JP5972435B1 - Coating liquid composition, method for producing coating liquid composition, and composition for preparing coating liquid composition - Google Patents

Abstract

Disclosed is a coating liquid composition that can reduce resin precipitation even when carbon dioxide is used as a diluent. A coating liquid composition according to the present invention has a resin component, a first solvent for dissolving the resin component, carbon dioxide, and a second solubility parameter of 23.5 to 40 (MPa) 0.5. Of solvents. [Selection] Figure 1

Description

  The present invention relates to a coating liquid composition containing carbon dioxide and the like.

  As a method for coating an object with ink or paint, a method is known in which carbon dioxide is mixed with ink or paint to prepare a coating liquid composition, and the obtained coating liquid composition is sprayed onto the object. In this method, carbon dioxide functions as a diluent, and the viscosity of the ink or paint is lowered to a level at which spraying is possible, so that spraying can be suitably performed.

  A number of techniques relating to coating using carbon dioxide have been developed, for example, as in Patent Documents 1 to 6.

Japanese Patent No. 4538625 Japanese Patent No. 5429928 Japanese Patent No. 5429929 Patent No. 5660605 Japanese Patent No. 5568801 Japanese Patent No. 5608864

  However, in the prior art, sufficient examination of the coating liquid composition has not been made. For this reason, the resin component precipitated in the coating liquid composition, often causing a blockage of the line through which the coating liquid composition passes.

  This invention is made | formed in view of the said subject, and it aims at providing the coating liquid composition etc. which can reduce precipitation of resin even when a carbon dioxide is used as a diluent.

As a result of intensive studies, the present inventors have found the following. Carbon dioxide has an SP value (solubility parameter) of about 10 MPa at 20 ° C. and about 15 (MPa) ^0.5, while the resin component is about 17 to 25 (MPa) ^0.5 , and the true solvent is about 16 to 23.3 (MPa) It has an SP value of about ^0.5 . And when carbon dioxide was mixed with the mixture of resin and a true solvent, it discovered that SP value of a mixed solvent tends to fall rather than resin, and there exists a tendency for resin to precipitate.

The coating liquid composition according to the present invention comprises a resin component, a first solvent having a solubility parameter of less than 23.5 (MPa) ^0.5 , carbon dioxide, and 23.5 to 40 (MPa) ^0.5 . A second solvent having a solubility parameter is included.

  According to the coating liquid composition of the present invention, in addition to the first solvent, since the second solvent having a higher SP value compared to carbon dioxide having an SP value of about 15 is contained, carbon dioxide having a low SP value is contained. Even if is mixed, the precipitation of the resin in the liquid can be suppressed, and suitable spraying can be performed.

Here, the solubility parameter SP _R [(MPa) ^0.5 ] of the resin component and the solubility parameter SP _MIX [(MPa) ^0.5 ] of the mixture of carbon dioxide and the second solvent are SP _R −6 <. SP _MIX <SP _R +10 can be satisfied.

According to this, the ratio of the second solvent for carbon dioxide, because SP _MIX is set to particularly close to SP _R, can be more suitably suppress the precipitation of the resin in the liquid.

  Here, the second solvent is formamide, hydrazine, glycerin, N-methylformamide, 1,4-diformylpiperazine, ethylenecyanohydrin, malononitrile, 2-pyrrolidine, ethylene carbonate, methylacetamide, ethylene glycol, methanol, dimethyl. Sulfoxide, phenol, 1,4-diacetylpiperazine, maleic anhydride, 2-piperidone, formic acid, methylethylsulfone, pyrone, tetramethylenesulfone, propiolactone, propylene carbonate, N-nitrosodimethylamine, N-formylmorpholine, 3 -Methylsulfolane, nitromethane, ethanol, ε-caprolactam, propylene glycol, butyrolactone, chloroacetonitrile, methylpropylsulfone, furfuryl alcohol, pheny Hydrazine, dimethyl phosphite, 2-methoxyethanol, diethylsulfone, ethylenediamine, ethylacetamide, 2-chloroethanol, benzyl alcohol, 4-ethyl-1,3-dioxolan-2-one, bis (2-ethylhexyl) phthalate , Dimethylformamide, diethylene glycol, 1,4-butanediol, tetrahydro-2,4-dimethylthiophene 1,1-dioxide, acrylic acid, 1-propanol, acetonitrile, allyl alcohol, 4-acetylmorpholine, 1,3-butanediol And at least one selected from the group consisting of formylpiperidine, pentanediol, isopropanol, ethylene glycol monophenyl ether, and ethyl cellosolve.

