CN106700875B - A kind of aqueous milling protection stripping lacquer and preparation method thereof - Google Patents
A kind of aqueous milling protection stripping lacquer and preparation method thereof Download PDFInfo
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Abstract
A kind of aqueous milling protection stripping lacquer and preparation method thereof; the coating includes 16%~25% water-borne dispersions; 20%~30% aqueous polyurethane can peelable resin, 6%~8% waterborne polyester polyurethane can peelable resin, 0.5%~1.5% aqueous silicone oil; 40%~45% slurry; 0.3%~1% defoaming agent, 4%~10% deionized water and 2%~6% thickener; wherein, the water-borne dispersions are by acrylate modified SBS resin and C5Hydrogenated petroleum resin is compounded and is obtained, and the acrylate modified SBS resin is obtained by hydrophilic acrylate modified SBS resin.The present invention by milling protective coating SBS thermoplastic elastomer (TPE) success Water-borne modification; the milling protective coating of preparation has excellent water resistance and alkali resistance; solve the problems, such as it is aqueous can peelable resin poor water resistance and adhesion is poor in chemical milling solution, realize milling protective coating Water-borne modification.
Description
Technical field
The present invention relates to paint fields, and in particular to a kind of aqueous milling protection stripping lacquer and preparation method thereof.
Background technique
Chemistry milling processing (abbreviation milling) is by chemical solution (acid solution, alkaline solution) to surface of workpiece
A kind of processing technology of dissolution utilizes the method workpieces processing of chemolysis.Compared with machining process, milling technique
Simply, quickly, the especially big thin material of area can only use chemistry milling that can just be processed to speed.
Milling protective coating is mainly one of chemistry milling process temporary protective coat, is played in process
Temporary protective effect, milling process remove the protective layer after the completion again, are mainly used in the chemistry milling of aluminium alloy, titanium alloy
The artistic products engraving of processing, the processing of high rigidity metal, the anodization of aluminium alloy, plating and complex process processes provisional guarantor
Shield, it may also be used for the anti-chemical corrosion masking protection in coated article face, or as preventing from scratching scratch on instrument surface, mechanical equipment
Interim protection field.
Water resistance and chemical resistance are always that water paint is difficult to the problem of capturing, and milling protective coating is being constructed and made
There are good water resistance and chemical resistance with paint film is generally required in the process.The water resistance of existing commercially available aqueous stripping lacquer and
Chemical resistance is poor, and in water after long period of soaking, and adhesive force and tensile strength sharp fall, adhesion is poor, and film is from substrate
Surface is detached from, and loses the protection to substrate.Therefore, a kind of low VOC emission is prepared, environmental-friendly, water resistance and chemical resistance are good,
Smaller on adhesive force and tensile strength influence after long period of soaking, the good aqueous milling protective coating of fissility becomes milling protection and applies
Expect the Main way of future development.
The chemistry milling protective coating used both at home and abroad at present is solvent based coating, mainly there is external Henkel KGaA
The HX-150 of TURCO5580G, the AC-850 of AC company of the U.S. and domestic North Paint & Coating Industry Research and Design Insitute of China Haohua Chemical (Group) Corporation
(HX-500) chemistry milling protective coating, these existing chemistry milling protective coatings are all often to utilize toluene, dimethylbenzene, tetrachloro
The non-environmental protections type organic solvent such as ethylene is as diluent, and at high cost, smell is big, and environmental pollution is serious, is used for a long time to applying
Each organ of the body of work person causes seriously to damage.
Summary of the invention
The object of the present invention is to provide a kind of aqueous milling protection stripping lacquer and preparation method thereof, the milling protective coatings
With excellent water resistance and alkali resistance, solve it is aqueous can peelable resin poor water resistance and adhesion difference is asked in chemical milling solution
Topic realizes milling protective coating Water-borne modification.
In order to achieve the above objectives, main technical schemes of the invention are as follows:
A kind of aqueous milling protection stripping lacquer, including following component, by mass percentage:
The water-borne dispersions are by acrylate modified SBS resin and C5Hydrogenated petroleum resin is compounded and is obtained, and is specifically included
Following component, by mass percentage:
Wherein, the acrylate modified SBS resin includes following component, by mass percentage:
The formula of the slurry is, by mass percentage:
Wherein, the wetting dispersing agent is at least one of BYK-151, BYK-333, BYK-154, BYK-2012.
