JP5380967B2 - Water dispersion manufacturing apparatus and polyester resin water dispersion manufacturing method - Google Patents

Description

  The present invention relates to a water dispersion manufacturing apparatus and a method for manufacturing a polyester resin water dispersion.

  For example, as a method for producing a polyester resin aqueous dispersion, after dissolving a water-dispersible polyester resin in an organic solvent, water is added while stirring to obtain a polyester resin aqueous dispersion. A method of obtaining a polyester resin aqueous dispersion by dispersing a water-dispersible polyester resin in a mixture of the above, and further, after producing a polyester resin aqueous dispersion containing an organic solvent once using an organic solvent, the aqueous dispersion A method is known in which an organic solvent is distilled off from a body at room temperature or under reduced pressure to obtain a polyester resin aqueous dispersion containing substantially no solvent.

  On the other hand, Patent Document 1 discloses that a polyester resin having a polar group in a molecule is dissolved in a mixed solution of a solvent and water, and further self-emulsified by passing the phase inversion point while adding water. It has been proposed to produce polyester resin water dispersions.

JP 2006-290963 A

  An object of the present invention is to provide an apparatus for producing an aqueous dispersion and a method for producing an aqueous dispersion of a polyester resin that reduce the amount of waste generated during the production of an aqueous dispersion and reduce the amount of a newly used organic solvent. And

  The present invention is as follows.

  (1) An aqueous dispersion production tank for producing an aqueous dispersion, a distillate composition detecting means for detecting the composition of a distillate recovered in the process of removing the solvent from the aqueous dispersion production tank, and depending on the distillate composition And at least two or more distillate collection tanks for separating and collecting the distillate, and a supply means for supplying the distillate stored in at least one of the distillate collection tanks to the water dispersion production tank. It is the water dispersion manufacturing apparatus which has.

  (2) A water dispersion production tank for producing a polyester resin aqueous dispersion by phase inversion and self-emulsification of a polyester resin having a polar group in the molecule using an organic solvent, water and a basic component, and the water A distillate composition detecting means for detecting the composition of the distillate recovered in the process of removing the solvent from the dispersion production tank, and at least two or more distillate recovery tanks for separating and collecting the distillate according to the distillate composition And a supply means for supplying the distillate stored in at least one of the distillate collection tanks to the water dispersion production tank, and at the first production of the polyester resin water dispersion, the water dispersion In a production tank, a polyester resin having a polar group in the molecule is dissolved in a mixed solution containing water and / or a basic component mainly composed of an organic solvent, and then neutralized by adding the basic component. Add more water, phase inversion, self-emulsification The polyester resin aqueous dispersion is manufactured, and after the first production of the polyester resin aqueous dispersion, the distillate supplied by the supply means is used as at least a part of the mixed solution in the aqueous dispersion production tank. Water in which a polyester resin aqueous dispersion is produced by dissolving a polyester resin having a polar group in the molecule, then adding and neutralizing a basic component, adding water, phase inversion and self-emulsification It is a dispersion manufacturing apparatus.

  (3) The distillate composition detection means is the water dispersion production apparatus according to (1) or (2) above, which is a detection means using a detection principle mainly composed of ultrasonic waves.

(4) A water dispersion production process for producing a polyester resin aqueous dispersion by phase inversion and self-emulsification of a polyester resin having a polar group in the molecule, using an organic solvent, water and a basic component, and the water A distillate composition detection step for detecting the composition of the distillate recovered in the process of removing the solvent from the dispersion, and at least two or more distillate collection tanks for separating and collecting the distillate according to the distillate composition; Supplying the distillate stored in one tank to the aqueous dispersion production process, and at the first production of the polyester resin aqueous dispersion, in the aqueous dispersion production process, polar groups in the molecule After dissolving the polyester resin having water in a mixed solution mainly containing an organic solvent and water and / or a basic component, the basic component is added to neutralize, and water is further added to perform phase inversion. Self-emulsified polyester tree An aqueous dispersion is produced, and after the initial production of the polyester resin aqueous dispersion, in the aqueous dispersion production process, the distillate supplied by the supply process is used as at least part of the mixed solution, to dissolve the polyester resin having a polar group, then the basic component further added to neutralize, and further addition of water, phase inversion, polyester resin aqueous and self emulsified you produce a polyester resin aqueous dispersion It is a manufacturing method of a dispersion.

  (5) The polyester resin water according to (4), wherein the mixed solution is a mixed solution composed of at least one selected from the group consisting of a ketone solvent and an ester solvent, an alcohol solvent, and a basic aqueous solution. It is a manufacturing method of a dispersion.

  According to the invention described in claim 1 of the present application, since the distillate separated and recovered in accordance with the composition of the distillate recovered in the process of solvent removal is used for the production of an aqueous dispersion, it is finally manufactured in the conventional manner. Compared to the case where the distillate is discharged every time, the amount of waste discharged is reduced, and the amount of newly used organic solvent is reduced.

