JP2008214459A - Method for cleaning hard surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning method capable of sufficiently cleaning a hard surface with a resin adhered, a cleaning agent used in the cleaning method, an electrophotographic toner production method wherein the deterging does not affect the toner obtained by using the deterging method and the environment, and to provide an electrophotographic toner obtained by the method. <P>SOLUTION: A hard surface cleaning method comprises cleaning a hard surface having a resin adhered with a water-based cleaning agent at a cleaning temperature of 85°C or higher, wherein the water-based cleaning agent comprises (a) an alkali agent, (b) a nonionic surfactant represented by formula (1), and water and has a pH≥13. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for cleaning a hard surface to which a resin is adhered, a cleaning agent used in the cleaning method, a method for producing a toner including cleaning by the above-described cleaning method, and an electrophotographic toner obtained by the manufacturing method.

  In Patent Document 1, after supplying a monomer component into a reaction vessel, a cleaning liquid and / or virgin gas is introduced into the feed line of the monomer component to clean the feed line. A method for producing a coalescence is disclosed, and Patent Document 2 discloses a detergent composition containing a specific nonionic surfactant and an alkali agent and having a detergency at a low temperature, particularly rolling oil as a cleaning object. Has been.

JP 2003-268008 A JP 2001-64675 A

A hard surface such as a reaction vessel inner wall used in a production line for producing a polymer or using a polymer has a high viscosity or curing represented by a residual polymer after discharging the used polymer or the synthesized polymer. Residues of various inorganic and organic additives to be added to the polymer, and highly viscous or cured resin mixtures in which these resins and additives are mixed adhere to the resin (hereinafter referred to as the above resin, residue and resin). The mixture may simply be called “resin”). When the hard surface to which the resin adheres at each use is repeatedly used, it is necessary to wash the hard surface after each use and before the next use to remove the adhered resin and the like.
However, Patent Document 1 does not disclose a cleaning method for efficiently removing the resin adhering to the hard surface.

Further, for example, in the field of toner production, it is an important issue to wash a resin such as a binder resin adhering to a hard surface such as a reaction tank under the following circumstances.
That is, a so-called chemical toner in which the toner forming reaction is performed in a liquid phase is generally a coloring component composed of a pigment or a dye mainly composed of a binder resin such as styrene / acrylic copolymer, polyester, or polyether. Furthermore, it is constituted by additional components such as a plasticizer, a charge control agent, a release agent, etc. as necessary. When manufacturing a chemical toner containing these components, in the manufacturing apparatus including a reaction tank, the inner wall of the apparatus In addition, resinous deposits remain at the gas-liquid interface with the solvent used in the production. When the amount of staying material increases, when the toner type is changed, etc., cleaning of the inner wall of the manufacturing apparatus, particularly the reaction tank, will cause the staying material to be contained in the toner, which will deteriorate the thermal characteristics and development characteristics of the toner. This is essential.
On the other hand, when the above-mentioned production starts from monomers, the amount of volatile organic compounds in the toner such as volatile residual monomers such as styrene monomers remain in the toner or the organic solvent used remains in the toner. There is a concern about the negative impact on the global environment. Further, the toner in which the volatile organic compound remains reduces the thermal characteristics of the toner, causes in-machine fusion of a printer or a copying machine, or generates volatile organic substances from a fixing device such as a printer or a copying machine. There is a risk of adversely affecting the environment.

Retained material adhering to the inner wall of a reaction vessel during toner production is mainly composed of a highly viscous resin used as a toner raw material, and so far, generally, washing of a reaction vessel or the like requires an organic solvent capable of dissolving the polymer. The residue was removed by adding the mixture up to the gas-liquid interface at the time of synthesis and stirring or refluxing until the resin was completely dissolved.
However, when an organic solvent is used for cleaning the reaction tank or the like, the organic solvent remains, and there is a problem that the amount of volatile organic compounds in the toner increases in the toner to be produced next time. In addition, as described above, it is not desirable from the viewpoint of manufacturing the environmentally friendly chemical toner.

