CN107429117A - Coating fluid composition, the manufacture method of coating fluid composition and coating fluid composition modulation composition - Google Patents
Coating fluid composition, the manufacture method of coating fluid composition and coating fluid composition modulation composition Download PDFInfo
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- CN107429117A CN107429117A CN201580078609.3A CN201580078609A CN107429117A CN 107429117 A CN107429117 A CN 107429117A CN 201580078609 A CN201580078609 A CN 201580078609A CN 107429117 A CN107429117 A CN 107429117A
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- solvent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Inorganic Chemistry (AREA)
Abstract
The present invention provides one kind in the case that carbon dioxide is used as diluent, can also mitigate coating fluid composition of precipitation of resin etc..Coating fluid composition includes resin component, the first solvent of dissolving resin composition, carbon dioxide and has 23.5~40 (MPa)0.5Solubility parameter the second solvent.
Description
Technical field
The present invention relates to wrap carbonated coating fluid composition etc..
Background technology
As by ink or coatings in the method for object, it is known to adjusted to ink or coating mixing carbon dioxide
Coating fluid composition processed, the method that the coating fluid composition of gained is sprayed to object.In this method, carbon dioxide is as dilute
Release agent and play function, the viscosity of ink or coating is reduced to sprayable level, can compatibly sprayed.
On the technology of such coating for having used carbon dioxide, such as patent document 1~6 is developed perhaps
It is more.
Prior art literature
Patent document
Patent document 1：Japanese Patent No. 4538625
Patent document 2：Japanese Patent No. 5429928
Patent document 3：Japanese Patent No. 5429929
Patent document 4：Japanese Patent No. 5660605
Patent document 5：Japanese Patent No. 5568801
Patent document 6：Japanese Patent No. 5608864
The content of the invention
Invent problem to be solved
However, in conventional technology, coating fluid composition is not studied fully.Therefore, set in coating fluid composition
Fat causes the obstruction of the pipeline by coating fluid composition often into analyzing.
The present invention in view of above-mentioned problem and complete, and it is an object of the present invention to provide even in carbon dioxide is used as diluent
In the case of, coating fluid composition of precipitation of resin etc. can also be mitigated.
For solving the scheme of problem
Result of the present inventor through making great efforts to study, finds following facts.Carbon dioxide has about 15 at 10MPa, 20 DEG C
(MPa)0.5The SP values (solubility parameter) of left and right, on the other hand, resin component has such as 17~25 (MPa)0.5The SP of left and right
Value, true solvent have such as 16~23.3 (MPa)0.5The SP values of left and right.And to resin and the mixture mixing dioxy of true solvent
Change carbon when, find mixed solvent SP values have the tendency of it is lower than resin, exist resin separate out tendency.
Coating fluid composition of the present invention include resin component, have be less than 23.5 (MPa)0.5Solubility parameter
The first solvent, carbon dioxide and there are 23.5~40 (MPa)0.5Solubility parameter the second solvent.
According to coating fluid composition of the present invention, due to comprising the first solvent and with 15 or so SP values
Carbon dioxide second solvent high compared to SP values, therefore even if mixing the low carbon dioxide of SP values, can also suppress in liquid
The precipitation of resin, can suitably it be sprayed.
Herein, the solubility parameter SP of resin componentR[(MPa)0.5] and the mixture of carbon dioxide and the second solvent
Solubility parameter SPMIX[(MPa)0.5] SP can be metR-6<SPMIX<SPR+10。
Thus, with SPMIXEspecially close to SPRMode set ratio of second solvent relative to carbon dioxide, therefore can be more
Compatibly suppress the precipitation of the resin in liquid.
