CN109705278A - Aqueous acrylic emulsion and preparation method thereof for automobile electrophoresis finish - Google Patents
Aqueous acrylic emulsion and preparation method thereof for automobile electrophoresis finish Download PDFInfo
- Publication number
- CN109705278A CN109705278A CN201811603421.8A CN201811603421A CN109705278A CN 109705278 A CN109705278 A CN 109705278A CN 201811603421 A CN201811603421 A CN 201811603421A CN 109705278 A CN109705278 A CN 109705278A
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsion
- aqueous
- urethane acrylate
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Aqueous acrylic emulsion for automobile electrophoresis finish, belong to the technical field of automobile finiss lotion, according to parts by weight, according to parts by weight, including 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 200-250 parts of n-butyl acrylate, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic urethane acrylate, 3-15 parts of response type polymerisable emulsifier, 0-10 parts of aqueous solid acrylic resin, 1-5 parts of initiator, 430-600 parts of water, 0-5 parts of ammonium hydroxide, 0-3 parts of defoaming agent, 0-3 parts of fungicide.The present invention also provides the preparation method of the aqueous acrylic emulsion, the aqueous automobile finishing coat lotion of lotion of the present invention and synthesis is free of APEO, and low-methoxyl aldehyde, no benzene homologues and other disposals of pollutants, and particle diameter distribution is very narrow, and product stability is fine.
Description
Technical field
The invention belongs to the technical fields of automobile finiss lotion, are related to automobile finiss aqueous acrylic emulsion, tool
Body is related to the aqueous acrylic emulsion and preparation method thereof for automobile electrophoresis finish, aqueous acrylic emulsion of the present invention and bottom
The electrophoretic paint of material has good adhesive force, while adhesion during workshop processes and stores, and coating levelling effect is good, applies
Dress effect is good, and preparation method of the present invention is simple, easy to operate, and preparation process is stablized.
Background technique
With the development and progress of science and technology, more and more for the requirement of VOC emission amount in the world, the standard of appearance is more next
It is stringenter.Since the 1990s, American-European automobile factory is to meet environmental standard, gradually uses eco-friendly car coating
To replace conventional organic solvents type coating.And in the trend of China's painting dressing automobiles, equally sent out towards environmentally protective and Harmless
Exhibition, has generallyd use water paint, automobile water paint and its application techniques also reach its maturity.Kind is mating, coating quality
Aspect can also compare favourably with traditional solvent-borne.It can utilize from environmental protection, resource and coating quality etc. is evaluated, nowadays
Technique be all advanced vehicle body linging lacquer craftwork, almost 100% use is all cathode to the body of a motor car of a large amount of Production lines
Electrophoresis bottoming, is coated with topcoat paint outside later.And such harshness is often not achieved in existing common water borne acrylic emulsion
Requirement, the adhesive force on electrophoretic paint is often poor, paint film be easy peel off；During pyrolytic coating, levelling is poor, seriously
Affect the appearances such as gloss.
Summary of the invention
The present invention to solve the above problems, provide a kind of aqueous acrylic emulsion for automobile electrophoresis finish and its
Preparation method, during pyrolytic coating, the levelling and painting effect of coating are good.
The present invention be realize its purpose the technical solution adopted is that:
For the aqueous acrylic emulsion of automobile electrophoresis finish, according to parts by weight, including 50-80 parts of styrene, first
50-100 parts of base methyl acrylate, 200-250 parts of n-butyl acrylate, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, fat
1-8 parts of adoption urethane acrylate, 3-15 parts of response type polymerisable emulsifier, 0-10 parts of aqueous solid acrylic resin, cause
1-5 parts of agent, 430-600 parts of water, 0-5 parts of ammonium hydroxide, 0-3 parts of defoaming agent, 0-3 parts of fungicide.
Response type polymerisable emulsifier is emulsifier of the one end with double bond, participation emulsion polymerization.Such as selected from anti-
One or two kinds of compounding of type polymerisable emulsifier AR-10 or response type polymerisable emulsifier ER-10 are answered, but is not limited to this
Two kinds.When selecting two kinds of compoundings, the mass ratio of response type polymerisable emulsifier AR-10 and response type polymerisable emulsifier ER-10
For 1:9 to 9:1.
The aliphatic urethane acrylate is aliphatic urethane acrylate CN9002 and/or aliphatic poly ammonia
Ester acrylate CN996.
The compound proportion of aliphatic urethane acrylate CN9002 and aliphatic urethane acrylate CN996 are 2:8
To 8:2.
Selected aqueous solid acrylic resin be BASF 678 or Han Hua 60L, 70,74,90 it is one such or
The a variety of compound uses of person.