The levelling agent is at least one of BYK-380N, BYK-420, BYK-425, BYK-381.
Preferably, the defoaming agent be BYK-028, BYK-024, BYK-011, BYK-094BYK-1711 at least
It is a kind of.
Preferably, the thickener is at least one of RM-2020, BYK-425.
Again, the emulsifier in the water-borne dispersions is emulsifier CO436, is commercial industrial product.
Preferably, the mixed solvent in the acrylate modified SBS resin is hexamethylene, in butanone, cyclohexanone, toluene
At least one.
Preferably, the initiator in the acrylate modified SBS resin is benzoyl peroxide or azodiisobutyronitrile.
Heretofore described aqueous polyurethane can peelable resin, waterborne polyester polyurethane can peelable resin be commercially available industrial goods.
Further, the preparation method of acrylate modified SBS resin of the present invention is stocked up according to above-mentioned formula,
Mainly include the following steps: uniformly for SBS resin to be dissolved into 60~65% in the mixed solvent, be added in reaction system,
It is warming up to 80 ± 5 DEG C；In the case where system reflux, methyl methacrylate, butyl acrylate, methyl-prop are added dropwise into system
The mixed liquor of olefin(e) acid, initiator and remaining mixed solvent, time for adding are controlled in 3h ± 10min；1h is kept the temperature after being added dropwise completely
± 10min is cooled to 30 DEG C or less filtering and dischargings to get acrylate modified SBS resin of the invention.
The preparation method of water-borne dispersions of the present invention is stocked up according to above-mentioned formula, is mainly included the following steps:
By C5Hydrogenated petroleum resin is dissolved in toluene, and the acrylate modified SBS resin prepared is added, is warming up to 80 ± 5 DEG C, obtains
To oiliness mixed system；Emulsifier is distributed in the deionized water that temperature is 90 ± 5 DEG C, obtains emulsifier water granular media；?
Under the revolving speed at least stirring condition of 3000r/min, emulsifier water granular media is added drop-wise in oiliness mixed system, time for adding control
System during 30 ± 5min, dropwise addition emulsifier water granular media temperature be maintained at 90 ± 5 DEG C, after dripping continue revolving speed at least
It is stirred under conditions of 3000r/min, filtering and discharging is to get water-borne dispersions of the invention.
The preparation method of slurry of the present invention, formula stock, mainly includes the following steps: face as described above
Filler (i.e. white carbon black, titanium dioxide, talcum powder, kaolin and bentonite) and auxiliary agent (wetting dispersing agent and levelling agent) are separately added into
Into quick worker's bottle, deionized water and bead are added, grinding distribution obtains slurry of the invention in quick worker's disperse mill
Material.
The preparation method of aqueous milling protective coating of the present invention, formula is stocked up as described above, mainly includes
Following steps: by aqueous polyurethane can peelable resin, waterborne polyester polyurethane can peelable resin, water-borne dispersions, slurry, deionized water
Be added in beaker with aqueous silicone oil, stir 30 ± 5min, be added defoaming agent continue 30 ± 5min of stirring, revolving speed at least
Thickener is added dropwise under the stirring condition of 700r/min and reaches required working viscosity, continues 20 ± 5min of stirring, filtering and discharging,
Stripping lacquer is protected up to aqueous milling.
The present invention is directed to the requirement of chemistry milling processing, has synthesized a kind of water resistance and the good hydrophilic acrylic of alkali resistance
Ester modified SBS resin, the acrylate modified SBS resin and C5Water-borne dispersions are prepared in hydrogenated petroleum resin compounding.Water
Property dispersion and strong alkali resistance it is aqueous can peelable resin compounding to be prepared for water resistance, alkali resistance good, and long period of soaking is to coating
Adhesion, the anti-intensity effect that rises are smaller, and stripping lacquer is protected in the aqueous milling temporarily protected suitable for chemistry milling.
The present invention uses hydrophilic acrylate modified SBS resin, successfully accesses hydrophilic radical in SBS resin,
The bridge of oleaginous system and water-based system is made, thus realization and C5Hydrogenated petroleum resin compounding prepares water-borne dispersions.