  Accordingly, the present invention relates to a cleaning method having a sufficient cleaning property for a hard surface to which a resin is adhered, in particular, a cleaning method having a sufficient cleaning property for a hard surface constituting a toner production line, and the cleaning method. It is an object to provide a method for producing an electrophotographic toner that does not adversely affect the toner and environment obtained by using the cleaning method, and an electrophotographic toner obtained by the method using the cleaning method. To do.

The present invention
(1) A hard surface cleaning method for cleaning a hard surface to which a resin is adhered with an aqueous cleaning agent having a cleaning temperature of 85 ° C. or more, wherein the aqueous cleaning agent comprises (a) an alkaline agent, and (b) the following general formula: A method for cleaning a hard surface, comprising a nonionic surfactant represented by (1) and water and having a pH ≧ 13,

(In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, l, m, and n represent the average number of moles of oxyethylene group, oxypropylene group, and oxyethylene group, respectively. Each is 0-15, l and n are not 0 at the same time, and m ≦ l + n ≦ 30.)
(2) In a toner production line including a hard surface, a method for producing an electrophotographic toner comprising a step of forming a raw material component containing a binder resin in an aqueous medium, wherein at least the hard surface is (1) A method for producing an electrophotographic toner, wherein the toner is produced after washing with the washing method described in the above,
(3) an electrophotographic toner obtained by the production method described in (2) above, (4) (a) an alkali agent, and (b) a nonionic surfactant represented by the above general formula (1); A cleaning agent for cleaning a resin-attached hard surface containing water and having a pH ≧ 13 at a cleaning temperature of 85 ° C. or higher,
I will provide a.

  According to the present invention, a cleaning method having sufficient detergency for a hard surface to which a resin is adhered, in particular, a cleaning method having sufficient detergency for a hard surface constituting a toner production line, and the cleaning method And a method for producing an electrophotographic toner that does not adversely affect the resulting toner and environment by using the cleaning method, and an electrophotographic toner obtained by the method.

[Cleaning method of hard surface]
The hard surface cleaning method of the present invention is a hard surface cleaning method for cleaning a hard surface to which a resin is adhered with an aqueous cleaning agent having a cleaning temperature of 85 ° C. or more, wherein the aqueous cleaning agent comprises: (B) The nonionic surfactant represented by the general formula (1) and water are contained, and pH ≧ 13.
The cleaning agent used in the cleaning method of the present invention has good cleaning performance at a low temperature of 50 ° C. or lower when removing dirt that does not contain resins such as oils and fats and low molecular weight compounds. Rather, it exhibits an excellent cleaning effect at high temperatures for the target resin. Accordingly, the temperature of the water-based cleaning agent may be appropriately selected according to the attached resin, the material of the hard surface to which the resin is attached, etc., but from the viewpoint of cleaning performance, it is 85 ° C. or higher, and 85 to 105 ° C. Preferably, 85-100 degreeC is more preferable, and 90-100 degreeC is still more preferable. At such a high temperature, the nonionic surfactant represented by the general formula (1) penetrates into the resin and emulsifies, so it is considered that the contact opportunity between the alkaline agent and the resin is increased. For this reason, it is considered that the aqueous cleaning agent according to the present invention promotes the hydrolysis of the resin and improves the detergency of the resin attached to the hard surface.

(Water-based cleaning agent)
The cleaning agent for cleaning the resin-attached hard surface according to the present invention at a cleaning temperature of 85 ° C. or higher is (a) an alkali agent, (b) a nonionic surfactant represented by the following general formula (1), It contains water and has a pH ≧ 13.

(In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, l, m, and n represent the average number of moles of oxyethylene group, oxypropylene group, and oxyethylene group, respectively. Each is 0-15, l and n are not 0 at the same time, and m ≦ l + n ≦ 30.)

  The cleaning agent contains (a) an alkali agent, and any alkali-soluble agent that can achieve the pH value can be used as the alkali agent. Specific examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, sodium orthosilicate, sodium metasilicate, sodium sesquisilicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, etc. Salts, phosphates such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, carbonates such as disodium carbonate, sodium bicarbonate, dipotassium carbonate, potassium bicarbonate, boron such as sodium borate Examples include acid salts. Two or more water-soluble alkaline agents may be combined. From the viewpoint of detergency such as resin adhering to the hard surface, sodium hydroxide, potassium hydroxide, sodium orthosilicate, and sodium metasilicate have stronger detergency even at the same pH or blending amount. Sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is still more preferable.