The initiator is one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
The preparation method of aqueous acrylic emulsion for automobile electrophoresis finish, comprising the following steps:
A, raw material preparation: pressing following portions by weight, weigh 50-80 parts of styrene, and 50-100 parts of methyl methacrylate, third
200-250 parts of olefin(e) acid N-butyl, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic urethane acrylate,
2-10 parts of response type polymerisable emulsifier, 0-10 parts of aqueous solid acrylic resin, 1-5 parts of initiator, 430-600 parts of water, ammonia
It is 0-5 parts of water, 0-3 parts of defoaming agent, 0-3 parts of fungicide, spare；
B, the preparation of monomer pre-emulsion: 100-150 parts of water intaking, 2-10 parts of response type polymerisable emulsifier stirrings are abundant, then
Sequentially add 50-80 parts of styrene, 50-100 parts of methyl methacrylate, 200-250 parts of n-butyl acrylate, methacrylic acid
2-10 parts, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic urethane acrylate, into reaction kettle, are stirred 1-1.5h, it is pre- to obtain monomer
Lotion；
C, the preparation of initiator solution: initiator being dissolved in 30-50 parts of water, and stirring obtains initiator solution, standby
With；
D, the preparation of lotion: 300-400 parts of water intaking and 1-5 parts of response type polymerisable emulsifier and aqueous solid acrylic acid tree
0-10 parts of rouge mixing, stir and are warming up to 80-85 DEG C, and the monomer pre-emulsion of 1-10% is added, and keep the temperature 515min, 5- is added later
15% initiator solution, and 30-40min is kept the temperature, start that remaining monomer pre-emulsion and remaining initiation are added dropwise simultaneously later
Agent solution is added dropwise in 2.5-3.5h, keeps the temperature 1-1.5h later, is post-processed and is cooled down, and then adjusts pH with ammonium hydroxide
To 7-8, defoaming agent and fungicide is added, final finished emulsion is obtained after filtering.
The beneficial effects of the present invention are:
Aqueous solid acrylic resin is introduced in the present invention, the adhesive force with electrophoretic primer is substantially increased, with response type
Polymerisable emulsifier (preferably compounding AR10 and ER10) functionally mutually support, while improving paint film entirety water resistance,
A possibility that reducing emulsifier and emulsion particle removing, but also lotion has good levelling and light in spraying process
Pool.By introducing aqueous solid acrylic resin, so that lotion has and the extraordinary adhesive force of electrophoretic primer, and can have
Effect protects lotion not form a film during pyrolytic coating, has good levelling after so that paint film is attached to substrate and sprawls
Property, and can effectively keep gloss.
In addition, special polyurethanes the monomer CN9002 and CN996 that can be copolymerized with acrylate monomer is also introduced,
Further improving adhesive force and ground with pigments and fillers and substrate has extraordinary combination, while paint film entirety can be improved
Toughness and weatherability.
The aqueous automobile finishing coat product emulsion synthesized with lotion of the present invention, is free of APEO, and low-methoxyl aldehyde, no benzene homologues and its
His disposal of pollutants, particle diameter distribution is very narrow, and product stability is fine.In crucial performance, and main competition pair both at home and abroad
Hand is compared, and has excellent adhesive force and water resistance, during construction in later period, has good spraying effect, finally
Excellent product performance and environmentally protective.
It is compounded, be can be very good and monomer reaction using response type polymerisable emulsifier AR10 and ER10, be grafted on lotion
The surface of particle reduces wandering about as a refugee for emulsifier, lotion is made to protect latex particle well in spraying process, improves the steady of lotion
It is qualitative.
The present invention also has the advantage that
1, aliphatic urethane acrylate is added in lotion as special polyurethanes monomer, has curing rate
Fast effect；Due to the presence of acrylate, so that high molecular polymer molecule interchain is formed a variety of hydrogen bonds, there is paint film
Excellent mechanical endurance and flexibility, chemical resistance and resistant of high or low temperature.The present invention passes through two kinds of aliphatic polyurethane propylene
The ratio control of acid esters can balance rate of drying, and paint film will not occur during drying and shrink and crack, so that paint film
Have preferable compactness.The ratio control of two kinds of aliphatic urethane acrylates simultaneously can also adjust lotion and paint film
Viscosity, increases the wetability of paint film, improves levelling effect so that having stronger water imbibition before curing, have after solidification compared with
Strong water-resistance, at the same in the curing process participate in reaction form cross-linked network, make the paint film after solidify avoid occur migration with
Evolution guarantees painting quality；And due to the addition of methyl methacrylate, n-butyl acrylate, methacrylic acid, with fat
After the crosslinking of adoption urethane acrylate, cross-linked network is formed, paint film is made uniformly to generate attachment on electrophoretic primer, is improved and electricity
The adhesive force of swimming priming paint.
