suitable working viscosity, conventional propylene to guarantee that application property just needs to be added more diluent
Sour varnish generally original Qi Gu contains for 50% hereinafter, dilution rate is 15-25%, and construction solid content is only 40-45% or so, spraying
Inefficiency, VOC emission is high, all brings biggish burden to auto vendor's construction and environment.
Acrylic acid-amino varnish acid resistance status analysis in the prior art:
Chemical structure after conventional acrylic-amino varnish cross-linking reaction is diether linkage structure, and the chemical structure is weaker, is subject to
By the hydrionic invasion in acid with strong oxidizing property, it is destroyed and causes to corrode:
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of automobile external coating acid
Epoxy hot setting type coating varnish and preparation method thereof, gained varnish construction solid content is high, excellent appearance, and acid resistance is preferable.
The technical solution used to solve the technical problems of the present invention is that: in this specification, unless otherwise stated, the number
Parts by weight are referred both to, the percentage refers both to weight percent.
The sour epoxy hot setting type coating varnish of the automobile external coating of the present invention, mainly by the component of following parts by weight
Composition: the total acid number of 30-40 parts by weight be the thermosetting acrylic resin of 120-140,30-40 parts by weight epoxide number be
The thermosetting acrylic resin of 2.0-4.0, the anti-sag resin of 5-10 parts by weight, 1-10 parts by weight contain hexahydrophthalic anhydride list
The saturated polyester of body, the amino resins of 1-5 parts by weight, the ammonium bromide class catalyst of 0.1-1.0 parts by weight, 0.1-1.0 parts by weight
Catalyst sealer, the levelling agents of 0.2-1.0 parts by weight, 0.1-1.0 parts by weight polyacrylate defoaming agent, 0.5-1.5
The ultraviolet absorbing agent of parts by weight, the hindered amine light stabilizer of 0.2-1.0 parts by weight, 1-10 parts by weight contain gas phase dioxy
The anti-sag auxiliary agent of SiClx, 10-20 parts by weight alcohols solvent, 5-10 parts by weight diluent.
The thermosetting acrylic resin that the total acid number is 120-140 be n-butyl acrylate, n-BMA,
The copolymer of maleic anhydride monomer and styrene monomer；The dosage of maleic anhydride monomer is the thermosetting property that total acid number is 120-140
The 15-25wt% of acrylic resin；Too high levels, acid anhydrides amount is too high, unfavorable to resin storage stability, and content is too low, with ring
Density is insufficient when oxygen groups are crosslinked, weatherability decline；Thermosetting acrylic resin weight average molecular weight after synthesis is 3000-
5000。
Further, the total acid number be 120-140 thermosetting acrylic resin the preparation method is as follows:
1), by the parts by weight ingredient in following table 1:
1 raw material proportioning of table
| Material name | Parts by weight |
| N-BMA | 153.1 |
| N-butyl acrylate | 48.1 |
| Styrene | 131.3 |
| Maleic anhydride | 105.0 |
| Solvent: trimethylbenzene | 178.0 |
| Solvent: 3- ethoxyl ethyl propionate | 210 |
| Solvent: butanol | 55 |
| It is total | 890.5 |
2) in the four-hole boiling flask equipped with blender, thermometer, condenser, water segregator and logical nitrogen device, by 1 formula ratio of table
Styrene, n-BMA, n-butyl acrylate, 110 parts by weight of trimethylbenzene is added, is stirred until homogeneous, and using folder
Set is cooling to keep temperature of charge to 25 DEG C or less；After logical nitrogen to oxygen volumetric concentration is 8% hereinafter, stirring rises to 50RPM, make
150 DEG C or more are heated to collet, 3- ethoxy ethyl propionate, maleic anhydride is added dropwise to by 1 formula ratio of table, is protected before completion of dropwise addition
Temperature is held to stablize at 150 ± 2 DEG C；
3) 3- ethoxy ethyl propionate is added dropwise, after maleic anhydride complete 2 hours, improves speed of agitator to 60RPM, 3- ethoxy is added dropwise
After complete 4 hours of ethyl propionate, maleic anhydride, it is cooled to 110-115 DEG C after the completion of being cleaned with 30 parts by weight of trimethylbenzene, is added three
38 parts by weight of toluene and butanol are down to 92-96 DEG C after curing, keep containing to get to solid for 52-58%, total acid number for 2-3 hours
For 120-140, weight average molecular weight is the transparent flow dynamic resin of 3000-5000, as the total acid number thermosetting property that is 120-140
Acrylic resin；If total acid number is not up to 120-140, then can will extend the curing time, until total acid number reaches 120-140, it is ripe
Changing the time six hours is the upper limit.
The thermosetting acrylic resin that the epoxide number is 2.0-4.0 is n-butyl acrylate, methacrylic acid -2- hydroxyl
Ethyl ester, Isobutyl methacrylate, acrylic acid -4- hydroxybutyl, glycidyl methacrylate and styrene monomer are total to
Polymers；The dosage control of glycidyl methacrylate is the weight for the thermosetting acrylic resin that epoxide number is 2.0-4.0
30-40wt%；Glycidyl methacrylate amount is excessively high, and the decline of resin flexibility is obvious, and amount is too low, causes to be crosslinked close
Degree is insufficient, weatherability decline；The thermosetting acrylic resin molecular weight that epoxide number is 2.0-4.0 is 3000-5000.
Further, the epoxide number be 2.0-4.0 thermosetting acrylic resin the preparation method is as follows:
1), by the parts by weight ingredient in following table 2:
2 raw material proportioning of table
| Material name | Parts by weight |
| N-butyl acrylate | 150 |
| Methacrylic acid -2- hydroxy methacrylate | 120 |
| Isobutyl methacrylate | 60 |
| Acrylic acid -4- hydroxybutyl | 30 |
| Styrene | 30 |
| Glycidyl methacrylate | 210 |
| Catalyst: di t-amyl peroxide | 20 |
| Solvent: trimethylbenzene | 180 |
| Solvent: butanol | 68 |
| It is total | 868 |
2) it in the four-hole boiling flask equipped with blender, thermometer, condenser, water segregator and logical nitrogen device, is formulated by upper table 2
Styrene, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylate, n-butyl acrylate, methyl-prop is added in amount
Olefin(e) acid isobutyl ester, 10 parts of trimethylbenzene, acrylic acid -4- hydroxybutyl, stir evenly, and keep temperature of charge using collet is cooling
To 25 DEG C or less；Logical nitrogen to oxygen volumetric concentration 8% hereinafter, after stirring rises to 50RPM, using collet be heated to 160 DEG C with
On, di t-amyl peroxide and 15 parts by weight trimethylbenzenes is added dropwise by 2 formula ratio of table, until keeping temperature to stablize before completion of dropwise addition
160±2 ℃；
3) after di t-amyl peroxide is added dropwise in step 2), 15 parts by weight trimethylbenzenes are completed 4 hours, 130 weight of trimethylbenzene is added
Part cleaning is measured, is subsequently cooled to 115 DEG C, 25 mass parts of trimethylbenzene and butanol is added, 80 DEG C are down to after curing hereinafter, holding 2 is small
When to get to solid containing being 65-75%, the thermosetting acrylic resin that epoxide number 2.0-4.0, molecular weight are 3000-5000,
As epoxide number be 2.0-4.0 thermosetting acrylic resin.