Herein, foregoing second solvents can be selected from by formamide, hydrazine, glycerine, N-METHYLFORMAMIDE, Isosorbide-5-Nitrae-diformyl piperazine
Piperazine, ethylene cyanohydrin (Ethylene cyanohydrin), malononitrile, 2- pyrrolidines, ethylene carbonate, methylacetamide, second two
Alcohol, methanol, dimethyl sulfoxide (DMSO), phenol, 1,4- diacetyl piperazines, maleic anhydride, 2- piperidones, formic acid, Methylethyl sulfone, pyrrole
Mutter ketone (Pyrone), tetramethylene sulfone, propiolactone, propylene carbonate, N-Nitrosodimethylamine, N- N-formyl morpholine Ns, 3- methyl rings
Fourth sulfone, nitromethane, ethanol, epsilon-caprolactams, propane diols, butyrolactone, chloroacetonitrile, methyl-propyl sulfone, furfuryl alcohol, phenylhydrazine, phosphorous
Dimethyl phthalate, 2-methyl cellosolve, diethyl sulfone, ethylenediamine, ethyl acetamide, ethylene chlorhydrin, benzylalcohol, 4- ethyls -1,3- two
Butyl oxide link (Dioxolan) -2- ketone, phthalic acid double (2- ethylhexyls), dimethylformamide, diethylene glycol (DEG), 1,4- fourths two
Alcohol, tetrahydrochysene -2,4- thioxene 1,1- dioxide, acrylic acid, 1- propyl alcohol, acetonitrile, allyl alcohol, 4- acetyl morphines, 1,3-
At least one in the group that butanediol, formylpiperidine, pentanediol, isopropanol, ethylene glycol list phenyl ether, ethyl cellosolve are formed
Kind.
In addition, above-mentioned coating fluid composition can include 5~95 mass % carbon dioxide.
In addition, the solubility parameter of aforementioned resin composition can be 17~25 (MPa)0.5。
The forming method of coated film of the present invention possesses above-mentioned coating fluid composition from nozzle spray to object
Thing and the process and the foregoing liquid film of solidification and the process that forms coated film for forming liquid film.
The manufacture method of coating fluid composition of the present invention possess by resin component, have be less than 23.5 (MPa)0.5
The first solvent of solubility parameter, carbon dioxide and there are 23.5~40 (MPa)0.5The second solvent of solubility parameter enter
The process that row is obtained by mixing coating fluid composition.
Wherein, the mixing ratio of foregoing carbon dioxide and foregoing second solvents can be with the solubility parameter of aforementioned resin composition
SPR[(MPa)0.5] and the mixture of foregoing carbon dioxide and foregoing second solvents solubility parameter SPMIX[(MPa)0.5]
Meet SPR-6<SPMIX<SPR+ 10 mode determines.
In addition, the foregoing process mixed can possess the process for mixing foregoing carbon dioxide and foregoing second solvents, and
The mixture of aforementioned resin composition and foregoing first solvents is mixed with the mixture of foregoing second solvents to foregoing carbon dioxide
Process.
In addition, the foregoing process mixed can also possess to foregoing resin component, foregoing first solvents and foregoing second
The process that the mixture of solvent mixes foregoing carbon dioxide.
The manufacture device of coating fluid composition of the present invention possesses hybrid resin composition, dissolves aforementioned resin composition
First solvent, carbon dioxide and there are 23.5~40 (MPa)0.5Solubility parameter the second solvent and obtain coating fluid combination
The mixing unit of thing.
Coating fluid composition modulation composition of the present invention contain resin component, have be less than 23.5 (MPa)0.5
Solubility parameter the first solvent and there are 23.5 (MPa)0.5Second solvent of solubility parameter above.
Invention effect
According to the present invention, the precipitation of the resin in coating fluid composition can be mitigated.
Brief description of the drawings
[Fig. 1] represents one of the embodiment of continous way carbon dioxide painting device.
[Fig. 2] represents one of the embodiment of continous way carbon dioxide painting device.
Embodiment
Coating fluid composition of the present invention has resin component, the first solvent, carbon dioxide and the second solvent.With
Under, each composition is illustrated.
<Resin component>
As resin component, as long as commonly used resin is then not particularly limited, but epoxy resin can be for example enumerated
(about 22), acrylic resin (about 19), propenoic methyl carbamate resin (about 17~22), polyester resin (about 22), propylene
Silicon acid resinous (about 17~22), alkyd resin (about 17~25), UV solidified resins (about 17~23), Chlorovinyl-acetate vinyl
Resin (salt jealous woman PVC Trees fat) (about 19~22), SBR styrene butadiene rubberses (about 17~18), polyester urethane resin
(about 19~21), styrene-acrylic resin (about 19~21), amino resins (about 19~21), polyurethane resin (about 21),
Phenolic resin (about 23), vinyl chloride resin (about 19~22), nitrocellulose resin (about 22~24), cellulose acetate-butyrate resin
(about 20), styrene resin (about 17~21), melamine-urea resin (about 19~21) etc..These can individually or two or more
It is used in mixed way.Resin component can be 1 solution curing type resin, can be 2 solution curing type resins or UV isoreactivity energy
Line gel-type resin.Numerical value in bracket is the typical solubility parameter of each resin, and unit is (MPa)0.5。
Solubility parameter refers to Hildebrand solubility parameters.Solubility parameter (hereinafter referred to as SP values) is to represent material
Between compatibility yardstick thermodynamic parameter, it is known that with holding diffluent tendency between the material with similar SP values.