2, after styrene of the present invention, acrylonitrile and aliphatic urethane acrylate crosslinking, on the basis of cross-linked network
The network structure of interpenetrating is formed, aqueous solid acrylic resin is distributed shuttle in each network structure simultaneously, so that network structure
Connection is fine and close, and lotion can be effectively protected and do not form a film during pyrolytic coating, while solving emulsifier and reduction cream is added
Fluid viscosity and leads to the problem of bubble, close structure also improves the mechanical performance of paint film, and the ductility of paint film is good, improves and is broken
Elongation；Aqueous solid acrylic resin makes cross-linking monomer be distributed in micelle particle surface simultaneously, so that the water resistance of glue film
It all greatly improves, is stablized, the lotion that glossiness is good with mechanicalness.
3, in the present invention aqueous solid resin addition, the molecular weight of lotion can be preferably adjusted, so that molecular weight point
Cloth is more wide in range.The mobility of lotion can be improved in the part of low molecular weight, improves film forming speed, on the other hand also greatly mentions
High and substrate adhesive force；The part of high molecular weight assigns the features such as better mechanical performance of lotion, toughness and temperature-change resistance.
The control of aqueous solid acrylic resin dosage can be further improved paint film strength, bonding force and water resistance.
4, the present invention is using the polymerisable emulsifier AR-10 and ER-10 compounded, the addition of two kinds of emulsifiers and two kinds of rouge
Fat adoption urethane acrylate combines, and also has the function of reducing surface of the paint film tension, can be omitted stream when preparing finishing coat
The addition of flat agent and leveling auxiliary agent still obtains excellent levelling effect.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Embodiment 1
Prepare raw material, according to parts by weight, 60 parts of styrene, 50 parts of methyl methacrylate, n-butyl acrylate 220
Part, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 4 parts of aliphatic urethane acrylate CN9002, response type polymerisable emulsifier
3 parts of AR10,3 parts of ER10,5 parts of aqueous solid acrylic resin, 1 part of initiator, 500 parts of water, ammonium hydroxide, defoaming agent, fungicide.
150 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN9002 to reaction kettle
In, 1h is stirred, monomer pre-emulsion is obtained, it is spare.
Initiator is dissolved in 50 parts of water, stirs, obtain initiator solution, it is spare.
300 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 80
DEG C, 5% monomer pre-emulsion is added, keeps the temperature 5min, sequentially adds 5% initiator solution later, and keep the temperature 30min, later
Start while remaining monomer pre-emulsion and remaining initiator solution is added dropwise, is added dropwise in 2.5h, keeps the temperature 1h later, into
Row post-processes and cools down, and adjusts pH to 7 with ammonium hydroxide later, and defoaming agent and fungicide is added, and final finished product cream is obtained after filtering
Liquid.
Embodiment 2
Prepare raw material, according to parts by weight, including 60 parts of styrene, 50 parts of methyl methacrylate, n-butyl acrylate
220 parts, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 4 parts of aliphatic urethane acrylate CN996, the polymerizable emulsification of response type
3 parts of agent AR10,3 parts of ER10,5 parts of aqueous solid acrylic resin, 2 parts of initiator, 500 parts of water, ammonium hydroxide, defoaming agent, sterilization
Agent.
100 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 to reaction kettle
In, 1.5h is stirred, monomer pre-emulsion is obtained, it is spare.
Initiator is dissolved in 30 parts of water, stirs, obtain initiator solution, it is spare.
370 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 85
DEG C, 10% monomer pre-emulsion is added, keeps the temperature 15min, sequentially adds 15% initiator solution later, and keep the temperature 40min, it
After start that remaining monomer pre-emulsion and remaining initiator solution are added dropwise simultaneously, be added dropwise in 3.5h, keep the temperature later
1.5h is post-processed and is cooled down, and adjusts pH to 8 with ammonium hydroxide later, and defoaming agent and fungicide is added, obtains after filtering final
Finished emulsion.
Embodiment 3
Prepare raw material, according to parts by weight, including 60 parts of styrene, 50 parts of methyl methacrylate, n-butyl acrylate
220 parts, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 2 parts and 2 parts of CN996 of aliphatic urethane acrylate CN9002, reaction
3 parts of type polymerisable emulsifier AR10,3 parts of ER10,5 parts of aqueous solid acrylic resin, 3 parts of initiator, 500 parts of water, ammonium hydroxide,
Defoaming agent, fungicide.