Gained water-borne dispersions can improve it is aqueous can peelable resin water resistance and alkali resistance, and improve aqueous stripping lacquer in the hot water
Tensile strength after long period of soaking and the adhesion with substrate, finally by milling protective coating successfully Water-borne modification, and guaranteeization
The progress of miller skill.
Beneficial effects of the present invention:
1) hydrophilic acrylate modified SBS tree is successfully prepared using acrylate modified SBS resin in the present invention
Rouge makes water resistance and alkali resistance in aqueous peelable resin system be improved so that oleaginous system and water-based system be combined, and
Successfully by the SBS thermoplastic elastomer (TPE) success Water-borne modification in milling protective coating, and then replace having using water cheap and easy to get
Solvent, the drawbacks of reducing because of VOC emission environmental pollution, the aqueous milling protection for being successfully made environmentally friendly is peelable
Coating.
2) present invention uses C5Hydrogenated petroleum resin compounds acrylate modified SBS resin and prepares water-borne dispersions, mentions
It is high it is aqueous can peelable resin tensile strength and adhesive force, it is not easy to break when removing paint film, and during milling, avoid
Due to impregnated for a long time in buck decline paint film adhesion and cause milling while " when running " phenomenon generation, in milling plus
It ensure that the grazing on milling side during work.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but the contents of the present invention and unlimited
In this.
Raw material used in embodiment and comparative example are except being technical grade commercially available product in the present invention (specialty goods is otherwise noted).
The present embodiment demonstrates acrylate modified SBS resin and C5The water-borne dispersions and water of hydrogenated petroleum resin compounding
Property milling protection stripping lacquer preparation.
Embodiment 1
(1) preparation of acrylate modified SBS resin: molten with the mixing that the ratio of 1:1 prepares 100g hexamethylene and butanone
6.0g SBS resin is added to stirring (revolving speed 700r/min) in the three-necked flask equipped with 60.0g mixed solvent and is allowed to by agent
Dissolution, heats to 75 DEG C, system starts to flow back.35.0g methyl methacrylate, 57.0g third are separately added into beaker
Olefin(e) acid butyl ester, 1.4g methacrylic acid, 0.60g initiator benzoyl peroxide and residue 40.0g mixed solvent, after mixing evenly
It is slowly added dropwise into the three-necked flask equipped with SBS resin, time for adding 3h.1h is kept the temperature after being added dropwise completely, cooling filters out
Expect to get acrylate modified SBS resin is arrived.
(2) acrylate modified SBS resin and C5The preparation of the water-borne dispersions of hydrogenated petroleum resin compounding: 72.0g is taken
C5Hydrogenated petroleum resin is dissolved in 90.0g toluene, is stirred evenly, and the acrylate modified SBS resin 23.0g made is added,
Heating stirring makes whole system temperature be increased to 80 DEG C, obtains oiliness mixed system.25.0g emulsifier CO436 is distributed to
In 90 DEG C of the deionized water of 140.0g, heat emulsifier dispersion is obtained.It is taking revolving speed as the condition of 3200r/min high-speed stirred
The lower emulsifier dispersion by heat is slowly added drop-wise in the oiliness mixed system of heat (80 DEG C of system temperature of this process holding is constant),
Time for adding is 25min, with 3500r/min high-speed stirred 20 minutes after dripping, is cooled to 30 DEG C, and filtering and discharging is to get arriving
Acrylate modified SBS resin and C5The water-borne dispersions of hydrogenated petroleum resin compounding.
(3) preparation of slurry: quick worker bottle in sequentially add 5.0g white carbon black, 5.0g titanium dioxide, 20.0g talcum powder,
28.0g kaolin, 0.9g bentonite, 40.0g deionized water, are stirring evenly and then adding into 0.3g BYK-381,0.8g BYK-151
It is stirring evenly and then adding into 56.0g bead, quick worker's bottle is put into quick worker's disperse mill and disperses 2h, filtering obtains slurry.