  Moreover, the said coating liquid composition can contain 5-95 mass% of carbon dioxide.

The solubility parameter of the resin component may be 17 to 25 (MPa) ^0.5 .

  A method for forming a coating film according to the present invention includes a step of spraying the above-described coating liquid composition onto an object from a nozzle to form a liquid film, and a step of solidifying the liquid film to form a coating film. Prepare.

The method for producing a coating liquid composition according to the present invention comprises a resin component, a first solvent having a solubility parameter of less than 23.5 (MPa) ^0.5 , carbon dioxide, and 23.5 to 40 (MPa). ^And a second solvent having a solubility parameter of ^0.5 to obtain a coating liquid composition.

Here, the mixing ratio of the carbon dioxide and the second solvent includes the solubility parameter SP _R [(MPa) ^0.5 ] of the resin component and the solubility parameter of the mixture of the carbon dioxide and the second solvent. SP _MIX [(MPa) ^0.5 ] can be determined to satisfy SP _R −6 <SP _MIX <SP _R +10.

The mixing step includes
Mixing the carbon dioxide and the second solvent;
Mixing a mixture of the resin component and the first solvent with a mixture of the carbon dioxide and the second solvent.

  Further, the mixing step may include a step of mixing the carbon dioxide into a mixture of the resin component, the first solvent, and the second solvent.

An apparatus for producing a coating liquid composition according to the present invention includes a resin component, a first solvent for dissolving the resin component, carbon dioxide, and a solubility parameter of 23.5 to 40 (MPa) ^0.5 . A mixing section is provided for mixing the two solvents to obtain a coating liquid composition.

The composition for preparing a coating liquid composition according to the present invention includes a resin component, a first solvent having a solubility parameter of less than 23.5 (MPa) ^0.5 , and 23.5 (MPa) of ^0.5 or more. Contains a second solvent having a solubility parameter.

  According to the present invention, resin precipitation in the coating liquid composition can be reduced.

An example of embodiment of a continuous-type carbon dioxide coating apparatus is shown. An example of embodiment of a continuous-type carbon dioxide coating apparatus is shown.

  The coating liquid composition according to the present invention has a resin component, a first solvent, carbon dioxide, and a second solvent. Hereinafter, each component will be described.

<Resin component>
The resin component is not particularly limited as long as it is a commonly used resin. For example, epoxy resin (about 22), acrylic resin (about 19), acrylic urethane resin (about 17-22), polyester resin (about 22) , Acrylic silicon resin (about 17-22), alkyd resin (about 17-25), UV curable resin (about 17-23), vinyl chloride resin (about 19-22), styrene butadiene rubber (about 17-18) Polyester urethane resin (about 19-21), styrene acrylic resin (about 19-21), amino resin (about 19-21), polyurethane resin (about 21), phenol resin (about 23), vinyl chloride resin (about 19 To 22), nitrocellulose resin (about 22 to 24), cellulose acetate butyrate resin (about 20), styrene resin (about 17 to 21), mela Down urea resin (approximately 19-21), and the like. You may use these individually or in mixture of 2 or more types. The resin component may be a one-component curable resin, a two-component curable resin, or an active energy ray curable resin such as UV. The numbers in parentheses are typical solubility parameters for each resin, and the unit is (MPa) ^0.5 .

  The solubility parameter is a solubility parameter of Hildebrand. The solubility parameter (hereinafter referred to as SP value) is a thermodynamic parameter representing a measure of affinity between substances, and it is known that substances having similar SP values tend to be easily dissolved. ing.

The resin component can have an SP value of 17 (MPa) ^0.5 or more, 18 (MPa) ^0.5 or more, 19 (MPa) ^0.5 or more, 25 (MPa) ^0.5 or less, 24 ( MPa) ^0.5 below, can have an SP value of 23.5 (MPa) ^0.5 below.