120 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are arrived
In reaction kettle, 1.2h is stirred, monomer pre-emulsion is obtained, it is spare.
Initiator is dissolved in 40 parts of water, stirs, obtain initiator solution, it is spare.
340 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 83
DEG C, 8% monomer pre-emulsion is added, keeps the temperature 10min, sequentially adds 10% initiator solution later, and keep the temperature 35min, it
After start that remaining monomer pre-emulsion and remaining initiator solution are added dropwise simultaneously, be added dropwise in 3h, keep the temperature 1.3h later,
It is post-processed and is cooled down, adjust pH to 8 with ammonium hydroxide later, defoaming agent and fungicide is added, final finished product is obtained after filtering
Lotion.
Embodiment 4
Prepare raw material, according to parts by weight, including 60 parts of styrene, 50 parts of methyl methacrylate, n-butyl acrylate
220 parts, 2 parts of methacrylic acid, 10 parts of acrylonitrile, 2 parts and 2 parts of CN996 of aliphatic urethane acrylate CN9002, reaction
3 parts of type polymerisable emulsifier AR10,3 parts of ER10,7.5 parts of aqueous solid acrylic resin, 4 parts of initiator, 500 parts of water, ammonia
Water, defoaming agent, fungicide.
130 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are arrived
In reaction kettle, 1.2h is stirred, monomer pre-emulsion is obtained, it is spare.
Initiator is dissolved in 35 parts of water, stirs, obtain initiator solution, it is spare.
335 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 82
DEG C, 3% monomer pre-emulsion is added, keeps the temperature 8min, sequentially adds 12% initiator solution later, and keep the temperature 38min, later
Start while remaining monomer pre-emulsion and remaining initiator solution be added dropwise, is added dropwise in 2.8h, keeps the temperature 1.2h later,
It is post-processed and is cooled down, adjust pH to 8 with ammonium hydroxide later, defoaming agent and fungicide is added, final finished product is obtained after filtering
Lotion.
Embodiment 5
Prepare raw material, according to parts by weight, including 60 parts of styrene, 75 parts of methyl methacrylate, n-butyl acrylate
250 parts, 4 parts of methacrylic acid, 5 parts of acrylonitrile, 3 parts and 3 parts of CN996 of aliphatic urethane acrylate CN9002, reaction
2 parts of type polymerisable emulsifier AR10,2 parts of ER10,6 parts of aqueous solid acrylic resin, 5 parts of initiator, 550 parts of water, ammonium hydroxide,
Defoaming agent, fungicide.
145 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are arrived
In reaction kettle, 1.2h is stirred, monomer pre-emulsion is obtained, it is spare.
Initiator is dissolved in 45 parts of water, stirs, obtain initiator solution, it is spare.
360 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 84
DEG C, 2% monomer pre-emulsion is added, keeps the temperature 14min, sequentially adds 11% initiator solution later, and keep the temperature 33min, it
After start that remaining monomer pre-emulsion and remaining initiator solution are added dropwise simultaneously, be added dropwise in 3.2h, keep the temperature later
1.4h is post-processed and is cooled down, and adjusts pH to 8 with ammonium hydroxide later, and defoaming agent and fungicide is added, obtains after filtering final
Finished emulsion.
Embodiment 6
Prepare raw material, according to parts by weight, including 50 parts of styrene, 60 parts of methyl methacrylate, n-butyl acrylate
200 parts, 5 parts of methacrylic acid, 2 parts of aliphatic urethane acrylate CN9002, response type polymerisable emulsifier ER10 2
Part, 2.5 parts of initiator, 450 parts of water, ammonium hydroxide, defoaming agent, fungicide.
100 parts of water intaking and response type polymerisable emulsifier ER10 stirring sufficiently, sequentially add styrene, methacrylic acid
Methyl esters, n-butyl acrylate, methacrylic acid, aliphatic urethane acrylate CN9002 stir 1.1h, obtain into reaction kettle
It is spare to monomer pre-emulsion.
Initiator is dissolved in 50 parts of water, stirs, obtain initiator solution, it is spare.
300 parts of water intaking and response type polymerisable emulsifier mix, and stir and are warming up to 82 DEG C, the 1% pre- cream of monomer is added
Liquid keeps the temperature 12min, sequentially adds 12% initiator solution later, and keep the temperature 32min, start to be added dropwise simultaneously later remaining
Monomer pre-emulsion and remaining initiator solution, are added dropwise in 2.7h, keep the temperature 1.1h later, are post-processed and are cooled down,
PH to 8 is adjusted with ammonium hydroxide later, defoaming agent and fungicide is added, final finished emulsion is obtained after filtering.