The anti-sag resin is selected from non-aqueous dispersion type resin, and the further preferred beautiful Yanggao County's molecular material (Nantong) of Mitsubishi has
The NAD017 of limit company.
The saturated polyester containing hexahydrophthalic anhydride monomer, further, preferred brilliant same moral Chemical Co., Ltd., Foshan City
AK-3080-70.
The amino resins is preferably the melamine resin of methyl and butyl etherificate, further, preferably long vernalization
The MR2133 of work (Jiangsu) Co., Ltd.The melamine resin of methyl and butyl etherificate are as follows: melamine resin
Above while there are at least one methyl and at least one butyl etherificate.
The ammonium bromide class catalyst, further preferred dodecyl ammonium bromide or cetyl ammonium bromide.This two kinds are urged
Agent is common commercially available product, is dissolvable in water alcohols, reacts with ammonium bromide, volatilizable, moderate boiling point, cost is relatively low.
The catalyst sealer is phosphoric acid ester sealer, further, preferred Dong Bang chemical industrial company (Japan)
SM-172K。
The preferred polyacrylate flow agent of levelling agent, further, preferred this chemical conversion of nanmu (Japan) Co., Ltd.
DISOARLON NSH-8430。
The preferred polyacrylate defoaming agent of polyacrylate defoaming agent preferably further is selected from nanmu this chemical conversion (Japan)
The DISOARLON OX-750 of Co., Ltd..
The ultraviolet absorbing agent preferably 1,3,5 s-triazine ultraviolet absorbers, further, preferred BASF (Germany)
The Tinuvin 400 of joint-stock company.
The hindered amine light stabilizer is selected from least one of A, B；A is bis- (1- octyloxy -2,2,6,6- tetramethyls -
4- piperidyl) sebacic acid, the preferably Tinuvin 123 of BASF (Germany) joint-stock company；B be N- (acetyl group -2,2,6 1-,
6- tetramethyl -4- piperidyl) -2- dodecyl succinimide, the preferably Sanduvor 3058 of Clariant (Switzerland) company.
The anti-sag auxiliary agent containing fumed silica is that (Germany) work is created in the win containing 8-12% weight percent
The dispersion liquid of the AEROSIL R972 fumed silica of industry joint-stock company.
Further, the preparation principle of the above-mentioned anti-sag auxiliary agent containing fumed silica and the preparation method is as follows:
Preparation principle: being mixed with glass dispersible pearl with material, is existed under conditions of high speed is shaken using dispersion pearl and material
The fineness of fumed silica is reduced and stable is dispersed in resin the shearing force that generates when dividing concussion.
Preparation method, comprising the following steps:
1) weight of following table 3 is pressed:
3 raw material components of table and proportion
2) it is packed into the bead of the 1.0-1.4mm specification of container volume 60% in sealable container, table 3 is then added
In material, keep bead and dispersion liquid total volume to be no more than the 85% of container volume, sealing；
3) container being sealed is fixed in high speed oscillator and carries out concussion 30min or more, speed control 500-700
Secondary/min, until dispersion liquid fineness is less than 20 microns to get the anti-sag auxiliary agent containing fumed silica.
Alcohols solvent at least one preferably below: n-butanol, isobutanol, isooctanol.(these types of solvent power
Good, boiling point is unsuitable low or too high, and evaporation rate is moderate).
The diluent is known diluent, such as at least one of mesitylene, butyl acetate, n-butanol.
The preparation method of the sour epoxy hot setting type coating varnish of the automobile external coating of the present invention, including following step
It is rapid:
1) each component raw material is weighed in proportion, and the total acid number that 30-40 parts by weight are put into container A is the heat of 120-140
Solidity acrylic resin, 30-40 parts by weight epoxide number be that the thermosetting acrylic resin of 2.0-4.0,1-10 parts by weight contain
There are the saturated polyester of hexahydrophthalic anhydride monomer, the amino resins of 1-5 parts by weight, 5-10 parts by weight alcohols solvent, is stirred with dispersion machine
It mixes；
2) 5-10 parts by weight alcohols solvent is added in another container B, is carried out 40 DEG C of heating water bath and is made solvent liter
Temperature adds the powdered ammonium bromide class catalyst of 0.1-1.0 parts by weight in a solvent, becomes transparent after stirring and dissolving to 40 DEG C
Dispersion liquid, then add the catalyst sealer of 0.1-1.0 parts by weight, stir, place 10 minutes or more, obtain B dispersion liquid；
3) under stirring, anti-sag resin, the 0.2- of B dispersion liquid, 5-10 parts by weight are successively added into A container
The levelling agent of 1.0 parts by weight, the polyacrylate defoaming agent of 0.1-1.0 parts by weight, 1-10 parts by weight contain gas phase titanium dioxide
The anti-sag auxiliary agent of silicon, the ultraviolet absorbing agent of 0.5-1.5 parts by weight, 0.2-1.0 parts by weight hindered amine light stabilizer, so
After stir evenly, obtain AB product；
4) diluent (adjustment product viscosity) of 5-10 parts by weight is added into step 3) gained AB product, is stirred with dispersion machine
It mixes uniformly,.
Application method: gained varnish is diluted to appropriate viscosity [generally 28 seconds/20 DEG C Ford -4 (FC-4) cups]；In quilt
Coating substrate coating composition in coat, after obtaining the uncured film of substrate, then on the uncured film of substrate after coating dilution
Varnish, after obtaining transparent uncured film, heating (temperature that is preferably heating and curing be 130 DEG C -160 DEG C, with 15-30 minutes compared with
Properly), make the uncured film of substrate and transparent uncured curing of coating,.
Varnish of the present invention can pass through the methods of spraying, rotary-atomizing formula coating coating.Compared to conventional varnish, the present invention's
Varnish levelability is good, and the requirements such as and rotation cup revolving speed mechanical to coating substantially reduce, in addition, substrate is uncured in coating
Film and transparent uncured film heat simultaneously makes its solidification, and multilayer film is consequently formed.Being heating and curing the time can be according to solidification
The variation such as temperature.
The thickness of varnish film of the invention is in terms of dry film thickness, and preferably 30 microns (um) -45 microns (um).
The sour epoxy type coating varnish technical parameter of the automobile external coating of the present invention: viscosity is 28 ± 2S, -4 glasss of Ford
(FC-4)/20 it DEG C, constructs solid >=51%, gloss is G60 >=90 °.