The SP value of the resin component can be determined as follows. That is, until the resin is dissolved in the good solvent A, the poor solvent H having an SP value higher than that of the good solvent and the poor solvent L having an SP value lower than that of the good solvent are separately dropped until the resin precipitates and becomes cloudy. Record the amount of each anti-solvent required for. SP value [delta] _A of the good solvent _A, the SP value of the poor solvent H [delta] _H, the SP value of the poor solvent L and [delta] _L, good solvent A at a point that becomes cloudy, poor solvent H, the volume fraction of poor solvent L Is φ _A , φ _H , φ _L , the SP value of the mixed solvent at the two turbid points δ _{good solvent A + poor solvent H 1} , δ _{good solvent A + poor solvent L} are respectively represented by the volume average of SP values. And the following equation holds.
δ _{Good solvent A + Poor solvent H} = (φ _A · δ _A ² + φ _H · δ _H ² ) ^0.5
δ _{good solvent A + poor solvent L} = (φ _A · δ _A ² + φ _L · δ _L ² ) ^0.5
Therefore, SP value SP _R of resin,
SP _R = ((V _{good solvent A + poor solvent H} · δ _{good solvent A + poor solvent H} ² + V _{good solvent A + poor solvent L} · δ _{good solvent A + poor solvent L} ² ) / (V _{good solvent A + poor solvent H} + V _{good solvent) A + poor solvent L} )) ^0.5
Here, V _{good solvent A + poor solvent H,} V _{good solvent A + poor solvent L} are average molar volumes at the cloud point of the mixed solvent. For example, the former is obtained by the following equation.
1 / V _{good solvent A + poor solvent H} = φ _A / V _A + φ _H / V _H
Here, V _A and V _H are the molar volumes of the good solvent A and the poor solvent H, respectively.

<First solvent>
The first solvent is a solvent having an SP value of less than 23.5, and is a true solvent capable of dissolving the resin component. The first solvent can be a _SP R -7 ≦ SP _{first solvent} ≦ _SP R +4 relative SP value SP _R of the resin component. Examples of the first solvent include methyl isobutyl ketone (17.2), 3-methoxybutyl acetate (20.5), propylene glycol monomethyl ether acetate (18.7), Solvesso 100 (manufactured by TonenGeneral Sekiyu KK, product Name) (17.6), Solvesso 150 (trade name) (17.4) manufactured by TonenGeneral Sekiyu KK, ethyl diglycol acetate (18.5), n-butanol (23.3), diisobutyl ketone (16) , Ethyl acetate (18.6), butyl acetate (17.0), and the like. The numerical values in the parentheses are SP values and the unit is (MPa) ^0.5 . The first solvent may be a mixture of solvents having an SP value of less than 23.5. Although it will not specifically limit if the compounding quantity of a 1st solvent is a range which can melt | dissolve a resin component, It can be 25-10000 mass parts with respect to 100 mass parts of resin components, and should be 25-1000 mass parts. Is preferable, and it is more preferable that it is 87-461 mass parts.

<CO2>
Carbon dioxide is usually present as a liquid or supercritical liquid in the coating liquid composition before spraying. When the pressure is low, such as during spraying, it can become a gas.

  The compounding quantity of a carbon dioxide can be 5-95 mass% with respect to a coating liquid composition, It is preferable that it is 5-60 mass%, and it is more preferable that it is 5-30 mass%.

<Second solvent>
The second solvent has an SP value of 23.5-40 (MPa) ^0.5 .
Examples of the second solvent are formamide (39.3), hydrazine (37.3), glycerin (33.8), N-methylformamide (32.9), 1,4-diformylpiperazine (31.5 ), Ethylene cyanohydrin (31.1), malononitrile (30.9), 2-pyrrolidine (30.1), ethylene carbonate (30.1), methylacetamide (29.9), ethylene glycol (29.9), Methanol (29.7), dimethyl sulfoxide (29.7), phenol (29.3), 1,4-diacetylpiperazine (28.0), maleic anhydride (27.8), 2-piperidone (27.8) ), Formic acid (27.6), methyl ethyl sulfone (27.4), pyrone (27.4), tetramethylene sulfone (27.4), propiolactone (2) 7.2), propylene carbonate (27.2), N-nitrosodimethylamine (26.8), N-formylmorpholine (26.6), 3-methylsulfolane (26.4), nitromethane (26.0) , Ethanol (26.0), ε-caprolactam (26.0), propylene glycol (25.8), butyrolactone (25.8), chloroacetonitrile (25.8), methylpropylsulfone (25.6), full Furyl alcohol (25.6), phenylhydrazine (25.6), dimethyl phosphite (25.6), 2-methoxyethanol (25.4), diethylsulfone (25.4), ethylenediamine (25.2) , Ethylacetamide (25.2), 2-chloroethanol (25.0), benzyl alcohol (24.8), 4-ethyl-1,3 -Dioxolan-2-one (24.8), bis (2-ethylhexyl) phthalate (24.8), dimethylformamide (24.8), diethylene glycol (24.8), 1,4-butanediol (24. 8), tetrahydro-2,4-dimethylthiophene 1,1-dioxide (24.6), acrylic acid (24.6), 1-propanol (24.3), acetonitrile (24.3), allyl alcohol (24 .1), 4-acetylmorpholine (23.7), 1,3-butanediol (23.7), formylpiperidine (23.5), pentanediol (23.5), isopropanol (23.5), ethylene Glycol monophenyl ether (23.5), ethyl cellosolve (23.5). The numerical values in parentheses are SP values, and the unit is (MPa) ^0.5 . The second solvent may be a mixture of solvents having an SP value of 23.5-40 (MPa) ^0.5 . The SP value of the second solvent can be 24 (MPa) ^0.5 or more and can be 25 (MPa) ^0.5 or more.