Embodiment 7
Prepare raw material, according to parts by weight, including 70 parts of styrene, 80 parts of methyl methacrylate, n-butyl acrylate
235 parts, 7 parts of methacrylic acid, 25 parts of acrylonitrile, 3 parts and 4 parts of CN996 of aliphatic urethane acrylate CN9002, reaction
5 parts of type polymerisable emulsifier AR10,3 parts of ER10,3 parts of aqueous solid acrylic resin, 3.5 parts of initiator, 580 parts of water, ammonia
Water, defoaming agent, fungicide.
130 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are arrived
In reaction kettle, 1h is stirred, monomer pre-emulsion is obtained, it is spare.The present embodiment be added herein polyurethanes monomer CN9002 and
CN996 is pre-processed, and is first used supersonic oscillations 3-5min, is then washed 0.2-0.3s with nitrogen.Aliphatic polyurethane propylene
The pretreatment of acid esters both makes mutual support functionally, can play drop so that it is more preferable with the associativity of two kinds of emulsifiers
The effect of the surface tension of low monomer and water makes monomer and water form a stable homogeneous system, plays synergistic work
With, pigment, filler can be infiltrated faster when preparing finishing coat, and be deep into face, filler particles aggregation hole in, to mention
The stability of Gao Yan, filler dispersion effect and emulsion system make finishing coat have preferably wetting, attachment and leaching to electrophoretic primer surface
Saturating effect, levelability are improved, and keep film surface smoother, glossiness is higher.
Initiator is dissolved in 50 parts of water, stirs, obtain initiator solution, it is spare.
400 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 80
DEG C, 4% monomer pre-emulsion is added, keeps the temperature 7min, sequentially adds 10% initiator solution later, and keep the temperature 30min, later
Start while remaining monomer pre-emulsion and remaining initiator solution is added dropwise, is added dropwise in 2.5h, keeps the temperature 1h later, into
Row post-processes and cools down, and adjusts pH to 8 with ammonium hydroxide later, and defoaming agent and fungicide is added, and final finished product cream is obtained after filtering
Liquid.
The effect of ammonium hydroxide of the present invention is not only for pH value is adjusted, since the present invention is using special polyurethanes
Monomer CN9002 and CN996, and it is pre-processed, it is found surprisingly that it also to pretreated aliphatic polyurethane third
The effect of olefin(e) acid ester, can enhance cross-linking effect, accelerate curing rate, reduce the generation of stomata, further increase solidification regularity.
Embodiment 8
Prepare raw material, according to parts by weight, including 80 parts of styrene, 100 parts of methyl methacrylate, n-butyl acrylate
250 parts, 10 parts of methacrylic acid, 50 parts of acrylonitrile, 5 parts and 3 parts of CN996 of aliphatic urethane acrylate CN9002, instead
Answer 4 parts of type polymerisable emulsifier AR10,6 parts of ER10,10 parts of aqueous solid acrylic resin, 4.5 parts of initiator, 600 parts of water,
Ammonium hydroxide, defoaming agent, fungicide.
150 parts of water intaking and response type polymerisable emulsifier AR10, ER10 stirring sufficiently, sequentially add styrene, methyl
Methyl acrylate, n-butyl acrylate, methacrylic acid, acrylonitrile, aliphatic urethane acrylate CN996 and CN9002 are arrived
In reaction kettle, 1h is stirred, monomer pre-emulsion is obtained, it is spare.The present embodiment be added herein polyurethanes monomer CN9002 and
CN996 is pre-processed, and is first used supersonic oscillations 3-5min, is then washed 0.2-0.3s with nitrogen.
Initiator is dissolved in 50 parts of water, stirs, obtain initiator solution, it is spare.
400 parts of water intaking and response type polymerisable emulsifier, aqueous solid acrylic resin mix, and stir and are warming up to 85
DEG C, 6% monomer pre-emulsion is added, keeps the temperature 12min, sequentially adds 7% initiator solution later, and keep the temperature 34min, later
Start while remaining monomer pre-emulsion and remaining initiator solution is added dropwise, is added dropwise in 3h, keeps the temperature 1.5h later, into
Row post-processes and cools down, and adjusts pH to 8 with ammonium hydroxide later, and defoaming agent and fungicide is added, and final finished product cream is obtained after filtering
Liquid.
Comparative example
The raw materials such as existing acrylic acid-polyurethane emulsion, including acrylic compounds, polyurethanes, emulsifier, the poly- ammonia of selection
Polyurethane, the emulsifier of ester, emulsifier and non-present invention.