The automobile external coating of the present invention promotes film using following principle with sour epoxy hot setting type coating varnish
Appearance: using open loop crosslinking curing mechanism between carboxy-modified acrylic acid and epoxy-modified acrylic acid, no small molecule release is applied
Film is smooth plentiful；
Compared with conventional acrylic amino varnish, the invention has the following advantages that (1) high construction is solid to contain (> 50%)；(2)
Excellent appearance；(3) acid resistance is excellent.
Acid epoxy resin varnish crosslinking method according to the present invention is as follows:
As it appears from the above, the curing mechanism are as follows: carry out special modification to two class acrylic acid, be directed respectively into carboxylic group and epoxy
Group, and under the effect of the catalyst, carboxyl and epoxy reaction, epoxy group open loop are crosslinked, this is in the process without small point
Son release, no volume contraction, film richness are good.
Acid epoxy resin varnish involved in the present invention is that it is different from the crosslinking curing mechanism of conventional varnish, in two classes
It is crosslinked between modified acrylic acid, as described above, since the reactivity of epoxy group and carboxylic acid group crosslinking is high,
Crosslink density is obviously improved compared to conventional varnish, can guarantee the higher physicochemical property of paint film and weather resistance after solidifying, from
And can accomplish the low molecule quantization of acrylic resin, two class acrylic resin weight average molecular weight being related in the present invention are equal
For 3000-5000, it is 52-57%, dilution rate 5-10% that the former Qi Gu after coating, which contains, and construction is solid containing being greater than 50%, VOC
Discharge reduces.
Film after acid epoxy resin varnish crosslinking curing involved in the present invention is ester bond structure, steady chemical structure, acid
In hydrogen ion invade difficult, birds droppings or acid rain in environment are difficult to cause film any corrosion or lead to the deterioration of paint film.
Detailed description of the invention
Fig. 1 is that (left part is knot of the invention for the resistance to strong acid experimental result comparison diagram of products obtained therefrom of the present invention and comparative example 6
Fruit, right part are the result of comparative example 6).
Specific embodiment
The invention will be further described with reference to embodiments.But these embodiments must not be used to explain and protect to the present invention
Protect the limitation of range.It is all not depart from equivalents made by basic idea of the present invention, it all belongs to the scope of protection of the present invention.
Reference example 1,2,3:
Reference example 1: the total acid number that the present invention uses is being synthetically prepared for the thermosetting acrylic resin of 120-140:
Acid value is by having imported from maleic anhydride monomer.
1) resins synthesis raw materials distribution see the table below.
| Material name | Parts by weight |
| N-BMA | 153.1 |
| N-butyl acrylate | 48.1 |
| Styrene | 131.3 |
| Maleic anhydride | 105.0 |
| Solvent: trimethylbenzene | 178.0 |
| Solvent: 3- ethoxyl ethyl propionate | 210 |
| Solvent: butanol | 55 |
| It is total | 890.5 |
2) equipped with blender, thermometer, condenser, water segregator and logical nitrogen device four-hole boiling flask in, by formula ratio plus
Enter styrene, n-BMA, n-butyl acrylate, 110 parts by weight of trimethylbenzene, open and be stirred until homogeneous, and uses
Collet is cooling to keep temperature of charge to 25 DEG C；Logical nitrogen, hereinafter, after stirring rises to 50RPM, is used to oxygen volumetric concentration 8%
Collet is heated to 150 DEG C, and 3- ethoxy ethyl propionate (Jiangsu day sound), maleic anhydride (Tianjin Bohai Sea) is added by formula ratio in table
Temperature is kept to stablize at 150 ± 2 DEG C before to completion of dropwise addition；
3) after being added dropwise to complete 2 hours, speed of agitator is improved to 60RPM, after being added dropwise 4 hours, adds 30 parts by weight of trimethylbenzene
It is cooled to 115 DEG C after the completion of cleaning, 38 parts by weight of trimethylbenzene and butanol (Yueyang petrochemical industry) is added, 96 DEG C are down to after curing, keeps
2 hours to get to solid, containing being 55%, total acid number 125, weight average molecular weight is 3500 transparent flow dynamic resin, as total acid
Value is the thermosetting acrylic resin of 120-140.
Reference example 2: the present invention is synthetically prepared using the thermosetting acrylic resin that epoxide number is 2.0-4.0:
Epoxide number is by having imported from glycidyl methacrylate.
1) resins synthesis raw materials distribution see the table below.
| Material name | Parts by weight |
| N-butyl acrylate | 150 |
| Methacrylic acid -2- hydroxy methacrylate | 120 |
| Isobutyl methacrylate | 60 |
| Acrylic acid -4- hydroxybutyl | 30 |
| Styrene | 30 |
| Glycidyl methacrylate | 210 |
| Catalyst: di t-amyl peroxide | 20 |
| Solvent: trimethylbenzene | 180 |
| Solvent: butanol | 68 |
| It is total | 868 |
2) in the four-hole boiling flask equipped with blender, thermometer, condenser, water segregator and logical nitrogen device, by upper table formula
Styrene, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylate, n-butyl acrylate, methyl-prop is added in amount
Olefin(e) acid isobutyl ester, 10 parts of trimethylbenzene, acrylic acid -4- hydroxybutyl, unlatching are stirred until homogeneous, and keep object using collet is cooling
Material temperature degree is to 25 DEG C；Logical nitrogen, hereinafter, after stirring rises to 50RPM, is heated to 160 using collet to oxygen volumetric concentration 8%
DEG C, di t-amyl peroxide, 15 parts by weight trimethylbenzenes is added dropwise by table formula ratio, until keeping temperature to stablize 160 before completion of dropwise addition
±2℃；
3) after di t-amyl peroxide is added dropwise in step 2), 15 parts by weight trimethylbenzenes are completed 4 hours, 130 weight of trimethylbenzene is added
Part cleaning is measured, is subsequently cooled to 115 DEG C, 25 mass parts of trimethylbenzene and butanol is added, 80 DEG C are down to after curing hereinafter, holding 2 is small
When to get to solid, containing being 70%, epoxide number 2.5, the transparent flow dynamic resin that molecular weight is 3500, as epoxide number are 2.0-
4.0 thermosetting acrylic resin.
Reference example 3: the preparation for the anti-sag auxiliary agent containing fumed silica that the present invention uses:
Make to bring about the desired sensation by dispersing apparatus: aerosil is evenly spread in resin:
1) raw-material weight part proportion see the table below
2) it is packed into the bead of the 1.0-1.4mm specification of container volume 60% in sealable container, table 3 is then added
In material, keep bead and dispersion liquid total volume to be no more than the 85% of container volume, sealing；
3) container being sealed is fixed in high speed oscillator and carries out concussion 30min or more, speed control 500-700
Secondary/min, until dispersion liquid fineness is less than 20 microns to get the anti-sag auxiliary agent containing fumed silica.