Resin component can have 17 (MPa)0.5Above, 18 (MPa)0.5Above, 19 (MPa)0.5SP values above, can have
25(MPa)0.5Below, 24 (MPa)0.5Below, 23.5 (MPa)0.5Following SP values.
The SP values of resin component can be obtained as follows.That is, resin is dissolved in good solvent A, be added dropwise respectively more molten than good
The high lean solvent H of the agent SP values and lean solvent L lower than good solvent SP values, record institute untill resin separates out and produces gonorrhoea
The amount of the respective lean solvent needed.Good solvent A SP values are set to δA, lean solvent H SP values are set to δH, lean solvent L SP values
It is set to δL, the good solvent A for the point for producing gonorrhoea, lean solvent H, lean solvent L volume fraction are set to φA、φH、φLWhen, 2
The SP values δ of mixed solvent in cloud pointGood solvent A+ lean solvents H、δGood solvent A+ lean solvents LCan averagely it be represented with the volume of SP values respectively, following formula is set up.
δGood solvent A+ lean solvents H=(φA·δA 2+φH·δH 2)0.5
δGood solvent A+ lean solvents L=(φA·δA 2+φL·δL 2)0.5
Therefore, the SP values SP of resinRFor
SPR=((VGood solvent A+ lean solvents H·δGood solvent A+ lean solvents H 2+VGood solvent A+ lean solvents L·δGood solvent A+ lean solvents L 2)/(VGood solvent A+ lean solvents H+
VGood solvent A+ lean solvents L))0.5
Wherein, VGood solvent A+ lean solvents H、VGood solvent A+ lean solvents LBe mixed solvent cloud point in molar average volume, such as the former can be by
Following formula is obtained.
1/VGood solvent A+ lean solvents H=φA/VA+φH/VH
Wherein, VA、VHRespectively good solvent A and lean solvent H molal volume.
<First solvent>
First solvent is the solvent that SP values are less than 23.5, is the true solvent of soluble resin composition.First solvent relative to
The SP values SP of resin componentRCan be SPR-7≤SPFirst solvent≤SPR+4.As the first solvent, such as methyl iso-butyl ketone (MIBK) can be enumerated
(17.2), (east combustion is logical by acetic acid 3- methoxybutyls (20.5), propylene glycol monomethyl ether (18.7), Solvesso 100
With oil company's system, trade name) (17.6), Solvesso 150 (firing general oil company's system, trade name in east) (17.4), ethyl
Diethylene glycol (DEG) acetic acid esters (18.5), n-butanol (23.3), DIBK (16), ethyl acetate (18.6), butyl acetate (17.0)
Deng.It is explained, the numerical value in above-mentioned bracket is SP values, and unit is (MPa)0.5.First solvent can also be that SP values are less than 23.5
Solvent mixture.As long as the use level of the first solvent is not particularly limited in the range of soluble resin composition, phase
Can be 25~10000 mass parts, preferably 25~1000 mass parts for the mass parts of resin component 100, more preferably 87~
461 mass parts.
<Carbon dioxide>
Carbon dioxide exists before spraying generally in coating fluid composition as liquid or supercritical liq.During spraying etc.
During pressure step-down, gas can be turned into.
The use level of carbon dioxide can be 5~95 mass %, preferably 5~60 mass % relative to coating fluid composition,
More preferably 5~30 mass %.
<Second solvent>
Second solvent has 23.5~40 (MPa)0.5SP values.