(4) preparation of aqueous milling protection stripping lacquer: take 28.0g aqueous polyurethane can peelable resin (road profit chemistry respectively
Technology Co., Ltd.), 6.0g waterborne polyester polyurethane can peelable resin (the lucky Chemical Co., Ltd. in Zhuhai), the aqueous silicone oil of 0.5g,
The acrylate modified SBS resin of 18.0g and C5The water-borne dispersions of hydrogenated petroleum resin compounding are added to equipped with 4.0g deionization
In the beaker of water water, uniformly, 41.0g slurry is added in stirring (revolving speed 700r/min), continues to stir 20min, 0.5g is added
After BYK-028 stirs (revolving speed 700r/min) 20min, (10~15d/min of rate of addition) thickener RM- is slowly added dropwise
2020, it can be good at implementing doctor blade process when 2.0g thickener RM-2020 is added just, continue to stir (revolving speed 700r/min)
10min, filtering and discharging protect stripping lacquer to get to aqueous milling.
The performance test results of the aqueous milling protection stripping lacquer of the present embodiment preparation gained are referring to table 1.
Embodiment 2
(1) preparation of acrylate modified SBS resin: 10.0Kg is prepared with the ratio of 3:4 with hexamethylene and cyclohexanone and is mixed
0.6Kg SBS Petropols are added to stirring (revolving speed 800r/min) in the reaction kettle equipped with 7.0Kg mixed solvent by bonding solvent
It is allowed to dissolve, heats to 75 DEG C, system starts to flow back.Be separately added into beaker 3.8Kg methyl methacrylate,
5.4Kg butyl acrylate, 0.15Kg methacrylic acid, 0.05Kg azodiisobutyronitrile and residue 3.0Kg mixed solvent, stirring are equal
It is slowly added dropwise in the even backward reaction kettle equipped with SBS resin solution, time for adding 3.1h.1.1h, drop are kept the temperature after being added dropwise completely
Temperature, filtering and discharging to get arrive acrylate modified SBS resin.
(2) acrylate modified SBS resin and C5The preparation of the water-borne dispersions of hydrogenated petroleum resin compounding: 8.5Kg is taken
C5Hydrogenated petroleum resin is dissolved in 9.0Kg toluene, is stirred evenly, and the acrylate modified SBS resin 2.5Kg made is added,
Heating stirring (revolving speed 800r/min) makes whole system temperature be increased to 80 DEG C, obtains oiliness mixed system.By 4.0Kg emulsifier
CO436 is distributed in 90 DEG C of deionized waters of 16.0Kg, obtains heat emulsifier dispersion.It is being 3400r/min high speed with revolving speed
Under conditions of stirring by heat emulsifier dispersion be slowly added drop-wise to heat oiliness mixed system in (this process keep system temperature not
Become), time for adding 30min, with 3500r/min high-speed stirred 20min after dripping, cooling, filtering and discharging is to get arriving propylene
Acid esters modified SBS resin and C5The water-borne dispersions of hydrogenated petroleum resin compounding.
(3) preparation of slurry: sequentially added in material-compound tank 0.6Kg white carbon black, 0.6Kg titanium dioxide, 1.8Kg talcum powder,
2.8Kg kaolin, 0.1Kg bentonite, 4.0Kg deionized water, are stirring evenly and then adding into 0.02Kg BYK-381,0.08Kg
After BYK-2012 stirs (revolving speed 800r/min) uniformly, with basket type sand grid grinding machine grinding distribution 2h, filtering obtains slurry.
(4) preparation of aqueous milling protection stripping lacquer: take 2.5Kg aqueous polyurethane can peelable resin (one hundred source of Beijing respectively
Chemical Co., Ltd.), 0.75Kg waterborne polyester polyurethane can peelable resin (one hundred source Chemical Co., Ltd. of Beijing), the aqueous silicon of 0.07Kg
Oil, the acrylate modified SBS resin of 1.8Kg and C5Hydrogenated petroleum resin compounding aqueous dispersion be added to equipped with 0.6Kg go from
It in the material-compound tank of sub- water, stirs evenly, 4.0Kg slurry is added, continue to stir 30min, 0.03Kg BYK-011 stirring is added
Thickener RM-2020 is added dropwise after 30min, can be good at implementing doctor blade process when 0.25Kg thickener RM-2020 is added, continue
20min is stirred, filtering and discharging protects stripping lacquer to get to aqueous milling.
The performance test results of the aqueous milling protection stripping lacquer of the present embodiment preparation gained are referring to table 1.