  Among these, formamide, methanol, dimethyl sulfoxide, ethanol, propylene glycol, butyrolactone, dimethylformamide, isopropanol, acetonitrile, and a mixture of any combination thereof are preferable.

  When using a two-component curable resin as the resin component, it is preferable to use an aprotic solvent from the viewpoint of suppressing the reaction with the resin. Examples of aprotic solvents are 1,4-diformylpiperazine, malononitrile, ethylene carbonate, dimethyl sulfoxide, 1,4-diacetylpiperazine, methylethylsulfone, pyrone, tetramethylenesulfone, propiolactone, propylene carbonate, N- Nitrosodimethylamine, N-formylmorpholine, 3-methylsulfolane, nitromethane, butyrolactone, chloroacetonitrile, methylpropylsulfone, diethylsulfone, 4-ethyl-1,3-dioxolan-2-one, bis (2-ethylhexyl) phthalate , Dimethylformamide, tetrahydro-2,4-dimethylthiophene 1,1-dioxide, acetonitrile, 4-acetylmorpholine, and formylpiperidine. Among these, dimethyl sulfoxide, butyrolactone, dimethylformamide, acetonitrile, and a mixture of any combination thereof are preferable.

Further, the SP value SP _R of the resin component and the SP value SP _MIX of the mixture of carbon dioxide and the second solvent can satisfy SP _R −6 <SP _MIX and satisfy SP _R −5 <SP _MIX. Is preferable, and SP _R −4 <SP _MIX can be satisfied. Further, SP _MIX <SP _R +10 can be satisfied, SP _MIX <SP _R +9 can be satisfied, SP _MIX <SP _R +8 can be satisfied, SP _MIX <SP _R +7 can be satisfied, SP _MIX <SP _R +6 can be satisfied, SP _MIX <SP _R +5 can be satisfied, and SP _MIX <SP _R +4 can be satisfied. SP _MIX varies depending on the mixing ratio of the second solvent and carbon dioxide in the coating liquid composition.

The SP value SP _MIX of the mixture of carbon dioxide and the second solvent can be obtained as a volume average of the SP values of the respective components as described above.

  Moreover, as a compounding quantity in the coating liquid composition of a 2nd solvent, it is 5-95 mass parts normally with respect to a total of 100 mass parts of a carbon dioxide and a 2nd solvent, and 6-84 mass parts. It can be 20 to 80 parts by mass.

  In addition to the above, the coating liquid composition can contain various additives. For example, co-solvents, diluents, pigments, pigment dispersants, UV absorbers, light stabilizers, leveling agents, adhesion promoters, rheology control agents, polymerization initiators, and other additives that are usually added to paints and inks You may contain. When a two-component curable resin is used as the resin component, a curing agent may be included as an additive. Although it does not specifically limit as a hardening | curing agent of 2 liquid curable resin, The hardening | curing agent generally used as a hardening | curing agent of 2 liquid curable resins, such as isocyanate, can be used.