The following are specific embodiments:
In each embodiment and comparative example, unless otherwise stated, remaining selected species is described as follows:
The anti-sag resin is the NAD017 of beautiful Yanggao County's molecular material (Nantong) Co., Ltd, Mitsubishi.
The saturated polyester containing hexahydrophthalic anhydride monomer is the AK-3080- of brilliant same moral Chemical Co., Ltd., Foshan City
70。
The amino resins is the melamine resin that methyl and butyl are etherified, and is Changchun chemical industry (Jiangsu) limited public affairs
The MR2133 of department.
The ammonium bromide class catalyst is dodecyl ammonium bromide.
The catalyst sealer is phosphoric acid ester sealer, is the SM-172K of Dong Bang chemical industrial company (Japan).
The levelling agent is polyacrylate flow agent, is the DISOARLON NSH- of this chemical conversion of nanmu (Japan) Co., Ltd.
8430。
The polyacrylate defoaming agent is polyacrylate defoaming agent, is from nanmu this chemical conversion (Japan) Co., Ltd.
DISOARLON OX-750。
The ultraviolet absorbing agent is 1,3,5 s-triazine ultraviolet absorbers, is BASF (Germany) joint-stock company
Tinuvin 400。
The hindered amine light stabilizer is the Tinuvin 123 of BASF (Germany) joint-stock company.
The alcohols solvent is n-butanol.
The diluent is mesitylene.
Embodiment 1
The sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, is grouped by the group of following parts by weight
At: the total acid number of 35 parts by weight be the thermosetting acrylic resin of 120-140,35 parts by weight epoxide number be the heat of 2.0-4.0
Solidity acrylic resin, the anti-sag resin of 8 parts by weight, the saturated polyester containing hexahydrophthalic anhydride monomer of 5 parts by weight, 1 weight
Amino resins, the dodecyl ammonium bromide class catalyst of 0.5 parts by weight, the catalyst sealer of 0.1 parts by weight, 0.8 weight of part
Measure the levelling agent of part, the polyacrylate defoaming agent of 0.5 parts by weight, the ultraviolet absorbing agents of 0.8 parts by weight, 0.7 parts by weight
Hindered amine light stabilizer, the anti-sag auxiliary agent containing fumed silica of 2 parts by weight, 15 parts by weight alcohols solvents, 8 weight
The diluent of part.
The preparation method of the sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, including following step
It is rapid:
1) each component raw material is weighed in proportion, and the thermoset acrylics tree that total acid number is 120-140 is put into container A
Rouge, thermosetting acrylic resin, the saturated polyester containing hexahydrophthalic anhydride monomer, the amino resins, alcohol that epoxide number is 2.0-4.0
Class solvent, is stirred with dispersion machine；
2) alcohols solvent is added in another container B, carries out 40 DEG C of heating water bath and solvent is made to be warming up to 40 DEG C,
Powdered ammonium bromide class catalyst is added in solvent, becomes transparent dispersion liquid after stirring and dissolving, then adds catalyst closing
Agent, stirring place 10 minutes, obtain B dispersion liquid；
3) under stirring, B dispersion liquid, anti-sag resin, levelling agent, polyacrylate are successively added into A container
Defoaming agent, the anti-sag auxiliary agent containing fumed silica, ultraviolet absorbing agent, hindered amine light stabilizer, then stir evenly,
Obtain AB product；
4) diluent (adjustment product viscosity) is added into step 3) gained AB product, is stirred evenly with dispersion machine,.
Application method: gained varnish is diluted to appropriate viscosity [generally 28 seconds/20 DEG C Ford -4 (FC-4) cups]；In quilt
Coating substrate coating composition in coat, after obtaining the uncured film of substrate, then on the uncured film of substrate after coating dilution
Varnish, after obtaining transparent uncured film, heating (temperature that is heating and curing be 130 DEG C, 30 minutes) makes the uncured painting of substrate
Film and transparent uncured curing of coating,.
Embodiment 2
The sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, is grouped by the group of following parts by weight
At: the total acid number of 35 parts by weight be the thermosetting acrylic resin of 120-140,35 parts by weight epoxide number be the heat of 2.0-4.0
Solidity acrylic resin, the anti-sag resin of 8 parts by weight, the saturated polyester containing hexahydrophthalic anhydride monomer of 5 parts by weight, 1 weight
Amino resins, the dodecyl ammonium bromide catalyst of 0.5 parts by weight, the catalyst sealer of 0.1 parts by weight, 0.8 weight of part
Part levelling agent, the polyacrylate defoaming agent of 0.5 parts by weight, the ultraviolet absorbing agent of 0.8 parts by weight, 0.7 parts by weight by
Hinder amine light stabilizer, the anti-sag auxiliary agent containing fumed silica of 4 parts by weight, 15 parts by weight alcohols solvents, 8 parts by weight
Diluent.
The preparation method of the sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, including following step
It is rapid:
1) each component raw material is weighed in proportion, and the thermoset acrylics tree that total acid number is 120-140 is put into container A
Rouge, thermosetting acrylic resin, the saturated polyester containing hexahydrophthalic anhydride monomer, the amino resins, alcohol that epoxide number is 2.0-4.0
Class solvent, is stirred with dispersion machine；
2) alcohols solvent is added in another container B, carries out 40 DEG C of heating water bath and solvent is made to be warming up to 40 DEG C,
Powdered ammonium bromide class catalyst is added in solvent, becomes transparent dispersion liquid after stirring and dissolving, then adds catalyst closing
Agent, stirring place 10 minutes, obtain B dispersion liquid；
3) under stirring, B dispersion liquid, anti-sag resin, levelling agent, polyacrylate are successively added into A container
Defoaming agent, the anti-sag auxiliary agent containing fumed silica, ultraviolet absorbing agent, hindered amine light stabilizer, then stir evenly,
Obtain AB product；
4) diluent (adjustment product viscosity) is added into step 3) gained AB product, is stirred evenly with dispersion machine,.
Application method: gained varnish is diluted to appropriate viscosity [generally 28 seconds/20 DEG C Ford -4 (FC-4) cups]；In quilt
Coating substrate coating composition in coat, after obtaining the uncured film of substrate, then on the uncured film of substrate after coating dilution
Varnish, after obtaining transparent uncured film, heating (temperature that is heating and curing be 130 DEG C, 30 minutes) makes the uncured painting of substrate
Film and transparent uncured curing of coating,.
Embodiment 3
The sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, is grouped by the group of following parts by weight
At: the total acid number of 35 parts by weight be the thermosetting acrylic resin of 120-140,35 parts by weight epoxide number be the heat of 2.0-4.0
Solidity acrylic resin, the anti-sag resin of 8 parts by weight, the saturated polyester containing hexahydrophthalic anhydride monomer of 5 parts by weight, 1 weight
Amino resins, the dodecyl ammonium bromide catalyst of 0.5 parts by weight, the catalyst sealer of 0.1 parts by weight, 0.8 weight of part
Part levelling agent, the polyacrylate defoaming agent of 0.5 parts by weight, the ultraviolet absorbing agent of 0.8 parts by weight, 0.7 parts by weight by
Hinder amine light stabilizer, the anti-sag auxiliary agent containing fumed silica of 8 parts by weight, 15 parts by weight alcohols solvents, 8 parts by weight
Diluent.