The cleaning agent contains (b) a nonionic surfactant represented by the general formula (1). In the general formula (1), R is linear or branched having 8 to 18 carbon atoms. It is a chain alkyl group or an alkenyl group, and is preferably a linear or branched alkyl group having 10 to 14 carbon atoms from the viewpoint of detergency when the detergent is used a plurality of times. l, m, and n represent the average number of moles of oxyethylene group, oxypropylene group, and oxyethylene group, respectively, and are each 0 to 15, preferably from 0 to 12, more preferably from the above-mentioned repetitive cleaning point. Is 2-8. l + n is m or more and 30 or less, and is preferably 4 to 20, and more preferably 8 to 12 from the above-mentioned repetitive cleaning property.
In the present invention, as the nonionic surfactant represented by the general formula (1), those in which the carbon number of R is 10 to 14, l, m and n are 2 to 8, and l + n is 8 to 12 are preferable. .

Furthermore, the nonionic surfactant represented by the general formula (1) is preferably one having an HLB of 4.3 to 8.2, more preferably 5 to 7.9 from the viewpoint of detergency. The thing of 5.5-7.5 is still more preferable. In addition, HLB of a component (b) is HLB by the Davis (Davies) method, and is a value represented by a following formula. The number of hydrophilic groups and the number of lipophilic groups in the following formula are described in “New Edition Surfactant Handbook”, Engineering Books Co., Ltd., May 1, 1996, Table 5-1-3 on page 235. The value that is used is adopted.
HLB = Σ [base number of hydrophilic group of component (b)] + Σ [base number of lipophilic group of component (b)] + 7

Specific examples of the nonionic surfactant represented by the general formula (1) include R—O— (PO) ₂ (EO) ₁₂ —H (R: decyl group), R—O— (EO) ₅ (PO ) ₂ (EO) ₅ —H (R: decyl group), R—O— (EO) ₅ (PO) ₂ (EO) ₅ —H (R: dodecyl group), R—O— (EO) ₇ (PO ) ₂ (EO) ₇ —H (R: dodecyl group), R—O— (EO) ₉ (PO) ₂ (EO) ₉ —H (R: mixed alkyl group derived from C _12-15 synthetic alcohol), R —O— (EO) ₅ (PO) ₂ (EO) ₁₀ —H (R: mixed alkyl group derived from C _14-15 synthetic alcohol), R—O— (EO) ₉ (PO) ₂ (EO) ₉ — H (R: secondary dodecyl group), R—O— (EO) ₇ (PO) ₂ (EO) ₇ —H (R: secondary dodecyl group), R—O— (EO) ₅ (PO) ₂ ( EO) ₅ -H (R: 2 grade dodecyl group), and the like But from the viewpoint of detergency and low foaming, _{preferably, R-O- (EO) 5} (PO) 2 (EO) 5 -H (R: decyl group), R-O- (EO) 5 (PO ) ₂ (EO) ₅ —H (R: dodecyl group), R—O— (EO) ₅ (PO) ₂ (EO) ₅ —H (R: secondary dodecyl group), more preferably R—O. -(EO) ₅ (PO) ₂ (EO) _5- H (R: secondary dodecyl group).

  As the nonionic surfactant represented by the general formula (1), a commercially available product can be used. For example, BLAUNON EH-2 (R: 2-ethylhexyl group, l = m = 0, n = 2), BLAUNON EH-4 (R: 2-ethylhexyl group, l = m = 0, n = 4), BLAUNON EH-6 (R: 2-ethylhexyl group, l = m = 0, n = 6), BLAUNON EH-11 (R: 2-ethylhexyl group, l = m = 0, n = 11), Emulgen 109P manufactured by Kao Corporation (R: dodecyl group, l = m = 0, n = 9), Emulgen 120 (R: dodecyl group, l = m = 0, n = 12), softanol EP9050 (secondary dodecyl, l = 9, m = 5, n = 0), softanol EP12030 (secondary dodecyl, l = 12, m = , N = 0), Softanol 90 (R: secondary dodecyl group, l = m = 0, n = 9), Softanol 120 (R: secondary dodecyl group, l = m = 0) manufactured by Nippon Shokubai Chemical Industry Co., Ltd. N = 12), Softanol 150 (R: secondary dodecyl group, l = m = 0, n = 15), Softanol 200 (R: secondary dodecyl group, l = m = 0, n = 20), etc. it can. Two or more of the above compounds may be combined.