According to the inventions described in claims 2 and 4 of the present invention, in order to use the distillate separated and recovered according to the composition of the distillate recovered in the process of solvent removal for the production of the polyester resin water dispersion, finally, Compared to the case where the distillate is discharged for each production as in the prior art, the amount of waste discharged is reduced, and the amount of newly used organic solvent is reduced.

  According to the third aspect of the present invention, for example, the liquid composition detection means using the detection principle mainly composed of ultrasonic waves has higher detection accuracy of the liquid composition in real time than the other detection means.

  According to the invention described in claim 4 of the present application, after neutralizing the mixed solution for dissolving the polyester resin having a polar group in the molecule with a basic component, water is further added, and phase inversion is performed. Since self-emulsification is performed, the solubility of the polyester resin is higher than when neutralization is not performed using a basic component.

  According to the invention described in claim 5 of the present application, by using a mixed solution consisting of at least one kind selected from the group consisting of a ketone solvent and an ester solvent, an alcohol solvent and a basic aqueous solution, other mixing can be performed. Compared with a solution, particularly a mixed solution not containing a basic aqueous solution, the solubility of the polyester resin having a polar group in the molecule is increased.

  FIG. 1 shows the configuration of an example of the water dispersion manufacturing apparatus in the present embodiment. As shown in FIG. 1, the water dispersion manufacturing apparatus in the present embodiment includes a water dispersion manufacturing tank 10 that manufactures an aqueous dispersion, and a distillation that is recovered in the process of removing the solvent from the water dispersion manufacturing tank 10. A composition detector 19 that is a liquid composition detection means for detecting the composition of the liquid, at least two or more liquid collection tanks 30 and 31 for separating and collecting the liquid according to the liquid composition, and separated and recovered. And a distillate liquid feed line 33 which is a supply means for supplying the distillate from the distillate collecting tank 30 for storing the other distillate to the aqueous dispersion production tank 10.

  More specifically, as shown in FIG. 1, the water dispersion manufacturing apparatus in the present embodiment further includes a resin storage tank 22 in which the resin in the water dispersion is stored, and water from the resin storage tank 22. A resin supply line 12 for supplying resin to the dispersion production tank 10, a basic component storage tank 23 in which basic components are stored, and a basic component from the basic component storage tank 23 are supplied to the water dispersion production tank 10. A basic component supply line 13, a pure water storage tank 24 in which water (especially pure water) for dispersing the resin is stored, and pure water is supplied from the pure water storage tank 24 to the water dispersion manufacturing tank 10. A pure water supply line 14, a solvent storage tank 25 in which an organic solvent for dissolving the resin is stored, and a solvent supply line 15 for supplying the organic solvent from the solvent storage tank 25 to the water dispersion manufacturing tank 10 are provided. It has been. In addition, in FIG. 1, although the solvent storage tank 25 and the solvent supply line 15 are one each, it is not limited to this, When producing a mixed solution using a some solvent, in this Embodiment It goes without saying that the water dispersion production tank apparatus has a plurality of solvent storage tanks and a solvent supply line.

  Further, the water dispersion production tank 10 in the present embodiment is provided with a stirrer 16, and the stirrer 16 is connected to the drive source 17 and is stirred by the drive source 17.

  Moreover, the water dispersion manufacturing apparatus in the present embodiment is cooled by the aggregator 18 for cooling the vapor of the distillate collected in the process of removing the solvent from the water dispersion production tank 10, and the aggregator 18. A composition detector 19 for detecting the composition of the distillate, and distillate collection tanks 30 and 31 for separating and collecting the distillate according to the composition detected by the composition detector 19 are provided to produce an aqueous dispersion. From the distillate collection tank 30 in which a reusable composition having a reusable composition is stored in the tank 10, a distillate liquid feed line 33 is passed through a liquid feed pump 32, and a part of the distillate is the water dispersion production tank 10. To be supplied. In FIG. 1, the distillate collection tank is composed of two tanks of the distillate collection tanks 30 and 31, but is not limited to this. The distillate may be separated and recovered and reused.

  As the composition detector 19 in the present embodiment, for example, a detector using a detection principle mainly composed of ultrasonic waves or a detector using a detection principle mainly composed of electrical resistance is used. In the water dispersion manufacturing apparatus described above, since the distillate distilled off in the process of solvent removal is continuously or intermittently sent, mainly ultrasonic waves with high detection accuracy of the distillate composition in real time are mainly used. A composition detector using the detection principle is preferred. However, in the present embodiment, the present invention is not limited to the composition detector. For example, a temporary storage tank is provided between the aggregator 18 and the composition detector 19, and component analysis of the temporarily stored liquid is performed. After that, a method of intermittently collecting and collecting the distillate in the distillate collection tanks 30 and 31 may be employed. In such a case, for example, by preparing a calibration curve for each component in advance using gas chromatography or liquid chromatography, the composition of the temporarily stored distillate is determined, and the temporarily stored distillate is used as the distillate. You may distribute to the collection tank 30 or the distillate collection tank 31. In addition, the composition detector 19 is electrically connected to a CPU (not shown), and the CPU is preliminarily configured with the solvent removal conditions in the water dispersion production tank 10 and the composition with respect to the time of the distillate produced by the solvent removal conditions. The relationship with the change may be stored as a map, and the distillate may be distributed to the distillate collection tank 30 or the distillate collection tank 31 by the composition detector 19 based on this map.