The example of second solvent have formamide (39.3), hydrazine (37.3), glycerine (33.8), N-METHYLFORMAMIDE (32.9),
1,4- diformyls piperazine (31.5), ethylene cyanohydrin (31.1), malononitrile (30.9), 2- pyrrolidines (30.1), ethylene carbonate
(30.1), methylacetamide (29.9), ethylene glycol (29.9), methanol (29.7), dimethyl sulfoxide (DMSO) (29.7), phenol (29.3),
1,4- diacetyl piperazines (28.0), maleic anhydride (27.8), 2- piperidones (27.8), formic acid (27.6), Methylethyl sulfone
(27.4), pyranone (27.4), tetramethylene sulfone (27.4), propiolactone (27.2), propylene carbonate (27.2), N- nitrosos two
Methylamine (26.8), N- N-formyl morpholine Ns (26.6), 3- methyl sulfolanes (26.4), nitromethane (26.0), ethanol (26.0), ε-oneself
Lactams (26.0), propane diols (25.8), butyrolactone (25.8), chloroacetonitrile (25.8), methyl-propyl sulfone (25.6), furfuryl alcohol
(25.6), phenylhydrazine (25.6), dimethylphosphite (25.6), 2-methyl cellosolve (25.4), diethyl sulfone (25.4), ethylenediamine
(25.2), ethyl acetamide (25.2), ethylene chlorhydrin (25.0), benzylalcohol (24.8), 4- ethyl -1,3- dioxolan-2-ones
(24.8), phthalic acid double (2- ethylhexyls) (24.8), dimethylformamide (24.8), diethylene glycol (DEG) (24.8), 1,4- fourths
Glycol (24.8), tetrahydrochysene -2,4- thioxene 1,1- dioxide (24.6), acrylic acid (24.6), 1- propyl alcohol (24.3), second
Nitrile (24.3), allyl alcohol (24.1), 4- acetyl morphines (23.7), 1,3 butylene glycol (23.7), formylpiperidine (23.5), pentanediol
(23.5), isopropanol (23.5), ethylene glycol list phenyl ether (23.5), ethyl cellosolve (23.5).Numerical value in bracket is SP values,
Unit is (MPa)0.5.Second solvent can also have 23.5~40 (MPa)0.5SP values solvent mixture.Second is molten
The SP values of agent can be 24 (MPa)0.5More than, can be 25 (MPa)0.5More than.
Wherein, preferably formamide, methanol, dimethyl sulfoxide (DMSO), ethanol, propane diols, butyrolactone, dimethylformamide, different
The mixture of propyl alcohol, acetonitrile and any combination in these.
As resin component, in the case of using 2 solution curing type resins, from the viewpoint of the reaction with resin is suppressed,
It is preferred that use non-protonic solvent.The example of non-protonic solvent is selected from sub- by 1,4- diformyls piperazine, malononitrile, carbonic acid
Ethyl ester, dimethyl sulfoxide (DMSO), 1,4- diacetyl piperazines, Methylethyl sulfone, pyranone, tetramethylene sulfone, propiolactone, polypropylene carbonate
Ester, N-Nitrosodimethylamine, N- N-formyl morpholine Ns, 3- methyl sulfolanes, nitromethane, butyrolactone, chloroacetonitrile, methyl-propyl sulfone,
Diethyl sulfone, 4- ethyl -1,3- dioxolan-2-ones, phthalic acid double (2- ethylhexyls), dimethylformamide, tetrahydrochysene -
At least one of group that 2,4- thioxene 1,1- dioxide, acetonitrile, 4- acetyl morphines, formylpiperidine are formed.Its
In, the preferably mixture of dimethyl sulfoxide (DMSO), butyrolactone, dimethylformamide, acetonitrile and any combination in these.
In addition, the SP values SP of resin componentR, carbon dioxide and the second solvent mixture SP values SPMIXSP can be metR-6
<SPMIX, preferably meet SPR-5<SPMIX, SP can be metR-4<SPMIX.In addition, SP can be metMIX<SPR+ 10, SP can be metMIX<
SPR+ 9, SP can be metMIX<SPR+ 8, SP can be metMIX<SPR+ 7, SP can be metMIX<SPR+ 6, SP can be metMIX<SPR+ 5, it can expire
Sufficient SPMIX<SPR+4。SPMIXThe mixing ratio of the second solvent and carbon dioxide in coating fluid composition and change.
The SP values SP of the mixture of carbon dioxide and the second solventMIXCan as described above as each composition SP values body
Product is averagely tried to achieve.
In addition, the use level as the second solvent in coating fluid composition, relative to carbon dioxide and the second solvent
Total 100 mass parts, usually 5~95 mass parts, can be 6~84 mass parts, can be 20~80 mass parts.
Coating fluid composition can include various additives other than the above.Such as can contain cosolvent, diluent, pigment,
Pigment dispersing agent, ultra-violet absorber, light stabilizer, levelling agent, adherence imparting agent, rheology control agent, polymerization initiator etc.