Specific examples of the raw material alcohol to which ethylene oxide or propylene oxide is added when obtaining the nonionic surfactant represented by the general formula (1) include linear alcohols such as lauryl alcohol and myristyl alcohol (for example, Kao Corporation ), Commercial names such as “Calcoal 2098” and “Calcoal 4098”), branched alcohols synthesized using the oxo method or Ziegler method (for example, Kyowa Hakko Co., Ltd.) Trade names “Oxocol 1213”, “Tridecanol” manufactured by Mitsubishi Chemical Corporation, “Dobanol 23”, “Dovanol 25” manufactured by Mitsubishi Chemical Corporation, “Neodoll 23”, “Neodoll 25” manufactured by Shell Chemical Co., Ltd. And other specific examples of nonionic surfactants represented by the general formula (1). And those, SOFTANOL 30 (R is secondary dodecyl, l = m = 0, n = 3) or the like can also be used. These alcohols may be used in combination of two or more.
In addition, as a method for adding alkylene oxide to these alcohols and the like, a known alkoxylation method can be used.

The cleaning agent of the present invention preferably contains (c) a chelating agent from the viewpoints of stability and cleaning properties of a resin or the like attached to a hard surface.
The chelating agent is considered to play a role of enhancing the cleaning effect by binding to and removing metal atoms in the soil.
In particular, in the production of a chemical toner described later, in an emulsion aggregation method in which emulsion particles are aggregated, a water-soluble metal salt such as potassium, calcium, aluminum, or magnesium may be used as an aggregating agent. In this case, the staying material adhering to the inner wall of the reaction tank contains the metal and has hydrophobicity. In the case of using the above-mentioned flocculant, the cleaning agent of the present invention preferably contains a chelating agent in order to improve the cleaning performance of the resin or the like adhering to the inner wall of the reaction tank.
The chelating agent is preferably an alkali metal salt or a lower amine salt of gluconic acid, glucoheptonic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, hydroxyethylidene diphosphonic acid, more preferably sodium gluconate, sodium glucoheptonate , Sodium ethylenediaminetetraacetate, sodium citrate, sodium hydroxyethylidene diphosphonate.

  In addition, the cleaning agent according to the present invention has a phase separation when these components are concentrated in (a) an alkaline agent and (b) a nonionic surfactant from the viewpoint of cleaning properties of a resin or the like attached to a hard surface. Since it is preferable that the aqueous solution is stable without precipitation, (d) at least one selected from compounds represented by the following general formulas (2) and (3) (hereinafter also referred to as solubilizers) It is preferable to contain the above, and if necessary, it is preferable to contain the below-mentioned slurry agent for ensuring the fluidity of the concentrated system.

_{^{R 1 -X- (CH 2) pCOOM}} 1 (2)
R ² -COOM ² (3)
[Wherein, R ¹ represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 4 to 22 carbon atoms or an aromatic hydrocarbon group having 5 to 18 carbon atoms, and X represents a group> NH, > N (CH ₂ ) qCOOM ¹ or> CHCOOM ¹ is shown. R ² represents a saturated or unsaturated linear aliphatic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 5 to 18 carbon atoms. M ¹ and M ² each represent a hydrogen atom, an alkali metal, an aliphatic amine having 1 to 4 carbon atoms, ammonia or an alkanolamine, and p represents an integer of 1 to 3. ]
Examples of the compound represented by the general formula (2) include alkenyl succinic acid having 6 to 18 carbon atoms and a salt thereof, or a compound represented by the following formula.

Examples of the compound represented by the general formula (3) include hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, butyric acid, valeric acid, isobutyric acid, 2-ethylhexanoic acid, and salts thereof. .
Specific examples of M ¹ and M ² in the general formulas (2) and (3) include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, diethylenetriamine, ammonia, monoethanolamine, diethanolamine, triethanolamine, and the like. C2-C10 alkanolamine, potassium, sodium, a hydrogen atom, etc. are mentioned.