According to such a coating liquid composition, precipitation of the resin component is suppressed. That is, since carbon dioxide having an SP value of about 15 (MPa) ^0.5 at 20 ° C. has a relatively low SP value compared to the resin and the first solvent, the resin component dissolved in the first solvent When carbon is mixed with carbon dioxide, the resin component may be precipitated. Therefore, the precipitation of the resin component can be suppressed by adding a second solvent having a higher SP value than the resin component and raising the SP value of the mixed solvent having carbon dioxide and the second solvent.

Then, the manufacturing method of such a coating liquid composition is demonstrated.
Such a coating liquid is obtained by mixing the resin component, the first solvent, carbon dioxide, and the second solvent. An example of the mixing method is a line blend method using an in-line mixer. The order of mixing is not particularly limited, but the following examples are preferred.

<Three-component continuous mixing method>
The method includes a step of mixing carbon dioxide and a second solvent to obtain a mixture, and a step of mixing a mixture of the resin component and the first solvent with the mixture.

In the present embodiment, a three-liquid continuous mixing type carbon dioxide coating apparatus as shown in FIG. 1 can be used. The carbon dioxide stored in the CO ₂ cylinder 4 is cooled and liquefied by the CO ₂ cooler 5, pressurized to a predetermined pressure by the CO ₂ high pressure pump 6, and heated to a predetermined temperature by the CO ₂ heater 7. And then supplied to the first mixer 12. The second solvent stored in the solvent tank 10 is pressurized to a predetermined pressure by the solvent high-pressure pump 11 and then supplied to the first mixer 12. For example, an in-line mixer can be used as the first mixer 12. Usually, the carbon dioxide to be mixed is a liquid or a supercritical fluid, but may be a gas.

  Further, the mixture of the resin component and the first solvent stored in the paint tank 1 is pressurized to a predetermined pressure by the paint high-pressure pump 2, heated to a predetermined temperature by the paint heater 3, The two mixers 8 are supplied. For example, an in-line mixer can be used as the second mixer 8. The mixture stored in the paint tank 1 can contain the above-described additives.

  That is, carbon dioxide and the second solvent are mixed in the first mixer 12, and then this mixture is mixed with the mixture of the resin component and the first solvent in the second mixer 8, and the coating liquid composition Can do. In this embodiment, since carbon dioxide and the second solvent having a high SP value are mixed in advance, it is easy to suppress the precipitation of the resin component when the resin component and carbon dioxide are mixed.

  Subsequently, the coating liquid composition obtained by the second mixer 8 is in a pressurized state and can be discharged as mist into the atmosphere through a spray gun 9 having a nozzle or an orifice, and this mist is applied to an object to be coated. By contacting, a liquid film of the coating liquid composition is formed. Thereafter, the liquid film is solidified by drying, heating, curing with an active energy ray such as UV, or the like to form a coating film. By such a method, coating, printing, etc. can be performed on an object to be coated.

As temperature of the coating liquid composition to spray, 0-60 degreeC is preferable and it is more preferable that it is 10-30 degreeC. In the case of a two-component curable resin, if the temperature is higher than 60 ° C., the usable time (pot life) of the coating solution composition tends to be shortened. The heat exchanger for adjusting the temperature of the coating liquid composition may be provided downstream of the second mixer 8, but is not provided downstream of the second mixer 8, and the second mixer 8 or the first It is preferable to provide upstream of the two mixer 8. That is, by providing a heat exchanger in a line before mixing carbon dioxide with the resin component, it is possible to suppress the resin from being deposited on the heat exchanger. When the temperature of the coating liquid composition is 10 ° C. to 30 ° C., the CO ₂ heater 7 and the paint heater 3 may be omitted, and the heat exchanger for adjusting the temperature of the coating liquid composition may be omitted.

  The pressure of the coating liquid composition to be sprayed is preferably 2 MPa or more, and more preferably 2 to 15 MPa.

  The residence time of the coating liquid composition from the mixing of the resin component and carbon dioxide to the spraying is preferably 60 seconds or less, and preferably 5 seconds or less. You may adjust the residence time of the liquid from preparation of a coating liquid composition to coating by changing the capacity | capacitance of the piping which connects the 2nd mixer 8 and the spray gun 9. FIG.

  According to this embodiment, the deposition of the resin in the continuous carbon dioxide coating apparatus can be suppressed, and the coating film can be formed using the coating liquid composition without clogging the nozzle inside the spray gun 9. .