  Next, the operation of another water dispersion production apparatus in the present embodiment will be described below by taking a production method of a polyester resin dispersion as an example.

  First, at the initial production of the polyester resin water dispersion, the organic solvent is supplied from the solvent storage tank 25 to the water dispersion manufacturing tank 10 via the solvent supply line 15, and the pure water supply line 14 is supplied from the pure water storage tank 24. Pure water is supplied through the basic component storage tank 23 through the basic component supply line 13 to produce a mixed solution of water and / or basic components mainly composed of an organic solvent. Then, a polyester resin having a polar group in the molecule is supplied from the resin storage tank 22 through the resin supply line 12, and the stirrer 16 is driven using the drive source 17, and the polyester resin is added to the mixed solution. Is dissolved. Then, based on the output of a pH detector (not shown) provided in the water dispersion production tank 10, the basic composition is transferred from the basic component storage tank 23 to the water dispersion production tank 10 through the basic component supply line 13. Supplying components, neutralizing the solution containing the mixed solution and the polyester resin, and gradually supplying an appropriate amount of pure water from the pure water storage tank 24 via the pure water supply line 14; Phase inversion and self-emulsification are performed to prepare a solvent-containing emulsion.

  Next, the organic solvent is removed from the solvent-containing emulsion by evaporating the aqueous dispersion production tank 10 using at least one of a decompression unit and a heating unit (both not shown). The evaporated organic solvent-containing vapor is cooled in the agglomerator 18 and the composition is detected by the composition detector 19. The distillate suitable for resin dissolution and reusable according to the composition of the distillate is sent to the distillate collection tank 30. The distillate that cannot be reused is separated and collected in the distillate collection tank 31. Therefore, only the distillate that cannot be reused can be separated into waste, and the amount of waste discharged is reduced compared to the case where the distillate is discharged every time of production as in the prior art.

  In addition, after the initial production of the polyester resin aqueous dispersion, the composition of the distillate stored in the distillate collection tank 30 is the same as the composition detector 19 of any form described above (not shown). ) And the liquid feed pump 32 is controlled according to the composition, and a part of the distillate is supplied from the distillate collection tank 30 to the water dispersion production tank 10 via the distillate liquid feed line 33. To do. A small amount of pure water and an organic solvent are supplied to the water dispersion production tank 10 via the pure water supply line 14 and the solvent supply line 15, respectively, according to the amount of the supplied distillate, and mixed. A solution is made. Next, a polyester resin having a polar group in the molecule is supplied from the resin storage tank 22 through the resin supply line 12, and the stirrer 16 is driven using the driving source 17, so that the polyester resin is dissolved in the mixed solution. Is done. Here, although the basic component used in the present embodiment will be described later, for example, in the case of using a highly volatile amine compound, the prepared mixed solvent includes a highly volatile amine contained in the distillate. The basic component which consists of a compound will also be contained. On the other hand, a polyester resin having a polar group in the molecule has a high apparent molecular weight due to the association between the polar groups, poor solvent solubility, and in some cases, the addition amount of the organic solvent must be increased. It has been. Therefore, when the basic component is included in the mixed solution, the solubility of the polyester resin is higher than when the basic component is not included. As a result, the dissolution time is also reduced in the mixed solvent not including the basic component. Compared with, it is shortened. In addition, the amount of organic solvent in the mixed solution is reduced compared to the case where no basic component is contained, and furthermore, the amount of newly added organic solvent is reduced by using a part of the distillate in the mixed solution. The Further, in some cases, the dispersibility of the polyester resin having a polar group in the molecule is improved as compared with the case where no basic component is contained, so that the particle size distribution in the finally obtained polyester resin aqueous dispersion becomes narrow.

  In the present embodiment, the ratio of the distillate in the mixed solution at the time of producing the polyester resin aqueous dispersion for the second and subsequent times is 30/100 or more and 95/100 or less. From the viewpoint of reducing the amount of waste, 50 / 100 or more and 95/100. However, it is appropriately selected according to the type of organic solvent used for the production of the aqueous dispersion and the type of basic component.

  As the polyester resin described above, a polyester resin obtained by condensation polymerization of a polyester raw material composed of a polycarboxylic acid component and a polyol component can be used. As a raw material for the polyester resin, an acid (or an esterified product thereof) and a glycol component are used.