Generally additive of the addition in coating or ink.In the case of using 2 solution curing type resins as resin component, it can include solid
Agent is as additive.Curing agent as 2 solution curing type resins is not particularly limited, and isocyanates etc. can be used to be used as 2
The curing agent that solution curing type hardening of resin agent typically uses.
According to such coating fluid composition, suppress the precipitation of resin component.That is, due to having 15 (MPa at 20 DEG C
)0.5The carbon dioxide of the SP values of left and right has SP values relatively low compared with resin and the first solvent, therefore will be dissolved in first
When the resin component and carbon dioxide mix of solvent, the risk of resin component precipitation be present.Therefore, adding has and resin component
Compared to the second solvent of higher SP values, the SP values of the mixed solvent with carbon dioxide and the second solvent are improved, thus can be suppressed
The precipitation of resin component.
Next, the manufacture method of such coating fluid composition is illustrated.
Such coating fluid can be obtained by hybrid resin composition, the first solvent, carbon dioxide and the second solvent.It is mixed
The example of conjunction method is the pipeline mixing method using pipeline blender (イ Application ラ イ Application ミ キ サ ー).The order of mixing does not have
It is particularly limited to, preferably example below.
<3 liquid method for continuously mixing>
This method possesses mixing carbon dioxide and the second solvent and obtains the process of mixture, and to the mixture compound tree
The process of the mixture of fat composition and the first solvent.
In present embodiment, 3 liquid as shown in Figure 1 continuously hybrid carbon dioxide painting device can be used.It is stored in CO2
The carbon dioxide of bomb 4 passes through CO2The cooling of cooler 5 is liquefied, then passes through CO2High-pressure pump 6 is forced into defined pressure,
Pass through CO again2Heater 7 is heated up to defined temperature, is then supplied to the first blender 12.It is stored in the second of solvent tank 10
Solvent is forced into defined pressure by solvent high-pressure pump 11, is then supplied to the first blender 12.As the first blender 12,
Such as pipeline blender can be used.Generally, mixed carbon dioxide is liquid or supercritical fluid, or gas.
And then the mixture for the resin component and the first solvent for being stored in paint can 1 is forced into rule by coating high-pressure pump 2
Fixed pressure, then defined temperature is heated up to by paint heater 3, then it is supplied in the second blender 8.As the second mixing
Device 8, such as pipeline blender can be used.Above-mentioned additive can be contained by being stored in the mixture of paint can 1.
That is, carbon dioxide mixes with the second solvent in the first blender 12, next, the mixture is in the second blender
Mixed in 8 with resin component with the mixture of the first solvent, turn into coating fluid composition.In the present embodiment, due to by two
Carbonoxide second solvent high with SP values mixes in advance, thus resin when easily suppressing hybrid resin composition and carbon dioxide into
The precipitation divided.
Next, the coating fluid composition obtained by the second blender 8 is pressurized state, by with nozzle or aperture
Spray gun 9, can be released as mist into air, by making the mist be contacted with being applied thing, formed coating fluid composition liquid
Film.Then, solidify liquid film by drying, heating, using solidification of UV isoreactivity energy lines etc., thus can turn into coated film.
By such method, application, printing etc. can be carried out to being applied thing.
As the temperature for making its coating fluid composition sprayed, more preferably preferably 0~60 DEG C, 10~30 DEG C.2 liquid are consolidated
In the case of change type resin, when temperature is higher than 60 DEG C, the up time (working life) of coating fluid composition shortens.
The heat exchanger for adjusting the temperature of coating fluid composition may be provided at the downstream of the second blender 8, but preferably be not arranged in second
The downstream of blender 8, it is arranged on the upstream of the second blender 8 or the second blender 8.That is, by mixing two to resin component
Heat exchanger is set on pipeline before carbonoxide, separated out thus, it is possible to suppress resin in heat exchanger.Coating fluid composition
In the case that temperature is 10 DEG C~30 DEG C, can there is no CO2Heater 7 or paint heater 3, can also be without adjustment coating fluid
The heat exchanger of the temperature of composition.
As the pressure for making its coating fluid composition sprayed, more preferably preferably more than 2MPa, 2~15MPa.
After hybrid resin composition and carbon dioxide, the holdup time of the coating fluid composition untill spraying is preferably 60 seconds
Hereinafter, preferably less than 5 seconds.From the holdup time of the liquid of the modulation of coating fluid composition untill application, change can be passed through
The capacity of the second blender 8 and the pipe arrangement of spray gun 9 is connected to adjust.