The preparation method of the sour epoxy hot setting type coating varnish of the automobile external coating of the present embodiment, including following step
It is rapid:
1) each component raw material is weighed in proportion, and the thermoset acrylics tree that total acid number is 120-140 is put into container A
Rouge, thermosetting acrylic resin, the saturated polyester containing hexahydrophthalic anhydride monomer, the amino resins, alcohol that epoxide number is 2.0-4.0
Class solvent, is stirred with dispersion machine；
2) alcohols solvent is added in another container B, carries out 40 DEG C of heating water bath and solvent is made to be warming up to 40 DEG C,
Powdered ammonium bromide class catalyst is added in solvent, becomes transparent dispersion liquid after stirring and dissolving, then adds catalyst closing
Agent, stirring place 10 minutes, obtain B dispersion liquid；
3) under stirring, B dispersion liquid, anti-sag resin, levelling agent, polyacrylate are successively added into A container
Defoaming agent, the anti-sag auxiliary agent containing fumed silica, ultraviolet absorbing agent, hindered amine light stabilizer, then stir evenly,
Obtain AB product；
4) diluent (adjustment product viscosity) is added into step 3) gained AB product, is stirred evenly with dispersion machine,.
Application method: gained varnish is diluted to appropriate viscosity [generally 28 seconds/20 DEG C Ford -4 (FC-4) cups]；In quilt
Coating substrate coating composition in coat, after obtaining the uncured film of substrate, then on the uncured film of substrate after coating dilution
Varnish, after obtaining transparent uncured film, heating (temperature that is heating and curing be 130 DEG C, 30 minutes) makes the uncured painting of substrate
Film and transparent uncured curing of coating,.
Comparative example 1
Formula: acid value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 50 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, mixed 1 parts by weight of etherified melamine amine-formaldehyde resins, the dodecyl ammonium bromide class catalyst of 0.5 parts by weight, 15 weight of solvent
Measure part, the esters of acrylic acid levelling agent of 0.8 parts by weight, the esters of acrylic acid defoaming agent of 0.5 parts by weight, 0.8 parts by weight it is ultraviolet
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl-the 4- of 1,3,5 s-triazine of light absorbers, 0.7 parts by weight
Piperidyl) -2- dodecyl succinimide.
Preparation: acrylic resin, polyester resin, mixed etherified melamine amine-formaldehyde resins, 15 weights are put into stirring container
Part solvent is measured, stirs 15min with blender, then acidic catalyst, levelling agent, anti-sag auxiliary agent, ultraviolet is just added in side stirring
Light absorbers, light stabilizer, then stir 30min, are eventually adding 8 parts by weight diluent adjustment product viscosity,.Usage
With embodiment 1.
Comparative example 2
Formula: acid value is 50 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, mixed 1 parts by weight of etherified melamine amine-formaldehyde resins, the dodecyl ammonium bromide class catalyst of 0.5 parts by weight, 15 weight of solvent
Measure part, the esters of acrylic acid levelling agent of 0.8 parts by weight, the esters of acrylic acid defoaming agent of 0.5 parts by weight, 0.8 parts by weight it is ultraviolet
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl-the 4- of 1,3,5 s-triazine of light absorbers, 0.7 parts by weight
Piperidyl) -2- dodecyl succinimide.
Preparation: acrylic resin, polyester resin, mixed etherified melamine amine-formaldehyde resins, 15 weights are put into stirring container
Part solvent is measured, stirs 15min with blender, then acidic catalyst, levelling agent, anti-sag auxiliary agent, ultraviolet is just added in side stirring
Light absorbers, light stabilizer, then stir 30min, are eventually adding 8 parts by weight diluent adjustment product viscosity,.Usage
With embodiment 1.
Comparative example 3
Formula: acid value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, mixed 1 parts by weight of etherified melamine amine-formaldehyde resins, 15 parts by weight of solvent, the cetyl ammonium bromide class of 0.5 parts by weight are urged
Agent, the esters of acrylic acid levelling agent of 0.8 parts by weight, the esters of acrylic acid defoaming agent of 0.5 parts by weight, 0.8 parts by weight it is ultraviolet
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl-the 4- of 1,3,5 s-triazine of light absorbers, 0.7 parts by weight
Piperidyl) -2- dodecyl succinimide.
Preparation: acrylic resin, polyester resin, mixed etherified melamine amine-formaldehyde resins, 15 weights are put into stirring container
Part solvent is measured, stirs 15min with blender, then acidic catalyst, levelling agent, anti-sag auxiliary agent, ultraviolet is just added in side stirring
Light absorbers, light stabilizer, then stir 30min, are eventually adding 8 parts by weight diluent adjustment product viscosity,.Usage
With embodiment 1.
Comparative example 4
Formula: acid value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, mixed 1 parts by weight of etherified melamine amine-formaldehyde resins, 15 parts by weight of solvent, the dodecyl ammonium bromide class of 0.5 parts by weight are urged
Agent, the esters of acrylic acid levelling agent of 0.8 parts by weight, the esters of acrylic acid defoaming agent of 0.5 parts by weight, 0.8 parts by weight it is ultraviolet
(N- methyl -2,2,6,6- the tetramethyl of hindered amine light stabilizer sebacic acid two of 1,3,5 s-triazine of light absorbers, 0.7 parts by weight
Base -4- pyridyl group) ester.
Preparation: acrylic resin, polyester resin, mixed etherified melamine amine-formaldehyde resins, 15 weights are put into stirring container
Part solvent is measured, stirs 15min with blender, then acidic catalyst, levelling agent, anti-sag auxiliary agent, ultraviolet is just added in side stirring
Light absorbers, light stabilizer, then stir 30min, are eventually adding 8 parts by weight diluent adjustment product viscosity,.Usage
With embodiment 1.
Comparative example 5
Commercially available acrylic-amino varnish: HM-11.
Comparative example 6
Commercially available acrylic-amino varnish: FF76-025A.
Comparative example 7
The sour epoxy hot setting type coating varnish of the automobile external coating of this comparative example, is grouped by the group of following parts by weight
At: the heat that the epoxide number for 35 parts by weight of thermosetting acrylic resin that the acid value of total 35 parts by weight is 120-140 is 2.0-4.0
Solidity acrylic resin, the anti-sag resin of 10 parts by weight, the saturated polyester containing hexahydrophthalic anhydride monomer of 10 parts by weight, 2 weights
Measure the amino resins of part, the dodecyl ammonium bromide catalyst of 0.5 parts by weight, the phosphoric acid ester sealer of 0.5 parts by weight, 0.8
The polyacrylate flow agent of parts by weight, the polyacrylate defoaming agent of 0.5 parts by weight, 0.8 parts by weight 1,3,5 s-triazine
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl -4- the piperidines of class ultraviolet absorbing agent, 0.7 parts by weight
Base) -2- dodecyl succinimide, 10 parts by weight alcohols solvent isobutanols.