  Examples of the slurrying agent used in the present invention include water-soluble polymer carboxylic acid represented by the following general formula (4), naphthalenedicarboxylic acid, and alkali metal salts or amine salts thereof.

[Wherein, R ^{3 to} R ⁸ are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, COOM, or OH, and R ^{3 to} R ⁸ are all May be the same or different. M is any one of a hydrogen atom, an alkali metal, an alkylamine having 1 to 4 carbon atoms, and an alkanolamine having 1 to 6 carbon atoms. Both ends of the general formula (4) is not particularly limited, hydrogen, OH, alkyl group having 1 to 5 carbon atoms, (M is the same meaning as defined above) alkoxyl group or SO ₃ M 1 to 5 carbon atoms such as These may be the same or different. p and q each represent the number of moles of the monomer in [], and p may be 0. When p is 0, the monomer is a homopolymer represented by q. The copolymerization ratio p / q of p and q is 0/10 to 10/1, and the weight average molecular weight (Mw) is 1,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 20,000. The polymerization form may be block or random. ]

  The cleaning agent of the present invention further contains water such as deionized water and distilled water. The water is preferably contained in the cleaning agent of the present invention in an amount of 40% by weight or more, more preferably 50% by weight or more, from the viewpoint of detergency and safety.

  When the cleaning agent of the present invention is provided in the form of a concentrated cleaning agent, its composition is not particularly limited, but (a) the alkali agent is 1 to 50% by weight, more preferably 15 to 45% by weight, b) The nonionic surfactant is preferably 0.1 to 20% by weight, more preferably 0.5 to 5% by weight. Further, when (c) a chelating agent is contained, it is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and (d) when a solubilizing agent or a slurrying agent is contained, preferably Is 0.05 to 40% by weight, more preferably 0.1 to 10% by weight.

In addition to the above components, the cleaning agent of the present invention may contain components such as surfactants and antifoaming agents other than the general formula (1) that are usually used in cleaning agents as necessary.
Further, the cleaning agent of the present invention has a pH ≧ 13 at 25 ° C. From the viewpoint of detergency of the resin or the like on the hard surface, the pH of the cleaning agent is preferably 14 or more at 25 ° C. Even if pH ≧ 13, the alkaline agent is contained in the aqueous cleaning agent in the weight described later. % Is more preferable.
In the present invention, each of the above components is preferably contained in an aqueous medium, preferably water, and used as the pH range.

  The aqueous cleaning agent can be used as it is or diluted with water or the like, but the above-mentioned (a) alkaline agent, (b) nonionic surfactant in the composition (stock solution or diluted solution) at the time of use, The content of each component of (c) chelating agent and (d) solubilizer varies depending on the type of the object to be cleaned and the type of dirt, but from the viewpoint of cleaning of the resin adhering to the hard surface, in the aqueous cleaning agent, (A) The alkali agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, and still more preferably 0.5 to 3% by weight. Moreover, 0.005 to 5 weight% is preferable, (b) nonionic surfactant has more preferable 0.01 to 2 weight%, and 0.02 to 1 weight% is still more preferable. (C) When using a chelating agent, 0.005 to 3 weight% is preferable, 0.01 to 2 weight% is more preferable, and 0.02 to 1 weight% is still more preferable. (D) When using a solubilizer, from a viewpoint of low-temperature stability and economical efficiency, 0.01 to 3 weight% is preferable and 0.05 to 1 weight% is still more preferable.

In the present invention, the substance to be cleaned, which will be described later, is cleaned using the cleaning agent. However, the cleaning operation is not particularly limited, and normal cleaning operations can be used. For example, immersion cleaning, spray cleaning, brushes Either cleaning or the like can be used.
In addition, the cleaning agent can be reused after being stored in a storage facility such as a tank or a drum can after use. Therefore, it is desirable that the cleaning effect can be maintained even after storing the used cleaning agent. However, the cleaning agent of the present invention is excellent in such storage performance because it has high dirt durability. . From the above, the cleaning agent of the present invention can be used repeatedly 5 times or more, preferably 8 times or more, more preferably 10 times or more, on the hard surface to which the resin is adhered.