Two, coating application performance test and characterization
The acrylic emulsion prepared according to the method described above is carried out to the survey of application performance with the competing product lotion bought on the market
Examination comparison.It is mainly compared from the following aspects: water resistance, adhesive force test and levelability etc..
1, the comparison of water resistance
Prepared lotion knifing drying is subjected to soaked, the variation of observation paint film water resistance afterwards for 24 hours.
| Soaked 12h | It is soaked for 24 hours | Soaked 38h | |
| Embodiment 1 | It is not any change | It is not any change | Slight blueing |
| Embodiment 2 | It is not any change | It is not any change | Slight blueing |
| Embodiment 3 | It is not any change | It is not any change | Slight blueing |
| Embodiment 4 | It is not any change | It is not any change | Slight blueing |
| Embodiment 5 | It is not any change | It is not any change | Slight blueing |
| Embodiment 6 | It is not any change | It is not any change | Slight blueing |
| Embodiment 7 | It is not any change | It is not any change | Slight blueing |
| Embodiment 8 | It is not any change | It is not any change | Slight blueing |
| Comparative example | Slight blueing | Obvious blueing | Serious blueing |
| Competing product lotion | Slight blueing | Obvious blueing | Serious blueing |
2, adhesive force is tested
The acrylic emulsion of preparation to be matched into lacquering, is sprayed on after electrophoretic primer, the method for lattice of crossing tests adhesive force,
Acquired results are as follows:
| Adhesion results | Score value | |
| Embodiment 1 | Paint film is complete, no any to fall off | 5 |
| Embodiment 2 | Paint film is complete, no any to fall off | 5 |
| Embodiment 3 | Paint film is complete, no any to fall off | 5 |
| Embodiment 4 | Paint film is complete, no any to fall off | 5 |
| Embodiment 5 | Paint film is complete, no any to fall off | 5 |
| Embodiment 6 | Paint film is complete, no any to fall off | 5 |
| Embodiment 7 | Paint film is complete, no any to fall off | 5 |
| Embodiment 8 | Paint film is complete, no any to fall off | 5 |
| Comparative example | Pull-away is serious | 2 |
| Competing product lotion | Pull-away is serious | 2 |
Wherein 5 points it is best, paint film is without falling off and any variation；1 point worst, and paint film is completely fallen off.
3, levelability
The acrylic emulsion of preparation is matched into lacquering, is sprayed on after electrophoretic primer, paint film levelling situation, acquired results are observed
It is as follows:
| Levelability | |
| Embodiment 1 | Slight fold |
| Embodiment 2 | Levelling is very good |
| Embodiment 3 | Levelling is very good |
| Embodiment 4 | Slight fold |
| Embodiment 5 | Levelling is very good |
| Embodiment 6 | Slight fold, levelability are low compared with other |
| Embodiment 7 | Levelling is very good |
| Embodiment 8 | Levelling is very good |
| Comparative example | Paint film fold, is sprawled not open |
| Competing product lotion | Paint film fold, is sprawled not open |
It in summary it can be seen, acrylic emulsion of the present invention has good water resistance, has very on automobile electrophoretic primer
Good adhesive force and levelability, the competing product lotion for being better than comparative example lotion and buying on the market, in water-based automobile paint market
On have good application prospect.
4, the performance of lotion
Note: Calcium ion stability: by 1%, 3%, 5%CaCl2Solution is uniformly mixed with lotion with 4:1 (mass ratio), quiet
Observation is without layering or gel, i.e., qualified after setting 72h.
Centrifugal stability: take 1ml lotion injection centrifuge tube in, be put into height centrifuge, with 12000r/min,
20000r/min, centrifugation 60min, observe emulsion state, not to be demulsified as qualification.
5, the performance for the finishing coat that lotion is configured to
Note: levelling agent, leveling auxiliary agent, anti ultraviolet agent, age resister are not contained in finishing coat of the present invention.Comparative example prepares finishing coat
Contain.
Water resistance: 5 points best, unchanged without blistering and fall off；1 point worst.
Adhesive force: 5 points best, and paint film is without falling off；1 point worst.
QUV: the unchanged no color differnece of level-one paint film；Pyatyi is worst, and paint film has serious color difference.
According to above-mentioned data it is found that being found surprisingly that, levelling agent, leveling auxiliary agent, anti ultraviolet agent, age resister are not being contained
Deng auxiliary agent in the case of, the levelling effect of paint film of the invention is good, and still have excellent ultraviolet-resistent property, analyze as due to two
Kind emulsifier polymerize with two kinds of urethane crosslinks, interferes ultraviolet light in interface oriented attachment, so that paint film has anti-purple
Outer property, thus can be omitted when preparing finishing coat the addition of age resister or anti ultraviolet agent, while avoiding because of age resister
Or the addition of anti ultraviolet agent causes the defect of surface of the paint film shrinkage cavity.