Preparation: above two acrylic resin, anti-sag resin, saturated polyester resin, amino are added in stirring container
Resin, alcohols solvent stir 15min with blender, and then side stirring is just added acidic catalyst, sealer, levelling agent, disappears
Infusion, anti-sag auxiliary agent, ultraviolet absorbing agent, light stabilizer, then stir 30min, are eventually adding 5-10 parts by weight diluent
Product viscosity is adjusted,.
Usage: obtained varnish is diluted to 28 seconds/20 DEG C 4# glasss of Ford with diluent when use.On coated article
Coating substrate coating composition, after obtaining the uncured film of substrate, it is clear on the uncured film of the substrate to be coated with the automobile
Paint obtains transparent uncured film, and the uncured film of the substrate and transparent uncured film are heated simultaneously, make its solidification.
Comparative example 8
Formula: acid value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, ten dibrominated ammonium class catalyst of 0.5 parts by weight, 15 parts by weight of solvent, 0.8 parts by weight polyacrylate levelling agent,
The polyacrylate defoaming agent of 0.5 parts by weight, 1,3,5 s-triazine ultraviolet absorbers of 0.8 parts by weight, 0.7 parts by weight
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl -4- piperidyl) -2- dodecyl succinimide.
Preparation: above two acrylic resin, anti-sag resin, saturated polyester resin, amino are added in stirring container
Resin, alcohols solvent stir 15min with blender, and then side stirring is just added acidic catalyst, sealer, levelling agent, disappears
Infusion, anti-sag auxiliary agent, ultraviolet absorbing agent, light stabilizer, then stir 30min, are eventually adding 5-10 parts by weight diluent
Product viscosity is adjusted,.
Usage: obtained varnish is diluted to 28 seconds/20 DEG C 4# glasss of Ford with diluent when use.On coated article
Coating substrate coating composition, after obtaining the uncured film of substrate, it is clear on the uncured film of the substrate to be coated with the automobile
Paint obtains transparent uncured film, and the uncured film of the substrate and transparent uncured film are heated simultaneously, make its solidification.
Comparative example 9
Formula: acid value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 120-140, epoxy
Value is 35 parts by weight of thermosetting acrylic resin (molecular weight 3000-5000) of 2.0-4.0,5 weight of saturated polyester resin
Part, mixed 1 parts by weight of etherified melamine amine-formaldehyde resins, the dodecyl ammonium bromide class catalyst of 0.5 parts by weight, 15 weight of solvent
Measure part, the esters of acrylic acid levelling agent of 0.8 parts by weight, the esters of acrylic acid defoaming agent of 0.5 parts by weight, 0.8 parts by weight 1,3,
Hindered amine light stabilizer N- (1- acetyl group -2,2,6,6- tetramethyl-the 4- of 5 s-triazine ultraviolet absorbers, 0.7 parts by weight
Piperidyl) -2- dodecyl succinimide.
Preparation: above two acrylic resin, anti-sag resin, saturated polyester resin, amino are added in stirring container
Resin, alcohols solvent stir 15min with blender, and then side stirring is just added acidic catalyst, sealer, levelling agent, disappears
Infusion, anti-sag auxiliary agent, ultraviolet absorbing agent, light stabilizer, then stir 30min, are eventually adding 5-10 parts by weight diluent
Product viscosity is adjusted,.
Usage: obtained varnish is diluted to 28 seconds/20 DEG C 4# glasss of Ford with diluent when use.On coated article
Coating substrate coating composition, after obtaining the uncured film of substrate, it is clear on the uncured film of the substrate to be coated with the automobile
Paint obtains transparent uncured film, and the uncured film of the substrate and transparent uncured film are heated simultaneously, make its solidification.
[paint solution and paint film property evaluation procedure]
Take phosphatization plate (Nihon Parkerizing Co., Ltd. PB-L3020), and electrophoresis anaphoretic priming (25 μm of film thickness, Hunan
Xiang River Northwest coating Co., Ltd HT-8000 electrophoretic primer), 175 DEG C × 20min baking, after being placed at room temperature for 24 hours, spray
Apply aqueous middle painting (20-25 μm), after room temperature levelling 3min, 80 DEG C × 5min prebake conditions, levelling to room temperature, then spray aqueous face
It paints (11-15 μm), after room temperature levelling 3min, 80 DEG C × 5min prebake conditions, levelling to room temperature sprays above-mentioned configured varnish
(30-45 μm), room temperature levelling 7min, then 150 DEG C × 20min is toasted, and after being placed at room temperature for 24 hours, tests the property of film
Energy.
Experimental evaluation method:
1, ocular estimate method: the length of Germany BYK company tangerine peel instrument dual (model AW-4840) measurement test plate (panel) is used
Wave number, good appearance, Lw long wave number≤6, Sw shortwave value≤20；Appearance is qualified, 6 value≤30 < Lw value≤10,20 < Sw；Outside
See general, 10 value≤40 < Lw value≤20,20 < Sw；Poor appearance, Lw value > 20, Sw value > 40；
2, SDL ATLAS M238BB Model CM-5 friction instrument, the apparatus working scratch resistance evaluation method: are used
Speed is 60 revs/min, and the friction head of instrument applies the pressure of 9N (about 900g) to test plate (panel), carries out the wiping of 10 circulations,
Observe the gloss loss of film coated surface wiping situation and G20, calculation method are as follows: gloss loss=(G20 after original G20- wiping)/former
Beginning G20*100%；
4 paint solution of table and paint film property examination criteria and method
Paint solution and paint film property evaluation result, embodiment are shown in Table 5, comparative example and are shown in Table 6.
Table 5
Table 6
Ocular estimate
Experimental evaluation method: 1, it ocular estimate method: is surveyed using Germany BYK company tangerine peel instrument dual (model AW-4840)
Measure test plate (panel) appearance:
Remarks: the obscure degree of Du-, wavelength are less than the appearance of 0.1mm；The long wave number of Lw-, wavelength are greater than 0.6mm, are less than 10mm
Appearance；Sw-shortwave value, wavelength are greater than 0.1mm, the appearance less than 0.6mm；DOI-clarity, film, which influences clarity, to be commented
Price card is quasi-；CF-Ford Motor, the U.S. evaluates appearance of film standard
Table 7 (mating aqueous silver color finishing coat vertical plane appearance)
Table 8 (mating aqueous plain color black finishing coat vertical plane appearance)
Table 9 (mating water-soluble pearlescent white finishing coat vertical plane appearance)
Evaluation result:
By table 5 to table 9 it is found that in embodiment 1-3, appearance is overall all more excellent, since carboxyl is reacted with epoxy group
Sufficiently, curing of coating is preferable, wherein carboxy-modified acrylic acid mainly provides planarization, the main offer of epoxy group resists back
Gloss is blended, comparative example 1,2,3, as the amount of silica increases, sag resistance gets a promotion, and appearance is overall same
One is horizontal, and embodiment 3 is slightly decreased.