(Substance to be cleaned)
The to-be-cleaned material to which the cleaning method of the present invention can be applied is a resin deposit produced by using a polymer or formed during polymer formation. Such resin deposits are composed of various polymers, and there are no particular limitations on the polymer. For example, polyvinyl alcohol, cationized cellulose, which is a polymer for thickeners, and polymers for adhesives. Polyamide, polyester which is a polymer for plasticizers, and the like can be mentioned.

The cleaning method of the present invention is particularly applied to a substance to be cleaned in a toner production line, particularly a toner production line having a step of forming a raw material component containing a binder resin into an aqueous medium. The stagnant substance on the hard surface of the reaction tank, which is such a substance to be cleaned, is a substance in which a polymer-like adhering substance stays mainly at the gas-liquid interface with the solvent used for toner production, which will be described later. Ingredients such as binder resin and unreacted resin raw material monomer in toner production, various additives such as colorant, mold release agent, charge control agent, surfactant, flocculant, etc. It is a binder resin.
The cleaning method of the present invention is preferably applied to a solid residue containing each of the above-mentioned components as a substance to be cleaned, but more preferably to a substance mainly composed of the binder resin.

(Hard surface)
As described above, the aqueous detergent used in the cleaning method of the present invention is excellent not only at a low temperature of 50 ° C. or lower, but rather at a high temperature of 85 ° C. or higher, preferably 90 ° C. or higher, more preferably 95 ° C. or higher. Demonstrates cleaning effect.
Accordingly, the hard surface to which the resin to which the cleaning method of the present invention is applied adheres widely to metals, glass, ceramics, plastics, and the like. In particular, it is preferable to target a metal that has high alkali resistance and hardly undergoes temperature deformation.
Iron and stainless steel are preferable, and stainless steel is a more preferable target.

  In addition, the hard surface to which the resin to which the cleaning method of the present invention is applied is preferably a member in contact with a polymer. As such a member, for example, a polymer is used and / or a polymer is manufactured. The hard surface which comprises the manufacturing line to perform is mentioned preferably. Specifically, a production line using a polymer of a vinyl polymer such as styrene-acrylic, a production line using a polycondensation polymer such as polyester, polyethylene terephthalate or polyurethane, or a ring-opening polymerization system such as an epoxy resin. It is preferable to target the inner wall of an apparatus, particularly the inner wall of the reaction vessel, in a production line using a polymer or a production line such as a production line for synthesizing these polymers.

  In addition, the cleaning method of the present invention is a member that constitutes a production line used in the step of forming a raw material component containing a binder resin for toner in an aqueous medium as a member in contact with the polymer, specifically, It is preferably applied to a hard surface such as an inner wall of a production apparatus constituting a toner production line. More specifically, a production line including a step of preparing a resin emulsion from raw material components containing a binder resin in an aqueous medium, and a step of aggregating and coalescing resin particles in the obtained resin emulsion. It is preferable to use it for the member to comprise.

  As the toner production line, for example, a batch production line or a continuous production line is used, and as a reaction tank, toner production and the like are used, and any known ones are used. it can. In particular, in the production of toner, a reactor such as a reaction tank used in an emulsification process for dispersing and emulsifying a resin, a production apparatus such as a reaction tank used in an aggregation and coalescence process of an emulsion, and these are continuously performed. For example, a continuous production apparatus for the production process, an apparatus for performing the subsequent processes, and a liquid feed line for connecting them.

The cleaning method of the present invention can be applied to production lines of various scales, for example, from a small scale at a laboratory level to a large scale for mass production. Specifically, the reaction tank has a capacity of about 200 L. It can be applied to a reactor having a capacity of 10 m ³ or more, further about 20 m ³ or even larger.
Any of those mentioned as the hard surface can be used in the reaction vessel, but for example, those described in JP-A-9-258479 can be used. Specifically, the surface is glass-lined. Various materials such as a glass lining reactor, a reactor having a conductive surface, typically a reactor made of a corrosion-resistant metal such as stainless steel can be preferably used.

[Cleaning agent for hard surface]
The cleaning agent for cleaning the resin-attached hard surface of the present invention at 85 ° C. or higher includes (a) an alkali agent, (b) a nonionic surfactant represented by the general formula (1), and water. Although it contains (a) an alkaline agent and (b) its constituent components including the nonionic surfactant represented by the general formula (1), the above-described aqueous detergent according to the present invention is described. Is the same as The pH value is also the same.