According to present embodiment, the precipitation of the resin in continous way carbon dioxide painting device can be suppressed, do not blocked
The formation of the coated film using coating fluid composition is carried out in the case of nozzle inside spray gun 9.
<2 liquid method for continuously mixing>
Next, other mixed methods are illustrated.The method that second embodiment is related to possess to resin component,
The process of first solvent and the mixture mixing carbon dioxide of the second solvent.
In present embodiment, 2 liquid as shown in Figure 2 continuously hybrid carbon dioxide painting device can be used.It is stored in painting
The mixture (coating fluid composition modulation composition) of the resin component of batch can 1, the first solvent and the second solvent passes through coating
High-pressure pump 2 is forced into defined pressure, then is heated up to defined temperature by paint heater 3, is then supplied to the second mixing
Device 8.On the other hand, it is stored in CO2The carbon dioxide of bomb 4 passes through CO2The cooling of cooler 5 is liquefied, then passes through CO2It is high
Press pump 6 is forced into defined pressure, then passes through CO2Heater 7 is heated up to defined temperature, is then supplied to the second blender 8.
Mixture in paint can 1 can include above-mentioned additive.
Hybrid resin composition, the first solvent, carbon dioxide and the second solvent, turn into coating fluid in the second blender 8
Composition.Coating fluid composition is sprayed to coated object with foregoing likewise by spray gun 9.Condition other than the above etc. can be with
3 liquid method for continuously mixing are similarly carried out.
After hybrid resin composition and carbon dioxide, the holdup time of the coating fluid composition untill spraying is preferably 600
Below second.From the holdup time of the liquid of the modulation of coating fluid composition untill application, it can pass through and change the mixing of connection second
The capacity of device 8 and the pipe arrangement of spray gun 9 adjusts.In the method, by increasing the holdup time, even if resin separate out also to
It is redissolved before up to the nozzle of spray gun 9, so as to the tendency for being not susceptible to block caused by precipitation.
In the present embodiment, the precipitation of the resin in continous way carbon dioxide painting device can be mitigated and be coated
The application of liquid composition.In present embodiment, the mixture of pre-made resin component, the first solvent and the second solvent, then
Carbon dioxide is mixed thereto, therefore can suppress the precipitation of hybrid resin composition and resin component during carbon dioxide.
More than, to the present invention suitable embodiment be illustrated in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can be various modifications mode.Such as in 3 above-mentioned liquid method for continuously mixing, it is molten not comprising second in paint can 1
Agent, but the second solvent of a part can also be mixed in paint can in advance.
[embodiment]
Hereinafter, invention is specifically explained according to embodiment, but the present invention is not limited to following embodiment.
(embodiment 1~92)
With the ratio shown in table 5~13, blended resin composition, solvent (including solvent orange 2 A, solvent B), carbon dioxide and
Additive.It is explained, resin combination is shown in table 1 used in the present embodiment and comparative example, and additive shows in table 2
Go out, solvent is shown in table 3, CO2SP values shown in table 4.NV in table 1 means the non-volatile component of resin combination
The mass ratio of (i.e. resin component), in the case that NV is not 100%, the solvent of butyl acetate comprising dissolving resin etc. first into
Point.Wherein, in the case of embodiment 17 and 18, the second solvent composition is further comprised in resin combination.
【Table 2】
【Table 3】
【Table 4】
【Table 7】
【Table 8】
【Table 10】
【Table 11】
<3 liquid method for continuously mixing>
In 3 liquid as shown in Figure 1 continuously hybrid carbon dioxide painting device, in advance into paint can 1 load according to
The mixture 1 of resin combination, additive and solvent orange 2 A (the first solvent) that each embodiment modulation of table 5~13 forms.It will apply
Expect the flow set of high-pressure pump 2 at 50g/ points.Load solvent B (the second solvent) into solvent tank 10, with as the mixed of table 5~13
The flow of the mode setting solvent high-pressure pump 11 of composition and division in a proportion.CO is set in a manner of as the mixing ratio of table 5~132High-pressure pump 6
Flow.It is explained, the unit of the ratio of each composition of each table is quality %.And in the first blender 12, in table 5~13
At shown temperature and pressure condition, mix carbon dioxide and the second solvent and obtain mixture 2.Then, in the second blender 8
It is interior, at the temperature shown in table 5~13 and pressure condition, the mixture 2 and mixture 1 are mixed, obtains coating fluid composition.From
The holdup time of liquid of the modulation of coating fluid composition untill atomized spray painting is set as 5 seconds, 3 times one group carry out application examination
Test.