Embodiment 3
(1) preparation of acrylate modified SBS resin: molten with the mixing that the ratio of 1:1 prepares 200g hexamethylene and toluene
12.0g SBS Petropols are added to stirring in the three-necked flask equipped with 140.0g mixed solvent and are allowed to dissolve by agent, and heating rises
To 75 DEG C, system starts to flow back temperature.Be separately added into beaker 74.0g methyl methacrylate, 110.0g butyl acrylate,
2.8g methacrylic acid, 1.2g benzoyl peroxide and residue 60.0g mixed solvent, drop after stirring (revolving speed 700r/min) uniformly
It is added in the three-necked flask equipped with SBS resin, time for adding 2.8h.1.2h is kept the temperature after being added dropwise completely, is cooled down, filtering and discharging,
Obtain acrylate modified SBS resin.
(2) acrylate modified SBS resin and C5The preparation of the water-borne dispersions of hydrogenated petroleum resin compounding: 150.0g is taken
C5Hydrogenated petroleum resin is dissolved in 176g toluene, is stirred evenly, and the acrylate modified SBS resin 50.0g made is added, adds
Thermal agitation makes whole system temperature be increased to 85 DEG C, obtains oiliness mixed system.66.0g emulsifier CO436 is distributed to
In 90 DEG C of the deionized water of 308.0g, heat emulsifier dispersion is obtained.It is taking revolving speed as the condition of 3200r/min high-speed stirred
The lower emulsifier dispersion by heat is slowly added drop-wise in the oiliness mixed system of heat (this process keeps system temperature-resistant), is added dropwise
Time is 25min, with 3500r/min high-speed stirred 20min after dripping, is cooled down, and filtering and discharging is acrylate modified to get arriving
SBS resin and C5The water-borne dispersions of hydrogenated petroleum resin compounding.
(3) 5.0g white carbon black, 7.0g titanium white, 20.0g talcum powder, 26.0g the preparation of slurry: are sequentially added in quick worker's bottle
It is equal to be stirring evenly and then adding into 0.3g BYK-420,0.7g BYK-154 stirring for kaolin, 1.0g bentonite, 40.0g deionized water
60g bead is added after even, quick worker's bottle is put into quick worker's disperse mill and disperses 2h, filtering obtains slurry.
(4) preparation of aqueous milling protection stripping lacquer: take 20.0g aqueous polyurethane can peelable resin (Guangzhou sky standing grain respectively
Chemical products Co., Ltd), 8.0g waterborne polyester polyurethane can peelable resin (the lucky Chemical Co., Ltd. in Zhuhai), the aqueous silicon of 0.5g
Oil, the acrylate modified SBS resin of 20.0g and C5The aqueous dispersion of hydrogenated petroleum resin compounding is added to equipped with 4.0g deionization
In the beaker of water, uniformly, 45.0g slurry is added in stirring (revolving speed 700r/min), continues to stir 20min, 0.5g BYK- is added
2.0g thickener BYK-425 is added dropwise after 1711 stirring 20min, can be good at implementing doctor blade process, continues to stir 10min, mistake
It filters out material and protects stripping lacquer to get to aqueous milling.
The performance test results of the aqueous milling protection stripping lacquer of the present embodiment preparation gained are referring to table 1.
The aqueous milling protection stripping lacquer product of embodiment 1-3 is applied on aluminium sheet, in the drying 3 days of (35 DEG C) of lamp box
Afterwards, quarter type carries out chemistry milling technique (referring in particular to People's Republic of China (PRC) Aviation Industry standard HB 5453-2004), test
As a result referring to table 1.
As shown in Table 1, paint film warp during milling, after aqueous milling protection stripping lacquer spraying prepared by the present invention
After long-time chemical solvent impregnates, when paint film is without running, no volume is stuck up, and milling side grazing is good, and illustrating paint film still has very for milling
Good adhesive force, ensure that the grazing on milling side, and etch ratio also complies with milling technology requirement, and paint film is easy stripping after milling
It removes.