Claims (7)
1. being used for the aqueous acrylic emulsion of automobile electrophoresis finish, which is characterized in that according to parts by weight, including styrene
50-80 parts, 50-100 parts of methyl methacrylate, 200-250 parts of n-butyl acrylate, 2-10 parts of methacrylic acid, acrylonitrile
0-50 parts, 1-8 parts of aliphatic urethane acrylate, 3-15 parts of response type polymerisable emulsifier, aqueous solid acrylic resin
0-10 parts, 1-5 parts of initiator, 430-600 parts of water, 0-5 parts of ammonium hydroxide, 0-3 parts of defoaming agent, 0-3 parts of fungicide.
2. the aqueous acrylic emulsion according to claim 1 for automobile electrophoresis finish, which is characterized in that response type
Polymerisable emulsifier is emulsifier of the one end with double bond, participation emulsion polymerization.
3. the aqueous acrylic emulsion according to claim 1 for automobile electrophoresis finish, which is characterized in that described
Aliphatic urethane acrylate is aliphatic urethane acrylate CN9002 and/or aliphatic urethane acrylate
CN996。
4. the aqueous acrylic emulsion according to claim 3 for automobile electrophoresis finish, which is characterized in that aliphatic
The compound proportion of urethane acrylate CN9002 and aliphatic urethane acrylate CN996 are 2:8 to 8:2.
5. the aqueous acrylic emulsion according to claim 1 for automobile electrophoresis finish, which is characterized in that described
Aqueous solid acrylic resin is BASF 678 or Han Hua 60L, 70 Han Hua, Han Hua 74, Han Hua 90 one such or more
Kind is used in combination.
6. the aqueous acrylic emulsion according to claim 1 for automobile electrophoresis finish, which is characterized in that described
Initiator is one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
7. the preparation method of the aqueous acrylic emulsion for automobile electrophoresis finish, which comprises the following steps:
A, raw material preparation: pressing following portions by weight, weigh 50-80 parts of styrene, and 50-100 parts of methyl methacrylate, acrylic acid
200-250 parts of N-butyl, 2-10 parts of methacrylic acid, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic urethane acrylate, reaction
2-10 parts of type polymerisable emulsifier, 0-10 parts of aqueous solid acrylic resin, 1-5 parts of initiator, 430-600 parts of water, ammonium hydroxide 0-5
Part, it is 0-3 parts of defoaming agent, 0-3 parts of fungicide, spare；
B, the preparation of monomer pre-emulsion: 100-150 parts of water intaking, 2-10 parts of response type polymerisable emulsifier stirrings are abundant, then successively
Styrene 50-80 parts of addition, 50-100 parts of methyl methacrylate, 200-250 parts of n-butyl acrylate, methacrylic acid 2-10
Part, 0-50 parts of acrylonitrile, 1-8 parts of aliphatic urethane acrylate, into reaction kettle, are stirred 1-1.5h, obtain the pre- cream of monomer
Liquid；
C, the preparation of initiator solution: initiator being dissolved in 30-50 parts of water, and stirring obtains initiator solution, spare；
D, the preparation of lotion: 300-400 parts of water intaking and 1-5 parts of response type polymerisable emulsifier and aqueous solid acrylic resin 0-
10 parts of mixing, stir and are warming up to 80-85 DEG C, and the monomer pre-emulsion of 1-10% is added, and keep the temperature 515min, 5-15% is added later
Initiator solution, and keep the temperature 30-40min, start that remaining monomer pre-emulsion is added dropwise simultaneously later and remaining initiator is molten
Liquid is added dropwise in 2.5-3.5h, keeps the temperature 1-1.5h later, is post-processed and is cooled down, and then adjusts pH to 7- with ammonium hydroxide
8, defoaming agent and fungicide is added, final finished emulsion is obtained after filtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811603421.8A CN109705278B (en) | 2018-12-26 | 2018-12-26 | Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811603421.8A CN109705278B (en) | 2018-12-26 | 2018-12-26 | Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109705278A true CN109705278A (en) | 2019-05-03 |
| CN109705278B CN109705278B (en) | 2021-10-08 |
Family
ID=66258505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811603421.8A Active CN109705278B (en) | 2018-12-26 | 2018-12-26 | Water-based acrylic emulsion for automobile electrophoresis finish paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705278B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN113265182A (en) * | 2021-06-23 | 2021-08-17 | 广东金万联防水材料有限公司 | Preparation method of novel waterproof coating |
| CN114456671A (en) * | 2020-08-31 | 2022-05-10 | 北京国原新技术有限公司 | Coating and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532735A (en) * | 1991-07-31 | 1993-02-09 | Mitsubishi Rayon Co Ltd | Composition for plastic lens and production of plastic lens |