  Examples of the divalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid as aromatic dicarboxylic acids. Examples of the aliphatic carboxylic acid include succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and azelaic acid. Examples of the alicyclic polycarboxylic acid include alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and dimer acid. These may be used alone or in combination of two or more.

  When the total amount of the polycarboxylic acid component is 100 mol%, the amount of aromatic dicarboxylic acid is preferably 80 mol% or more. Preferably, it is 85 mol% or more, and more preferably 90 mol%. If the total of the above aromatic dicarboxylic acids is less than 80 mol%, the hydrolysis resistance of the resulting polyester resin and the hardness of the resulting coating film may be insufficient.

  Moreover, it is particularly preferable to use terephthalic acid and isophthalic acid in combination from the viewpoint of achieving both impact resistance and hardness of the resulting coating film, and the dispersibility and stability during the preparation of the aqueous dispersion are excellent.

  Among the above polycarboxylic acids, aliphatic dicarboxylic acids other than aromatic dicarboxylic acids and alicyclic dicarboxylic acids are sebacic acid and cyclohexanedicarboxylic acid from the viewpoint of hydrolysis resistance of the resulting polyester resin and weather resistance of the resulting coating film. Acids are preferred. Moreover, you may use polyvalent carboxylic acid together in the range which does not impair the effect of this invention. Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylene Carboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid and the like, and anhydrides or lower alkyl esters of these acids.

  In addition, as the polyol, specifically, as divalent aliphatic glycol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, triethylene glycol, 2-methyl-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 2 -Methyl-3-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc. It is. Examples of the divalent aromatic glycol include an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, p-xylene-α, α'-diol, m-xylene-α, α'-diol.

  Examples of the divalent alicyclic glycol include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, hydrogenated bisphenol A, and dimer diol.

  Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6, -hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4,- Butanetriol, 1,2,5, -pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4, -butanetriol, trimethylolethane, trimethylolpropane, 1,3,5,- And trihydroxymethylbenzene.

  The polyester resin needs to have a polar group in the molecule to enable water dispersion. The polar group may be a polar group other than a carboxyl group or a salt thereof. For example, a sulfonic acid group, a phosphoric acid group, or a salt thereof can be used, and these can be used alone or in combination of two or more. As a method of introducing a sulfonic acid metal base, metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, or 2-sulfo-1,4 Examples thereof include a method using a dicarboxylic acid or glycol containing a sulfonate metal base such as a metal salt such as butanediol or 2,5-dimethyl-3-sulfo-2,5-hexanediol.

  The method for introducing a carboxyl group into the polyester resin is, after polymerizing the resin, under normal pressure and nitrogen atmosphere, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol bisanhydro trimellitate, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene 1,8: 4,5-tetracarboxylic dianhydride, etc. After the condensation is completed, these acid anhydrides are put into the oligomer state before the method of adding the acid anhydrides described above or before the resin is made high molecular weight, and then under reduced pressure. By high molecular weight by condensation, and a method of introducing a carboxyl group into the resin. Of these, the acid value targeted by the former method is easily obtained, which is preferable.

The polyester resin preferably has a hydrophilic polar group concentration of 40 to 500 equivalents / 10 ⁶ g, preferably 80 to 400 equivalents / 10 ⁶ g, from the viewpoint of the stability of the aqueous dispersion and the solvent resistance. Is more preferable, and it is further more preferable that it is 120-350 equivalent / 10 < ⁶ > g. If the polar group concentration is less than 40 equivalents / 10 ⁶ g, the storage stability of the aqueous dispersion may decrease. Moreover, when it exceeds 500 equivalent / 10 < ⁶ > g, there exists a possibility that the water resistance of the coating film obtained may be inferior.

  The polyester resin used in the present invention is obtained by co-condensation polymerization of several types of monomers, and the polymerization method is not particularly limited, and a known method is used.

  When performing condensation polymerization of the polyester resin, a polymerization catalyst may be used. Examples of the polymerization catalyst include titanium compounds (tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylacetonate, etc.), antimony compounds (tributoxyantimony, antimony trioxide, etc.), germanium compounds (tetra-n-butoxy, etc.). Examples thereof include germanium and germanium oxide), zinc compounds (such as zinc acetate), aluminum compounds (such as aluminum acetate and aluminum acetyl acetate), and tin compounds (dibutyltin dilaurate, dibutyltin oxide). You may use the said polymerization catalyst 1 type (s) or 2 or more types. Titanium compounds are preferred from the viewpoint of polymerization reactivity.

  The polyester resin has a number average molecular weight of 2000 or more, and more preferably 3000 or more. The upper limit of the number average molecular weight is not particularly limited, but is preferably substantially 100,000 or less from the viewpoint of solvent solubility. When the number average molecular weight is less than 3000, the processability, impact resistance and corrosion resistance, and dispersion stability of the resulting coating film may be lowered. The said number average molecular weight can be determined by the polystyrene conversion value by a gel permeation chromatography measurement.