<Two-component continuous mixing method>
Subsequently, another mixing method will be described. The method according to the second embodiment includes a step of mixing carbon dioxide into a mixture of a resin component, a first solvent, and a second solvent.

In this embodiment, a two-component continuous mixing type carbon dioxide coating apparatus as shown in FIG. 2 can be used. A mixture of the resin component, the first solvent, and the second solvent (composition for preparing a coating liquid composition) stored in the paint tank 1 is pressurized to a predetermined pressure by the paint high-pressure pump 2, After being heated to a predetermined temperature by the paint heater 3, it is supplied to the second mixer 8. On the other hand, the carbon dioxide stored in the CO ₂ cylinder 4 is cooled and liquefied by the CO ₂ cooler 5, pressurized to a predetermined pressure by the CO ₂ high-pressure pump 6, and increased to a predetermined temperature by the CO ₂ heater 7. After being heated, it is supplied to the second mixer 8. The mixture in the paint tank 1 can contain the above-mentioned additives.

In the second mixer 8, the resin component, the first solvent, carbon dioxide, and the second solvent are mixed to form a coating liquid composition. The coating liquid composition is sprayed onto the object to be coated by the spray gun 9 as described above. Conditions other than the above can be the same as in the three-liquid continuous mixing method.
It is preferable that the residence time of the coating liquid composition from mixing of the resin component and carbon dioxide to spraying is 600 seconds or less. You may adjust the residence time of the liquid from preparation of a coating liquid composition to coating by changing the capacity | capacitance of the piping which connects the 2nd mixer 8 and the spray gun 9. FIG. In this method, even if the residence time is increased, even if the resin is deposited, the resin is re-dissolved before reaching the nozzle of the spray gun 9, so that clogging due to deposition tends not to occur.

  Also in this embodiment, the coating of the coating liquid composition can be performed while reducing the precipitation of the resin in the continuous carbon dioxide coating apparatus. In this embodiment, since a mixture of a resin component, a first solvent, and a second solvent is prepared in advance and carbon dioxide is mixed therewith, a resin component when mixing the resin component and carbon dioxide. Precipitation can be suppressed.

  The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the above-described embodiments, and various modifications can be made. For example, in the above three-liquid continuous mixing method, the paint tank 1 does not contain the second solvent, but a part of the second solvent may be mixed in advance in the paint tank.

EXAMPLES Hereinafter, although an invention is concretely demonstrated based on an Example, this invention is not limited to a following example.
(Examples 1-92)
Resin compositions, solvents (including solvent A and solvent B), carbon dioxide, and additives were mixed at the ratios shown in Tables 5-13. Incidentally, in Table 1 the resin composition used in Examples and Comparative Examples, the additives in Table 2, the solvent in Table 3 shows the SP value of the CO ₂ in Table 4. NV in Table 1 means a non-volatile component (that is, resin component) mass ratio of the resin composition. When NV is not 100%, a first solvent component such as butyl acetate that dissolves the resin is included. . However, in Examples 17 and 18, the resin composition further contains a second solvent component.

<Three-component continuous mixing method>
In the three-component continuous mixing type carbon dioxide coating apparatus as shown in FIG. 1, the resin composition, additive, and solvent A (No. 1 solvent) mixture 1 was charged. The flow rate of the paint high-pressure pump 2 was set to 50 g / min. Solvent B (second solvent) was charged into the solvent tank 10, and the flow rate of the solvent high-pressure pump 11 was set to the mixing ratios shown in Tables 5-13. The flow rate of the CO ₂ high pressure pump 6 was set so as to have the mixing ratios shown in Tables 5-13. In addition, the unit of the ratio of each component in each table is mass%. And the carbon dioxide and the 2nd solvent were mixed in the 1st mixer 12 on the temperature and pressure conditions shown to Tables 5-13, and the mixture 2 was obtained. Thereafter, the mixture 2 and the mixture 1 were mixed in the second mixer 8 under the temperature and pressure conditions shown in Tables 5 to 13 to obtain a coating liquid composition. The liquid residence time from the preparation of the coating liquid composition to spray coating was set to 5 seconds, and the coating test was performed three times.