<The continuously hybrid carbon dioxide application of 2 liquid>
In 2 liquid as shown in Figure 2 continuously hybrid carbon dioxide painting device, in advance into paint can 1 load according to
Resin combination, additive, solvent orange 2 A and solvent B that each embodiment modulation of table 5~13 forms mixture 3.By coating height
The flow set of press pump 2 is at 60g/ points.CO is set in a manner of as the ratio of table 5~132The flow of high-pressure pump 6.Second
In blender 8, at the temperature shown in table 5~13 and pressure condition, blend mixture 3 and carbon dioxide and obtain coating fluid group
Compound.It is set as 5 seconds, 60 seconds and 300 from the holdup time of the liquid of the modulation of coating fluid composition untill atomized spray painting
Second, respectively 3 times one group carry out application experiment.
(comparative example 1~19)
In addition to as the ratio of components as shown in table 14 and 15, others operate in the same manner as embodiment 1~92, carry out
Application is tested.It is no in comparative example to use the second solvent.
【Table 14】
(evaluation)
The result that each application is tested to 3 times one group of progress is shown in table 5~15.Mark in table corresponds to as follows.◎ means
Success 3 times, zero means success 2 times, and △ means success 1 time, × mean not succeed ,-mean not implement.It is so-called
Successfully it is meant to not complete with blocking the coating of 5 minutes.
In the embodiment 1~92 using the coating fluid composition containing the second solvent, 3 liquid continuous hybrid two of implementation
Application is carried out in 3 times of carbonoxide application experiment with can not having nozzle blockage at least 1 time, even in 2 liquid continuous hybrid two
In carbonoxide application experiment, by the way that the time from the modulation of coating fluid composition untill application is arranged on 300 seconds, most feelings
Application is carried out under condition with can not having nozzle blockage at least 1 time.On the other hand, the coating fluid group for not containing the second solvent is being used
In the comparative example 1~19 of compound, 3 liquid continuously continuously appoint for hybrid carbon dioxide application and 2 liquid by hybrid carbon dioxide application
One kind all can not without nozzle blockage carry out application.It can be seen from result above, by using the coating fluid containing the second solvent
Composition, the obstruction of nozzle can be mitigated.
Symbol description
1：Paint can；2：Coating high-pressure pump；3：Paint heater；4：CO2Bomb；5：CO2Cooler；6：CO2High pressure
Pump；7：CO2Heater；8：Second blender；9：Spray gun；10：Solvent tank；11：Solvent high-pressure pump；12：First blender.
Claims (12)
1. a kind of coating fluid composition, it includes resin component, has and is less than 23.5 (MPa)0.5Solubility parameter it is first molten
Agent, carbon dioxide and there are 23.5~40 (MPa)0.5Solubility parameter the second solvent.
2. the coating fluid composition described in claim 1, wherein, the solubility parameter SP of resin componentR[(MPa)0.5] and two
The solubility parameter SP of the mixture of carbonoxide and the second solventMIX[(MPa)0.5] meet SPR-6<SPMIX<SPR+10。
3. the coating fluid composition described in claim 1 or 2, wherein, second solvent be selected from by formamide, hydrazine, glycerine,
N-METHYLFORMAMIDE, 1,4- diformyls piperazine, ethylene cyanohydrin, malononitrile, 2- pyrrolidines, ethylene carbonate, methylacetamide,
Ethylene glycol, methanol, dimethyl sulfoxide (DMSO), phenol, 1,4- diacetyl piperazines, maleic anhydride, 2- piperidones, formic acid, Methylethyl
Sulfone, pyranone, tetramethylene sulfone, propiolactone, propylene carbonate, N-Nitrosodimethylamine, N- N-formyl morpholine Ns, 3- methyl ring fourths
Sulfone, nitromethane, ethanol, epsilon-caprolactams, propane diols, butyrolactone, chloroacetonitrile, methyl-propyl sulfone, furfuryl alcohol, phenylhydrazine, phosphorous acid
Dimethyl ester, 2-methyl cellosolve, diethyl sulfone, ethylenediamine, ethyl acetamide, ethylene chlorhydrin, benzylalcohol, 4- ethyl -1,3- dioxies
Penta ring -2- ketone, phthalic acid double (2- ethylhexyls), dimethylformamide, diethylene glycol (DEG), 1,4- butanediols, tetrahydrochysene -2,4- two
Methylthiophene 1,1- dioxide, acrylic acid, 1- propyl alcohol, acetonitrile, allyl alcohol, 4- acetyl morphines, 1,3 butylene glycol, carbamoyl piperidine
At least one of group that pyridine, pentanediol, isopropanol, ethylene glycol list phenyl ether, ethyl cellosolve are formed.