  The polyester resin preferably has a glass transition temperature of a lower limit of 20 ° C. and an upper limit of 100 ° C. Preferably, the lower limit is preferably 30 ° C, more preferably 40 ° C. The upper limit is preferably 90 ° C, and more preferably 80 ° C. The glass transition temperature can be determined by measurement with a differential scanning calorimeter.

  In view of the production efficiency of the aqueous dispersion, the polyester resin is desirably amorphous so that no crystalline melting point is observed by a differential operation calorimeter.

  In the production of the polyester resin, the ratio of organic solvent / water / basic component is 980/19/1 to 500/490/10, preferably 970/29/1 to 600/391/9. More preferably, it is 960/38/2 to 700/292/8, and further preferably 950/48/2 to 800/192/8. When the water concentration is less than 2% and the basic component is less than 0.1%, the solubility is not different from that of the organic solvent alone, and the effect of adding water and the basic component may not be observed. On the other hand, if the water concentration is 50% or more and the basic component is 1% or more, the solubility may be reduced.

  Examples of organic solvents include ketone solvents such as methyl ethyl ketone and acetone, cyclic ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and dioxolane, ester solvents such as methyl acetate and ethyl acetate, methanol, and ethanol. Alcohol solvents such as isopropyl alcohol, n-propanol, n-butanol, diacetone alcohol, and 2-ethylhexanol can be used. In addition, acetonitrile, dimethylacetamide, dimethylformamide, n-methylpyrrolidone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like can also be used. Among these, use of methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, ethyl acetate, methanol, ethanol, isopropyl alcohol is preferable because of easy removal from the system.

  As the organic solvent in the present embodiment, it is possible to use at least one kind selected from the group consisting of a ketone solvent and an ester solvent and an alcohol solvent in combination with the solubility of the polyester resin having a polar group in the molecule. From the viewpoint that the balance of hydrophilicity / hydrophobicity in the system is moderately adjusted and the particle size distribution of the aqueous dispersion can be made narrower.

  In the present embodiment, it is necessary to dissolve the polyester resin in a mixed solution composed of an organic solvent and water, and then add water to the system to perform phase inversion and self-emulsification. If water is added in a large amount at once, the polyester resin may be aggregated. Therefore, it is preferable to add water little by little. It is also a preferable prescription to add warm water (hot water).

  In this embodiment, when preparing an aqueous dispersion of a polyester resin into which a carboxyl group has been introduced, in order to stabilize the dispersion, a part or all of polar groups such as carboxyl groups on the surface of the dispersion is used as described above. Neutralize with basic components as described.

  Examples of basic components that can be used for the neutralization include amine compounds typified by ammonia and triethylamine, and inorganic bases typified by sodium hydroxide, potassium hydroxide, and lithium hydroxide. For example, in order to contain substantially no basic component in the finally obtained polyester resin aqueous dispersion, an amine compound having high volatility is preferable.

  Specific examples of the highly volatile amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, Diethanolamine or triethanolamine, N-methanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamon, diisopropanolamine, triisopropanolamine, N, N-dimethylethanolamine, or N, N -Dimethylpropanolamine etc. can be mentioned. Particularly preferred are triethylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-dimethylpropanolamine and the like. Two or more of these highly volatile amine compounds may be used in combination.

  Furthermore, in the polyester resin aqueous dispersion in the present embodiment, the polyester resin may be composed of one or more kinds, and may further include an acrylic resin, an alkyd resin, an epoxy resin, a urethane resin, and the like.

  The aqueous dispersion in the present embodiment may contain a curing agent. As the curing agent, commonly used ones can be used, such as melamine compounds, block isocyanates, water-dispersed isocyanate curing agents, epoxy compounds, aziridine compounds, carbodiimide compounds, Examples include oxazoline compounds and metal ions. Melamine-based compound resins and / or blocked isocyanates are generally used from the viewpoints of various performances and costs of the obtained coating films.

  The melamine-based curing agent as the curing agent is not particularly limited, and may be either water-soluble or water-insoluble. For example, alkyl etherified melamine resin is preferable, and methoxy group and A melamine resin substituted with a butoxy group is more preferred. As such a melamine resin, those having a methoxy group alone, Sumimar M-30W, Sumimar M-40W, Sumimar M-50W, Sumimar MC-1 (all manufactured by Sumitomo Chemical Co., Ltd.), Cymel 325, Cymel 327 Cymel 370, My Coat 723; Cymel 202, Cymel 204, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 254, Cymel 266, Cymel 267 (all of which have both a methoxy group and a butoxy group) Product name, manufactured by Mitsui Cytec Co., Ltd.); Mycoat 506 (trade name, manufactured by Mitsui Cytec Co., Ltd.), Uban 20N60, Uban 20SE (both trade names, manufactured by Mitsui Chemicals Co., Ltd.), Super Bekka Min (Dai Nippon Ink Chemical) Gosha, Ltd.), and the like. These may be used alone or in combination of two or more. Among these, Sumimar M-40W and Sumimar MC-1 are more preferable.