<Two-component continuous mixing carbon dioxide coating>
In the two-component continuous mixing type carbon dioxide coating apparatus as shown in FIG. 2, the resin composition, additive, solvent A, and solvent prepared in advance in the coating tank 1 according to the respective examples in Tables 5 to 13 B mixture 3 was charged. The flow rate of the paint high pressure pump 2 was set to 60 g / min. The flow rate of the CO ₂ high-pressure pump 6 was set to have the ratios shown in Tables 5-13. In the second mixer 8, the mixture 3 and carbon dioxide were mixed under the temperature and pressure conditions shown in Tables 5 to 13 to obtain a coating liquid composition. The residence time from the preparation of the coating liquid composition to spray coating was set to be 5 seconds, 60 seconds, and 300 seconds, and the coating test was performed three times each.

(Comparative Examples 1-19)
A coating test was performed in the same manner as in Examples 1 to 92 except that the composition ratios shown in Tables 14 and 15 were used. In the comparative example, the second solvent was not used.

(Evaluation)
The result of having performed each coating test 3 times is shown in Tables 5-15. The symbols in the table correspond as follows. ◎ means 3 successes, ○ means 2 successes, Δ means 1 success, × means no success, − means not implemented. Success means that the application for 5 minutes was completed without blockage.
In Examples 1 to 92 using the coating solution composition containing the second solvent, the coating can be performed without clogging the nozzle at least once out of the three times of the three-component continuous mixed carbon dioxide coating test. Even in the two-component continuous mixing type carbon dioxide coating test, it was possible to paint at least once without clogging the nozzle by providing 300 seconds from the preparation of the coating solution composition to the coating. . On the other hand, in Comparative Examples 1 to 19 using the coating liquid composition not containing the second solvent, clogging of the nozzle was observed in both the three-liquid continuous mixed carbon dioxide coating and the two-liquid continuous mixed carbon dioxide coating. It was not possible to paint without. From the above results, it was possible to reduce clogging of the nozzles by using the coating liquid composition containing the second solvent.

1 ... paint tank, 2 ... paint high-pressure pump, 3 ... paint heater 4 ... CO ₂ cylinder, 5 ... CO ₂ cooler, 6 ... CO ₂ high-pressure pump, 7 ... CO ₂ heater, 8 ... second mixer , 9 ... Spray gun, 10 ... Solvent tank, 11 ... Solvent high pressure pump, 12 ... First mixer.

Claims (20)