Since epoxy group is excessive in comparative example 1, the anti-back permeability of film is good, and du value is low, but levelability is insufficient, long shortwave compared with
Difference.Then on the contrary, carboxylic acid group, which has to have more than needed to cause to resist, bleeds back decline in comparative example 2, du value is larger.And the crosslinking of embodiment is anti-
Not fully aging should be caused the problem of aging such as xanthochromia, cracking, loss of gloss occur, comparative example 3 is then due to the catalyst of importing
Type is improper, causes film crosslink density insufficient, and performance is unqualified, and comparative example 4 has imported the hindered amine light stabilizer of alkalinity
The acid-base property that agent influences system causes catalyst effect to fail, film crosslink density is insufficient and in ageing process due to occurring
Upper infiltration causes performance unqualified.
Comparative example 5 is commercially available acrylic-amino varnish product HM-11, and constructing, it is not high to contain admittedly, and acid resistance is poor, mating aqueous
System poor appearance, comparative example 6 are commercial product FF76-025A, and the comparison (referring to Fig. 1) with example of the present invention, product of the present invention exists
Construction contains admittedly, is acidproof and with the obvious advantage in appearance.
Resistance to strong acid detection method: the H for being 20% in varnish film coated surface drop 2ml mass concentration2SO4Solution, can be close with top
The ring of envelope is closed, and lower end is sealed with vaseline, is placed in 85 DEG C of environment lower 1 hour, and observation film is cleaned in cleaning after taking-up
Surface appearance (left part is of the invention as a result, right part is the result of comparative example 6).
Saturated polyester and amino dosage are excessive in comparative example 7, cause appearance of film without advantage.8 hardness of comparative example is poor, by
It is assisted in no amino, hardness only has the level of HB.Comparative example 9 has lacked the auxiliary of silica auxiliary agent, although appearance
It is excellent, but sag resistance is unqualified, and there are the risks of sagging for vehicle body facade.
Claims (10)
1. the sour epoxy hot setting type coating varnish of automobile external coating, which is characterized in that mainly by the group of following parts by weight
Be grouped as: the total acid number of 30-40 parts by weight be the thermosetting acrylic resin of 120-140,30-40 parts by weight epoxide number be
The thermosetting acrylic resin of 2.0-4.0, the anti-sag resin of 5-10 parts by weight, 1-10 parts by weight contain hexahydrophthalic anhydride monomer
Saturated polyester, the amino resins of 1-5 parts by weight, the ammonium bromide class catalyst of 0.1-1.0 parts by weight, 0.1-1.0 parts by weight
Catalyst sealer, the levelling agent of 0.2-1.0 parts by weight, the polyacrylate defoaming agent of 0.1-1.0 parts by weight, 0.5-1.5 weight
The amount ultraviolet absorbing agent of part, the hindered amine light stabilizer of 0.2-1.0 parts by weight, 1-10 parts by weight contain fumed silica
Anti-sag auxiliary agent, 10-20 parts by weight alcohols solvent, 5-10 parts by weight diluent；
The thermosetting acrylic resin that the total acid number is 120-140 is n-butyl acrylate, n-BMA, Malaysia
The copolymer of anhydride monomers and styrene monomer；The dosage of maleic anhydride monomer is the thermosetting property propylene that total acid number is 120-140
The 15-25wt% of acid resin；Thermosetting acrylic resin weight average molecular weight after synthesis is 3000-5000；
The thermosetting acrylic resin that the epoxide number is 2.0-4.0 is n-butyl acrylate, methacrylic acid -2- hydroxyl second
The copolymerization of ester, Isobutyl methacrylate, acrylic acid -4- hydroxybutyl, glycidyl methacrylate and styrene monomer
Object；The dosage control of glycidyl methacrylate is the weight for the thermosetting acrylic resin that epoxide number is 2.0-4.0
30-40wt%；The thermosetting acrylic resin molecular weight that epoxide number is 2.0-4.0 is 3000-5000.
2. the sour epoxy hot setting type coating varnish of automobile external coating according to claim 1, which is characterized in that institute
State total acid number be 120-140 thermosetting acrylic resin the preparation method is as follows:
1) following parts by weight ingredient: 153.1 parts of n-BMA, 48.1 parts of n-butyl acrylate, styrene, is pressed
131.3 parts, 105.0 parts of maleic anhydride, 178.0 parts of solvent trimethylbenzene, 210 parts of solvent 3- ethoxyl ethyl propionate, solvent butanol
55 parts；
2) it in the four-hole boiling flask equipped with blender, thermometer, condenser, water segregator and logical nitrogen device, is added by 1 formula ratio of table
Styrene, n-BMA, n-butyl acrylate, 110 parts by weight of trimethylbenzene, are stirred until homogeneous, and cold using collet
But keep temperature of charge to 25 DEG C or less；After logical nitrogen to oxygen volumetric concentration is 8% hereinafter, stirring rises to 50RPM, folder is used
Set is heated to 150 DEG C or more, is added dropwise to 3- ethoxy ethyl propionate, maleic anhydride by 1 formula ratio of table, and temperature is kept before completion of dropwise addition
Degree is stablized at 150 ± 2 DEG C；
3) 3- ethoxy ethyl propionate is added dropwise, after maleic anhydride complete 2 hours, improves speed of agitator to 60RPM, 3- ethoxy propionic acid is added dropwise
After complete 4 hours of ethyl ester, maleic anhydride, it is cooled to 110-115 DEG C after the completion of being cleaned with 30 parts by weight of trimethylbenzene, trimethylbenzene 38 is added
Parts by weight and butanol are down to 92-96 DEG C after curing, keep containing to get to solid for 52-58%, total acid number 120- for 2-3 hours
140, weight average molecular weight be 3000-5000 transparent flow dynamic resin, as total acid number be 120-140 thermoset acrylics tree
Rouge.
3. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the thermosetting acrylic resin that, the epoxide number is 2.0-4.0 the preparation method is as follows:
1) following parts by weight ingredient: 150 parts of n-butyl acrylate, 120 parts of methacrylic acid -2- hydroxy methacrylate, metering system, is pressed
60 parts of sour isobutyl ester, 30 parts of acrylic acid -4- hydroxybutyl, 30 parts of styrene, 210 parts of glycidyl methacrylate, catalysis
20 parts of agent di t-amyl peroxide, 180 parts of solvent trimethylbenzene, 68 parts of solvent butanol；
2) in the four-hole boiling flask equipped with blender, thermometer, condenser, water segregator and logical nitrogen device, add by upper 2 formula ratio of table
It is different to enter styrene, glycidyl methacrylate, methacrylic acid -2- hydroxy methacrylate, n-butyl acrylate, methacrylic acid
Butyl ester, 10 parts of trimethylbenzene, acrylic acid -4- hydroxybutyl, stir evenly, and use collet it is cooling keep temperature of charge to 25 DEG C with
Under；Logical nitrogen, hereinafter, after stirring rises to 50RPM, is heated to 160 DEG C or more using collet, by table 2 to oxygen volumetric concentration 8%
Di t-amyl peroxide and 15 parts by weight trimethylbenzenes are added dropwise in formula ratio, until keeping temperature to stablize at 160 ± 2 DEG C before completion of dropwise addition；
3) after di t-amyl peroxide is added dropwise in step 2,15 parts by weight trimethylbenzenes are completed 4 hours, 130 parts by weight of trimethylbenzene are added
Cleaning, is subsequently cooled to 115 DEG C, and 25 mass parts of trimethylbenzene and butanol is added, and 80 DEG C are down to after curing hereinafter, being kept for 2 hours, i.e.,
Obtain solid contain for 65-75%, the thermosetting acrylic resin that epoxide number 2.0-4.0, molecular weight are 3000-5000, as epoxy
Value is the thermosetting acrylic resin of 2.0-4.0.
4. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the anti-sag resin is selected from non-aqueous dispersion type resin；The saturated polyester containing hexahydrophthalic anhydride monomer；The amino tree
Rouge is the melamine resin that methyl and butyl are etherified, the melamine resin of methyl and butyl etherificate are as follows: trimerization
There are at least one methyl and at least one butyl etherificate on cyanamide formaldehyde resin simultaneously.
5. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the ammonium bromide class catalyst is dodecyl ammonium bromide or cetyl ammonium bromide；The catalyst sealer is phosphoric acid
Esters sealer；The levelling agent is polyacrylate flow agent.
6. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the polyacrylate defoaming agent is polyacrylate defoaming agent；The ultraviolet absorbing agent is that 1,3,5 s-triazines are ultraviolet
Light absorbers；The hindered amine light stabilizer is selected from least one of A, B, and A is bis- (1- octyloxy -2,2,6,6- tetramethyls -
4- piperidyl) sebacic acid；B is N-(1- acetyl group -2,2,6,6- tetramethyl -4- piperidyl) -2- dodecyl succinimide.
7. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the anti-sag auxiliary agent containing fumed silica is the AEROSIL R972 gas phase two containing 8-12% weight percent
The dispersion liquid of silica.
8. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In, the preparation principle of the anti-sag auxiliary agent containing fumed silica and the preparation method is as follows:
Preparation principle: mix with material with glass dispersible pearl, is utilized under conditions of high speed is shaken and to be dispersed pearl and material and dividing
The fineness of fumed silica is reduced and stable is dispersed in resin by the shearing force generated when concussion；
Preparation method, comprising the following steps:
1) following weight: 10 parts of fumed silica AEROSIL R972, the thermosetting property that total acid number is 120-140 is pressed
32.5 parts of acrylic resin, 57.5 parts of n-butanol；
2) it is packed into the bead of the 1.0-1.4mm specification of container volume 60% in sealable container, is then added in table 3
Material keeps bead and dispersion liquid total volume to be no more than the 85% of container volume, sealing；
3) container being sealed is fixed in high speed oscillator and carries out concussion 30min or more, speed control be 500-700 times/
Min, until dispersion liquid fineness is less than 20 microns to get the anti-sag auxiliary agent containing fumed silica.
9. automobile external coating according to claim 1 or 2 is existed with sour epoxy hot setting type coating varnish, feature
In the alcohols solvent is at least one below: n-butanol, isobutanol, isooctanol；The diluent is mesitylene, second
At least one of acid butyl ester, n-butanol.
10. the preparation of the sour epoxy hot setting type coating varnish of automobile external coating described in one of -9 according to claim 1
Method, which comprises the following steps:
1) each component raw material is weighed in proportion, and the total acid number that 30-40 parts by weight are put into container A is the thermosetting property of 120-140
Acrylic resin, 30-40 parts by weight epoxide number be that the thermosetting acrylic resin of 2.0-4.0,1-10 parts by weight contain six
The saturated polyester of hydrogen phthalic anhydride monomer, the amino resins of 1-5 parts by weight, 5-10 parts by weight alcohols solvent, are stirred with dispersion machine；
2) 5-10 parts by weight alcohols solvent is added in another container B, carries out 40 DEG C of heating water bath and solvent is warming up to
40 DEG C, the powdered ammonium bromide class catalyst of 0.1-1.0 parts by weight is added in a solvent, becomes transparent dispersion after stirring and dissolving
Liquid, then the catalyst sealer of 0.1-1.0 parts by weight is added, it stirs, place 10 minutes or more, obtain B dispersion liquid；
3) under stirring, B dispersion liquid, the anti-sag resin of 5-10 parts by weight, 0.2-1.0 weight are successively added into A container
Measure the levelling agent of part, the polyacrylate defoaming agent of 0.1-1.0 parts by weight, 1-10 parts by weight it is anti-containing fumed silica
Sagging auxiliary agent, the ultraviolet absorbing agent of 0.5-1.5 parts by weight, 0.2-1.0 parts by weight hindered amine light stabilizer, then stirring is equal
It is even, obtain AB product；
4) diluent that 5-10 parts by weight are added into step 3) gained AB product adjusts product viscosity, is stirred with dispersion machine equal
It is even,.
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| CN110964393A (en) * | 2019-12-05 | 2020-04-07 | 廊坊立邦涂料有限公司 | Varnish composition with anti-indentation self-repairing function of protective film and preparation method and application thereof |
| CN111138930A (en) * | 2020-01-20 | 2020-05-12 | 东莞大宝化工制品有限公司 | VOC (volatile organic compound) reducing odor-free automobile paint and preparation method thereof |
| CN111454627A (en) * | 2020-04-30 | 2020-07-28 | 广州立邦涂料有限公司 | Black finishing varnish for automobile and preparation method and application thereof |
| CN114836123A (en) * | 2021-02-02 | 2022-08-02 | 台湾永光化学工业股份有限公司 | Self-repairing resin composition and application thereof |
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| CN101445690A (en) * | 2008-12-23 | 2009-06-03 | 湖南湘江关西涂料有限公司 | Acrylic-amino finish varnish for automobile external coating |
| CN106700785A (en) * | 2017-01-16 | 2017-05-24 | 广东四方威凯新材料有限公司 | Aluminum alloy wheel finishing varnish capable of thick-film spraying and re-coating and preparation method thereof |
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| CN111454627A (en) * | 2020-04-30 | 2020-07-28 | 广州立邦涂料有限公司 | Black finishing varnish for automobile and preparation method and application thereof |
| CN114836123A (en) * | 2021-02-02 | 2022-08-02 | 台湾永光化学工业股份有限公司 | Self-repairing resin composition and application thereof |
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