  The blocked isocyanate can be obtained by adding a blocking agent having active hydrogen to a polyisocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and is blocked by heating. Examples include agents that dissociate to generate isocyanate groups that react with the functional groups in the resin component and cure.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.

[Preparation of polyester resin having polar group in molecule]
In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, dimethyl terephthalate 23 mol%, isophthalic acid 10 mol%, dodecenyl succinic anhydride 15 mol%, trimellitic anhydride 3 mol%, bisphenol A ethylene oxide 2 mol adduct 5 mol% and bisphenol A propylene oxide 2 mol adduct 45 mol% were charged and the reaction vessel was purged with dry nitrogen gas, and then added as a catalyst at a rate of 0.06 mol% dibutyltin oxide and nitrogen gas. The reaction was stirred for about 7 hours at about 190 ° C. under a stream of air, and the temperature was further raised to about 250 ° C. for about 5.0 hours. After that, the reaction vessel was depressurized to 10.0 mmHg and about 0.0. A kind of non-crystalline polyester polyester resin having a polar group in the molecule after stirring for 5 hours. To give an ester resin. The obtained amorphous polyester resin had a glass transition point (Tg) of 55 ° C. The weight average molecular weight (Mw) was 21,200, and the acid value of the resin was 15.2 mgKOH / g.

  Each characteristic value of the amorphous polyester resin was measured as follows.

-Measuring method of glass transition temperature-
The glass transition temperature of the toner was determined by DSC (Differential Scanning Calorimetry) measurement method, and was determined from the main maximum peak measured according to ASTM D3418-8.

  DSC-7 manufactured by Perkin Elmer Co. can be used for measurement of the main maximum peak. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

-Molecular weight measurement method for resin particles-
The molecular weight distribution is performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” apparatus, and two columns use “TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm)”. , THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Resin acid value)
The resin acid value was measured as follows. About 1 g of resin is precisely weighed and dissolved in 80 ml of tetrahydrofuran. Phenolphthalein was added as an indicator, titrated with a 0.1N KOH ethanol solution, and the end point was when the color lasted for 30 seconds. From the amount of 0.1N KOH ethanol solution used, the acid value (contained in 1 g of resin) The number of mg of KOH necessary to neutralize free fatty acids was calculated according to JIS K0070: 92).

<Comparative Example 1>
[Preparation of polyester resin aqueous dispersion A]
100 parts of the prepared amorphous polyester resin supplied via the resin supply line 12 to the water dispersion production tank 10 (FIG. 1) equipped with a stirrer, a condenser, and a thermometer, the solvent supply line 15, When dissolved in a mixed solution of 60 parts of ethyl acetate, 60 parts of isopropanol and 4 parts of ion-exchanged water supplied via the water supply line 14 (both in FIG. 1), the mixture was stirred at 70 ° C. at a stirring speed of 40 rpm for 2 hours. The resin was dissolved. After dissolution, 28% aqueous ammonia was added to adjust the pH of the solution to 7.0. Thereafter, 380 parts of ion-exchanged water (also referred to as pure water) at 65 ° C. was added, phase-inverted and self-emulsified to obtain a solvent-containing polyester resin aqueous dispersion (hereinafter also referred to as “solvent-containing emulsion”). The water dispersion production tank 10 (FIG. 1) is depressurized to 10.0 mmHg, and the vapor containing the vapor organic solvent and ammonia evaporated under the reduced pressure is cooled by the aggregator 18 (FIG. 1). The composition was recovered in the distillate recovery tank 31 without being detected. The above production process was repeated 5 batches.

<Example 1>
[Preparation of polyester resin aqueous dispersion B]
The solvent-containing polyester resin aqueous dispersion produced for the first time was produced according to Comparative Example 1. Next, the inside of the aqueous dispersion production tank 10 (FIG. 1) is depressurized to 10.0 mmHg, and the vapor containing the vapor organic solvent and ammonia evaporated under reduced pressure is cooled by the aggregator 18 (FIG. 1), and the composition detector 19, the composition of the distillate is detected by “FUD-1 Kai” (manufactured by Seika Sangyo Co., Ltd.) using ultrasonic detection as the main component, and suitable for resin dissolution based on a moisture content of 50% or less. The distillate that can be used was separated and collected in the distillate collection tank 30 (FIG. 1), and the non-reusable distillate was separated and collected in the distillate collection tank 31 (FIG. 1). At this time, 90 mass% of the total distillate was stored in the distillate collection tank 30. The distillate stored in the distillate collection tank 30 is supplied to the water dispersion production tank 10 (FIG. 1) via the liquid feed pump 32 and the distillate liquid feed line 33, and the polyester resin water dispersion for the second time. It was used for the preparation of