17-25 (MPa) Resin component having a solubility parameter of ^0.5 , 23.5 (MPa) First solvent having a solubility parameter of less than ^0.5 , carbon dioxide, and 23.5-40 (MPa) look including a second solvent having a solubility parameter of ^0.5,
SP value SP of _{the first solvent} SP _{The first solvent} [(MPa) ^0.5 ] is SP _R −7 ≦ SP _{number with} respect to the SP value SP _R [(MPa) ^0.5 ] of the resin component _{. One solvent} ≦ SP _R +4 .   Furthermore, the coating liquid composition of Claim 1 containing a pigment.   The coating liquid composition of Claim 1 or 2 except the thing containing a catalyst or a catalyst precursor. The solubility parameter SP _R [(MPa) ^0.5 ] of the resin component and the solubility parameter SP _MIX [(MPa) ^0.5 ] of the mixture of carbon dioxide and the second solvent are SP _R −6 <SP _MIX < meet SP _R +10, coating liquid composition according to claim 1.   The second solvent is formamide, hydrazine, glycerin, N-methylformamide, 1,4-diformylpiperazine, ethylene cyanohydrin, malononitrile, 2-pyrrolidine, ethylene carbonate, methylacetamide, ethylene glycol, methanol, dimethyl sulfoxide, phenol 1,4-diacetylpiperazine, maleic anhydride, 2-piperidone, formic acid, methylethylsulfone, pyrone, tetramethylenesulfone, propiolactone, propylene carbonate, N-nitrosodimethylamine, N-formylmorpholine, 3-methylsulfolane , Nitromethane, ethanol, ε-caprolactam, propylene glycol, butyrolactone, chloroacetonitrile, methylpropylsulfone, furfuryl alcohol, phenyl Razine, dimethyl phosphite, 2-methoxyethanol, diethylsulfone, ethylenediamine, ethylacetamide, 2-chloroethanol, benzyl alcohol, 4-ethyl-1,3-dioxolan-2-one, bis (2-ethylhexyl) phthalate , Dimethylformamide, diethylene glycol, 1,4-butanediol, tetrahydro-2,4-dimethylthiophene 1,1-dioxide, acrylic acid, 1-propanol, acetonitrile, allyl alcohol, 4-acetylmorpholine, 1,3-butanediol Coatin according to any one of claims 1 to 4, which is at least one selected from the group consisting of: formylpiperidine, pentanediol, isopropanol, ethylene glycol monophenyl ether, and ethyl cellosolve. Liquid composition.   The coating liquid composition according to any one of claims 1 to 5, comprising 5 to 95% by mass of carbon dioxide. A step of spraying the coating liquid composition according to any one of claims 1 to 6 onto an object from a nozzle to form a liquid film, and a step of solidifying the liquid film to form a coating film. A method for forming a coating film. A resin component having a solubility parameter of 17 to 25 (MPa) ^0.5 , a first solvent having a solubility parameter of less than 23.5 (MPa) ^0.5 , carbon dioxide, and 23.5 to 40 (MPa) And a second solvent having a solubility parameter of ^0.5 to obtain a coating liquid composition ,
SP value SP of _{the first solvent} SP _{The first solvent} [(MPa) ^0.5 ] is SP _R −7 ≦ SP _{number with} respect to the SP value SP _R [(MPa) ^0.5 ] of the resin component _. it is _{one solvent} ≦ _SP R +4, the production method of the coating liquid composition. The method for producing a coating liquid composition according to claim 8 , wherein in the mixing step, a pigment is further mixed to obtain the coating liquid composition. The method for producing a coating liquid composition according to claim 8 or 9 , wherein the coating liquid composition does not contain a catalyst or a catalyst precursor. The mixing ratio of the carbon dioxide and the second solvent includes a solubility parameter SP _R [(MPa) ^0.5 ] of the resin component and a solubility parameter SP _MIX of a mixture of the carbon dioxide and the second solvent. ^{(MPa) 0.5]} _is, SP _{R -6} <defined so as to satisfy the SP MIX _<SP R +10, the production method of the coating liquid composition according to any one of claims 8-10. The mixing step comprises:
Mixing the carbon dioxide and the second solvent;
The mixture of the second solvent and the carbon dioxide method according to any one of claims 8-11 comprising the steps of mixing the mixture of the first solvent and the resin component. Wherein the step of mixing, with the resin component, and the first solvent, the mixture of the second solvent, comprising the step of mixing the carbon dioxide according to any one of claims 8-11 the method of. After the step of the mixing, further said resin component, said first solvent, said second solvent, a mixture of the carbon dioxide, comprising the step of staying 60-300 seconds, to claim 13 The method described. A resin component having a solubility parameter of 17 to 25 (MPa) ^0.5 , a first solvent having a solubility parameter of less than 23.5 (MPa) ^0.5 and dissolving the resin component, carbon dioxide, A second solvent having a solubility parameter of 23.5 to 40 (MPa) ^0.5 , and a mixing unit for obtaining a coating liquid composition ,
SP value SP of _{the first solvent} SP _{The first solvent} [(MPa) ^0.5 ] is SP _R −7 ≦ SP _{number with} respect to the SP value SP _R [(MPa) ^0.5 ] of the resin component _{. one} is a _solvent ≦ _SP R +4, apparatus for producing a coating solution composition. The said mixing part is a manufacturing apparatus of the coating liquid composition of Claim 15 which further mixes a pigment and obtains the said coating liquid composition. The said coating liquid composition is a manufacturing apparatus of the coating liquid composition of Claim 15 or 16 which does not contain a catalyst or a catalyst precursor. Resin component having a solubility parameter of 17 to 25 (MPa) ^0.5 , 23.5 (MPa) a first solvent having a solubility parameter of less than ^0.5 , and 23.5 to 40 (MPa) ^0.5 Containing a second solvent having a solubility parameter of
SP value SP of _{the first solvent} SP _{The first solvent} [(MPa) ^0.5 ] is SP _R −7 ≦ SP _{number with} respect to the SP value SP _R [(MPa) ^0.5 ] of the resin component _{. A} composition for preparing a carbon dioxide-containing coating liquid composition, wherein _{one solvent} ≦ SP _R +4 . The composition for preparing a carbon dioxide-containing coating liquid composition according to claim 18 , further comprising a pigment. 20. The composition for preparing a carbon dioxide-containing coating liquid composition according to claim 18 or 19 , excluding those containing a catalyst or a catalyst precursor.

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