Table 1
Claims (7)
1. stripping lacquer, including following component are protected in a kind of aqueous milling, by mass percentage:
Wherein, the water-borne dispersions are by acrylate modified SBS resin and C5Hydrogenated petroleum resin is compounded and is obtained, and is specifically included
Following component, by mass percentage:
Wherein, the emulsifier in the water-borne dispersions be emulsifier C0436, the preparation method of the water-borne dispersions it is main
Include the following steps: C5Hydrogenated petroleum resin is dissolved in toluene, and the acrylate modified SBS resin prepared is added, and is risen
Temperature obtains oiliness mixed system to 80 ± 5 DEG C；Emulsifier is distributed in the deionized water that temperature is 90 ± 5 DEG C, is emulsified
Agent aqueous dispersion；Under the revolving speed at least stirring condition of 3000r/min, emulsifier water granular media is added drop-wise to oiliness mixed system
In, time for adding control emulsifier water granular media temperature during 30 ± 5min, dropwise addition is maintained at 90 ± 5 DEG C, after dripping
Continuation is stirred under conditions of revolving speed at least 3000r/min, and filtering and discharging is to get the water-borne dispersions；
The acrylate modified SBS resin includes following component, by mass percentage:
The slurry includes following component, by mass percentage:
2. stripping lacquer is protected in aqueous milling according to claim 1, which is characterized in that the defoaming agent be BYK-028,
At least one of BYK-1711, BYK-011, BYK-094, BYK-024；The thickener is in RM-2020, BYK-425
It is at least one；The wetting dispersing agent is at least one of BYK-151, BYK-154, BYK-333, BYK-2012；The stream
Flat agent is at least one of BYK-380N, BYK-381, BYK-420, BYK-425.
3. stripping lacquer is protected in aqueous milling according to claim 1, which is characterized in that the acrylate modified SBS
Mixed solvent in resin is at least one of hexamethylene, butanone, cyclohexanone, toluene.
4. stripping lacquer is protected in aqueous milling according to claim 1, which is characterized in that the acrylate modified SBS
Initiator in resin is benzoyl peroxide or azodiisobutyronitrile.
5. the preparation method of aqueous milling protection stripping lacquer according to any one of claims 1-4, which is characterized in that according to
Stock is formulated described in claim 1, mainly including the following steps: can peelable resin, waterborne polyester polyurethane by aqueous polyurethane
Can peelable resin, water-borne dispersions, slurry, deionized water and aqueous silicone oil be added in beaker, stir 30 ± 5min, be added defoaming
Agent continues 30 ± 5min of stirring, and it is viscous that construction required for thickener reaches is added dropwise under the revolving speed at least stirring condition of 700r/min
Degree, continues 20 ± 5min of stirring, and filtering and discharging protects stripping lacquer to get the aqueous milling.
6. the preparation method of aqueous milling protection stripping lacquer according to claim 5, which is characterized in that the acrylic acid
The preparation method of ester modified SBS resin is stocked up according to being formulated described in claim 1, is mainly included the following steps: SBS tree
Rouge is uniformly dissolved into 60~65% in the mixed solvent, is added in three-necked flask, is warming up to 80 ± 5 DEG C；It flows back in system
In the case where, methyl methacrylate, butyl acrylate, methacrylic acid, initiator and remaining mixing are added dropwise into system
The mixed liquor of solvent, time for adding are controlled in 3h ± 10min；Be added dropwise completely after keep the temperature 1h ± 10min, be cooled to 30 DEG C hereinafter,
Filtering and discharging is to get the acrylate modified SBS resin.
7. the preparation method of aqueous milling protection stripping lacquer according to claim 5, which is characterized in that the slurry
Preparation method, formula stock described in accordance with the claim 1, mainly includes the following steps: white carbon black, titanium dioxide, talcum
Powder, kaolin, bentonite and wetting dispersing agent and levelling agent are added separately in quick worker's bottle, add deionized water and glass
Glass pearl, grinding distribution obtains the slurry in quick worker's disperse mill.
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| CN111040562A (en) * | 2019-11-29 | 2020-04-21 | 山东天汇防水股份有限公司 | Colorless modified emulsion suitable for waterproof coating |
| CN112608654A (en) * | 2020-12-07 | 2021-04-06 | 中昊北方涂料工业研究设计院有限公司 | Dip-coating type chemical milling protective adhesive |
| CN115815078B (en) * | 2022-10-08 | 2024-01-02 | 中昊北方涂料工业研究设计院有限公司 | Method for improving quality of aluminum alloy chemical milling adhesive film |
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