4. coating fluid composition according to any one of claims 1 to 3 is comprising 5~95 mass % carbon dioxide.
5. coating fluid composition according to any one of claims 1 to 4, wherein, the solubility parameter of the resin component is
17~25 (MPa)0.5。
6. a kind of forming method of coated film, it possesses coating fluid composition according to any one of claims 1 to 5 from spray
The process that mouth is sprayed to object and forms liquid film, and the process for solidifying the liquid film and forming coated film.
7. a kind of manufacture method of coating fluid composition, it possesses resin component, has and be less than 23.5 (MPa)0.5Solubility
First solvent of parameter, carbon dioxide and there are 23.5~40 (MPa)0.5Solubility parameter the second solvent mixed and
Obtain the process of coating fluid composition.
8. the manufacture method of the coating fluid composition described in claim 7, wherein, the carbon dioxide and second solvent
Mixing ratio is with the solubility parameter SP of the resin componentR[(MPa)0.5] and the carbon dioxide and second solvent
The solubility parameter SP of mixtureMIX[(MPa)0.5] meet SPR-6<SPMIX<SPR+ 10 mode determines.
9. the method described in claim 7 or 8, wherein, the process mixed possesses the mixing carbon dioxide and institute
The process for stating the second solvent, and mix the resin component and institute with the mixture of second solvent to the carbon dioxide
The process for stating the mixture of the first solvent.
10. the method described in claim 7 or 8, wherein, the process mixed possesses to the resin component, described
The process that the carbon dioxide is mixed in the mixture of first solvent and second solvent.
11. a kind of manufacture device of coating fluid composition, it possesses hybrid resin composition, the first of the dissolving resin component molten
Agent, carbon dioxide and there are 23.5~40 (MPa)0.5Solubility parameter the second solvent and obtain the mixed of coating fluid composition
Conjunction portion.
12. a kind of carbonated coating fluid composition modulation composition, it contains resin component, had less than 23.5
(MPa)0.5Solubility parameter the first solvent and there are 23.5 (MPa)0.5Second solvent of solubility parameter above.
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| JP2015-149902 | 2015-07-29 | ||
| JP2015149902A JP5972435B1 (en) | 2015-07-29 | 2015-07-29 | Coating liquid composition, method for producing coating liquid composition, and composition for preparing coating liquid composition |
| PCT/JP2015/076503 WO2017017860A1 (en) | 2015-07-29 | 2015-09-17 | Coating liquid composition, coating liquid composition manufacturing method, and composition for preparing coating liquid composition |
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| JP (1) | JP5972435B1 (en) |
| KR (1) | KR101852330B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112236237A (en) * | 2018-06-08 | 2021-01-15 | 长濑产业株式会社 | Coating apparatus and coating method |
| CN112724600A (en) * | 2020-12-28 | 2021-04-30 | 陕西生益科技有限公司 | Thermosetting resin composition, prepreg containing thermosetting resin composition, laminated board and printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6755525B2 (en) * | 2016-02-19 | 2020-09-16 | 東洋紡株式会社 | UV curable paint coating method and UV curable film manufacturing method |
| JP6140329B1 (en) * | 2016-04-06 | 2017-05-31 | 長瀬産業株式会社 | Coating apparatus and coating method |
| JP6198913B1 (en) * | 2016-09-06 | 2017-09-20 | 関西ペイント株式会社 | Coating composition suitable for carbon dioxide coating |
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| Publication number | Publication date |
|---|---|
| WO2017017860A1 (en) | 2017-02-02 |
| CN107429117B (en) | 2018-12-21 |
| KR101852330B1 (en) | 2018-04-27 |
| JP2017031251A (en) | 2017-02-09 |
| TWI613265B (en) | 2018-02-01 |
| KR20170113665A (en) | 2017-10-12 |
| JP5972435B1 (en) | 2016-08-17 |
| TW201718791A (en) | 2017-06-01 |
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