  In the second preparation of the polyester resin aqueous dispersion, 90 parts of the distillate stored in the distillate collection tank 30, 6 parts of ethyl acetate and isopropanol 6 newly supplied to the water dispersion production tank 10 (FIG. 1). 100 parts of an amorphous polyester resin was dissolved in a mixed solution of 0.4 parts of ion-exchanged water and stirred at 70 ° C. at a stirring speed of 40 rpm, and the resin dissolved in 1 hour. After dissolution, 28% aqueous ammonia was added to adjust the pH of the solution to 7.0. Thereafter, 380 parts of ion-exchanged water (also referred to as pure water) at 65 ° C. was added, and phase inversion and self-emulsification were carried out to obtain a solvent-containing polyester resin aqueous dispersion. The inside of the water dispersion production tank 10 (FIG. 1) is depressurized to 10.0 mmHg, and the vapor containing the vapor organic solvent and ammonia evaporated under the reduced pressure is cooled by the aggregator 18 (FIG. 1). The composition is detected using "FUD-1 Kai" (manufactured by Seika Sangyo Co., Ltd.) using ultrasonic detection as the main component, and is a reusable distillate suitable for resin dissolution based on a moisture content of 50% or less. Was collected in the distillate collection tank 30 (FIG. 1), and the non-reusable distillate was separated and collected in the distillate collection tank 31 (FIG. 1). At this time, 90 mass% of the total distillate was stored in the distillate collection tank 30. The distillate stored in the distillate collection tank 30 is supplied to the water dispersion production tank 10 (FIG. 1) via the liquid feed pump 32 and the distillate liquid feed line 33, and the polyester resin water dispersion for the third time. It was used for the preparation of When the above production process was repeated 5 batches, the amount of the distillate collected in the distillate collection tank 31 in Example 1 was 1/10 of the amount of the distillate collected in the distillate collection tank 31 in Comparative Example 1. there were. In addition, the amount of newly used organic solvent decreased compared to Comparative Example 1. Furthermore, the resin dissolution time for the second and subsequent times was shortened from 2 hours to 1 hour.

<Example 2>
[Preparation of polyester resin aqueous dispersion C]
A polyester resin aqueous dispersion was prepared in accordance with Example 1 except that “OM-11 type modified” (manufactured by Yamamoto Instruments Co., Ltd.) using a detection principle mainly composed of electrical resistance was used as the composition detector 19. did. The composition of the distillate is detected by the above-mentioned “OM-11 type modification” (manufactured by Yamamoto Instruments Co., Ltd.). The distillate that could not be reused was separated and collected into the distillate collection tank 31 (FIG. 1). At this time, 80% by mass of the total distillate was stored in the distillate collection tank 30. The distillate stored in the distillate collection tank 30 is supplied to the water dispersion production tank 10 (FIG. 1) via the liquid feed pump 32 and the distillate liquid feed line 33, and the polyester resin water dispersion for the second time. It was used for the preparation of

  In the second preparation of the polyester resin aqueous dispersion, 90 parts of the distillate stored in the distillate collection tank 30, 6 parts of ethyl acetate and isopropanol 6 newly supplied to the water dispersion production tank 10 (FIG. 1). 100 parts of an amorphous polyester resin was dissolved in a mixed solution of 0.4 parts of ion-exchanged water and stirred at 70 ° C. at a stirring speed of 40 rpm, and the resin dissolved in 1 hour. After dissolution, 28% aqueous ammonia was added to adjust the pH of the solution to 7.0. Thereafter, 380 parts of ion-exchanged water (also referred to as pure water) at 65 ° C. was added, and phase inversion and self-emulsification were carried out to obtain a solvent-containing polyester resin aqueous dispersion. The inside of the water dispersion production tank 10 (FIG. 1) is depressurized to 10.0 mmHg, and the vapor containing the vapor organic solvent and ammonia evaporated under the reduced pressure is cooled by the aggregator 18 (FIG. 1). The composition is detected using “OM-11 Kai” (manufactured by Yamamoto Instruments Co., Ltd.) using the detection principle with electrical resistance as the main component, and it is suitable for resin dissolution and can be reused based on a moisture content of 50% or less. The distillate was separated and collected in the distillate collection tank 30 (FIG. 1), and the non-reusable distillate was separated and collected in the distillate collection tank 31 (FIG. 1). At this time, 80% by mass of the total distillate was stored in the distillate collection tank 30. The distillate stored in the distillate collection tank 30 is supplied to the water dispersion production tank 10 (FIG. 1) via the liquid feed pump 32 and the distillate liquid feed line 33, and the polyester resin water dispersion for the third time. It was used for the preparation of When the above production process was repeated 5 batches, the amount of the distillate collected in the distillate collection tank 31 in Example 2 was 1/5 of the amount of the distillate collected in the distillate collection tank 31 in Comparative Example 1. there were. In addition, the amount of newly used organic solvent decreased compared to Comparative Example 1. Furthermore, the resin dissolution time after the second time was shortened from 2 hours to 1.2 hours. In addition, in the solvent-containing polyester resin aqueous dispersion obtained in the third and subsequent preparations, a small amount of coarse powder, which seems to be poorly dissolved, was observed, but at a level that does not affect the quality. there were.