| US20110287190A1 (en) * | 2010-01-15 | 2011-11-24 | Texas Research International, Inc. | Ultraviolet light curing compositions for composite repair |
| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
| CN107523143A (en) * | 2017-08-08 | 2017-12-29 | 江苏丽王科技股份有限公司 | A kind of general no fat mill base of water nano and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811603421.8A patent/CN109705278B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532735A (en) * | 1991-07-31 | 1993-02-09 | Mitsubishi Rayon Co Ltd | Composition for plastic lens and production of plastic lens |
| US20110287190A1 (en) * | 2010-01-15 | 2011-11-24 | Texas Research International, Inc. | Ultraviolet light curing compositions for composite repair |
| CN106147672A (en) * | 2015-04-07 | 2016-11-23 | 宏峰行化工(深圳)有限公司 | A kind of for moulding/mould compound aqueous polyurethane acrylate binding agent and preparation method thereof |
| CN107523143A (en) * | 2017-08-08 | 2017-12-29 | 江苏丽王科技股份有限公司 | A kind of general no fat mill base of water nano and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 彭嘉明: "木器高光面漆用丙烯酸酯树脂的制备与性能研究", 《涂料工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456671A (en) * | 2020-08-31 | 2022-05-10 | 北京国原新技术有限公司 | Coating and preparation method and application thereof |
| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN113265182A (en) * | 2021-06-23 | 2021-08-17 | 广东金万联防水材料有限公司 | Preparation method of novel waterproof coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109705278B (en) | 2021-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705278A (en) | Aqueous acrylic emulsion and preparation method thereof for automobile electrophoresis finish | |
| US6538059B1 (en) | Polymer | |
| CN101153155A (en) | Priming coating composition and preparation method thereof | |
| CN110317298B (en) | Water-based chlorinated polypropylene modified acrylic resin for PP plastic coating and preparation method thereof, paint and paint preparation method | |
| JP2002542350A (en) | polymer | |
| CN104744639B (en) | A kind of preparation method of organic-silicon-modified normal-temperature multiple self-cross-linking epoxy resin emulsion | |
| WO1997030097A1 (en) | Waterborne coating compositions | |
| CN108997925A (en) | A kind of coloured dual cure UV coating of automotive upholstery | |
| CN110028858A (en) | A kind of wettable matched paint for squirting construction and preparation method thereof and construction technology | |
| CN109666396A (en) | Novel water-based low-gloss ultraviolet curing coating and preparation and use methods thereof | |
| CN110028617A (en) | A kind of no soap self-crosslinking nanometer acrylic emulsion and its synthesis technology and application | |
| CN107177299B (en) | Aqueous middle painting coating composition and preparation method thereof for the vehicles | |
| US5166272A (en) | Emulsion polymers and coating compositions prepared therefrom | |
| CN109280477A (en) | A kind of preparation method of coloured dual cure UV coating | |
| CN106675295A (en) | Finish-coat-free matte water-based colored paint and preparation method thereof | |
| CN108276890A (en) | A kind of aqueous automobile floating coating composition and preparation method thereof | |
| US20220235239A1 (en) | Thermoplastic gel coat | |
| CN102086332B (en) | Coating composition for polyolefin substrate and coating and product thereof | |
| CN101691693B (en) | Water PU polish processing agent for synthetic leather | |
| CN1355267A (en) | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure | |
| US5225456A (en) | Aqueous polyacrylate dispersion for coatings | |
| CN107513325A (en) | Thick slurry anticorrosive paint of a kind of weather resistant epoxy and preparation method thereof | |
| CN109868051A (en) | A kind of wooden furniture high aloof from politics and material pursuits polyurethane matte finishing coat of high-solid lower-viscosity and preparation method thereof | |
| CN109608960A (en) | A kind of preparation method of automobile finish | |
| CN109836991A (en) | A kind of automobile interior decoration water transfer spraying UV gloss oil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 512400 5 North Road, Nanxiong fine chemical park, Shaoguan, Guangdong. Applicant after: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Address before: 512400 Dalingshan (Nanxiong) Industrial Transfer Industrial Park, Dongguan City, Guangdong Province, No. 5 North National Road Applicant before: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Waterborne acrylic lotion for automotive electrophoretic finish and its preparation method Effective date of registration: 20230506 Granted publication date: 20211008 Pledgee: Agricultural Bank of China Limited Nanxiong Sub branch Pledgor: GUANGDONG HENGGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980039881 |