<Comparative example 2>
[Preparation of polyester resin aqueous dispersion D]
A polyester resin aqueous dispersion was prepared in accordance with Comparative Example 1 except that 28% ammonia water was not neutralized when the amorphous polyester resin was dissolved, and the stirring speed during resin dissolution stirring was increased to 50 rpm. did.

  It took 1.2 hours for the resin to stir and dissolve, and phase-inversion and self-emulsification were carried out. The resulting solvent-containing polyester resin aqueous dispersion contained coarse powder that was thought to be poorly dissolved. Further, the inside of the water dispersion production tank 10 (FIG. 1) is depressurized to 10.0 mmHg, and the vapor containing the vapor organic solvent and ammonia evaporated under the reduced pressure is cooled by the aggregator 18 (FIG. 1). The composition was recovered in the distillate collecting tank 31 without being detected in 19. The amount of the distillate discarded was the same as in Comparative Example 1.

It is a schematic diagram which shows an example of a structure of the water dispersion manufacturing apparatus in this Embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 Water dispersion manufacturing tank, 12 Resin supply line, 13 Basic component supply line, 14 Pure water supply line, 15 Solvent supply line, 16 Stirrer, 17 Drive source, 18 Aggregator, 19 Composition detector, 22 Resin storage Tank, 23 Basic component storage tank, 24 Pure water storage tank, 25 Solvent storage tank, 30, 31 Distillate collection tank, 32 Liquid feed pump, 33 Distillate liquid feed line.

Claims (5)

An aqueous dispersion production tank for producing an aqueous dispersion;
A distillate composition detection means for detecting the composition of the distillate recovered in the process of removing the solvent from the aqueous dispersion production tank;
At least two or more distillate collection tanks for separating and collecting distillate according to the distillate composition;
A water dispersion production apparatus comprising: a supply unit configured to supply the liquid dispersion stored in at least one tank of the liquid collection tank to the water dispersion production tank. An aqueous dispersion production tank for producing a polyester resin aqueous dispersion by phase inversion and self-emulsification using an organic solvent, water and a basic component, a polyester resin having a polar group in the molecule,
A distillate composition detection means for detecting the composition of the distillate recovered in the process of removing the solvent from the aqueous dispersion production tank;
At least two or more distillate collection tanks for separating and collecting distillate according to the distillate composition;
A supply means for supplying a distillate stored in at least one of the distillate collection tanks to the water dispersion production tank,
In the first production of the polyester resin aqueous dispersion, in the aqueous dispersion production tank, the polyester resin having a polar group in the molecule is mixed with a mixed solution containing water and / or a basic component mainly composed of an organic solvent. After being dissolved, the basic component is added to neutralize, water is further added, phase inversion and self-emulsification are carried out to produce a polyester resin aqueous dispersion,
After the initial production of the polyester resin aqueous dispersion, the polyester resin having a polar group in the molecule, using the distillate supplied by the supply means as at least part of the mixed solution in the aqueous dispersion production tank. An aqueous dispersion production apparatus, wherein a polyester resin aqueous dispersion is produced by dissolving water, neutralizing by adding a basic component, further adding water, phase inversion and self-emulsification.   The water dispersion manufacturing apparatus according to claim 1 or 2, wherein the distillate composition detection means is detection means using a detection principle mainly composed of ultrasonic waves. An aqueous dispersion production process for producing an aqueous polyester resin dispersion by phase inversion and self-emulsification of a polyester resin having a polar group in the molecule, using an organic solvent, water, and a basic component ;
A distillate composition detection step of detecting the composition of the distillate recovered in the process of removing the solvent from the aqueous dispersion;
A supplying step of supplying the water dispersion stored in at least one of the two or more distillate collection tanks for separating and collecting the distillate according to the distillate composition to the water dispersion production process;
Including
At the first production of the polyester resin aqueous dispersion, in the aqueous dispersion production process, the polyester resin having a polar group in the molecule is mixed with water and / or a basic component mainly composed of an organic solvent. After dissolving, neutralize by adding a basic component, add water further, phase inversion, self-emulsified to produce a polyester resin aqueous dispersion,
After the first production of the polyester resin aqueous dispersion, in the aqueous dispersion production process, the polyester resin having a polar group in the molecule, using the distillate supplied in the supply process as at least part of the mixed solution. dissolved, then the basic component further added to neutralize, and further addition of water, phase inversion, polyester resin aqueous dispersions and self-emulsifying characterized that you produce a polyester resin aqueous dispersion Manufacturing method.   The polyester resin according to claim 4, wherein the mixed solution is a mixed solution composed of at least one selected from the group consisting of ketone solvents and ester solvents, an alcohol solvent, and a basic aqueous solution. A method for producing an aqueous dispersion.

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