[Method for producing toner for electrophotography]
The present invention is a method for producing an electrophotographic toner having a step of granulating a raw material component containing a binder resin in an aqueous medium in a toner production line including a hard surface, and at least the hard surface, The present invention relates to a method for producing an electrophotographic toner, wherein the toner is produced after washing by the washing method. The toner production line including the hard surface and the cleaning method are as described above.
Hereinafter, a method for producing an electrophotographic toner having a step of forming a raw material component containing a binder resin into an aqueous medium will be described.
Specifically, the method for producing a toner of the present invention includes (A) a step of preparing a resin emulsion from a raw material component containing a binder resin in an aqueous medium, and (B) in the obtained resin emulsion. It has a process of aggregating and coalescing resin particles.

(Process (A))
Step (A) is a step of preparing a resin emulsion from a raw material component containing a binder resin in an aqueous medium.
Examples of the binder resin used here include known resins used for toner, such as styrene-acrylic copolymer, epoxy, polycarbonate, polyether, polyurethane, and the like. From the viewpoint of toner fixing properties and durability, it is preferable that a styrene / acrylic copolymer and polyester having high viscosity and high adhesion are contained. When the polyester is included, the content of the polyester is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and substantially 100% by weight from the viewpoint of fixability and durability. More preferably.

  In the present invention, polyester includes not only polyester but also polyester modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.

The raw material monomer of the polyester is not particularly limited, and a known alcohol component and a known carboxylic acid component such as carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester are used.
Examples of the alcohol component include alkylenes of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane (carbon number of 2 to 3). ) Oxide (average addition mole number 1-16) adduct, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or their alkylene (2-4 carbon atoms) oxide (average) Addition mole number 1-16) Additions etc. are mentioned.
This alcohol component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The carboxylic acid component includes dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid and succinic acid, alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octenyl succinic acid, or carbon. Trivalent or higher polyvalent carboxylic acids such as succinic acid, trimellitic acid and pyromellitic acid substituted with alkenyl groups of 2 to 20, anhydrides of these acids and alkyls of these acids (1 to 3 carbon atoms) ) Esters and the like. This carboxylic acid component may be used individually by 1 type, and may be used in combination of 2 or more type.

The polyester can be produced, for example, by subjecting an alcohol component and a carboxylic acid component to condensation polymerization at a temperature of about 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.
As the esterification catalyst, an esterification catalyst such as a tin compound such as dibutyltin oxide or tin dioctylate or a titanium compound such as titanium diisopropylate bistriethanolamate can be used. The amount of the esterification catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

From the viewpoint of storage stability of the toner, the softening point of the polyester is preferably 70 to 165 ° C, and the glass transition point is preferably 50 to 85 ° C. The acid value is preferably 6 to 35 mgKOH / g, more preferably 10 to 35 mgKOH / g, and still more preferably 15 to 35 mgKOH / g, from the viewpoint of manufacturability during emulsification.
From the viewpoint of the durability of the toner, the number average molecular weight of the polyester is preferably 1,000 to 10,000, and more preferably 2,000 to 8,000.

The aqueous medium for dispersing and emulsifying the resin is mainly composed of water. From the environmental viewpoint, the content of water in the aqueous medium is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 100% by weight.
Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, can be used. In the present invention, it is preferable to atomize the binder resin using only water without substantially using an organic solvent.

The resin emulsion obtained by emulsifying the resin in the aqueous medium contains various additives that are usually contained in the toner, such as a colorant, a release agent, and a charge control agent, if necessary. Can be made.
The colorant is not particularly limited, and any known colorant can be used. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, Acridine, Xanthene, Azo Benzoquinone, azine, anthraquinone, indico, thioindico, phthalocyanine, aniline black, thiazole One of the various dyes and the like, alone or in combination of two or more can be used.
The content of the colorant is preferably 20 parts by weight or less, and more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles.

As release agents, low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide; carnauba Plant waxes such as wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; mineral and petroleum systems such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax Wax etc. are mentioned.
The content of the release agent is preferably 1 to 20 parts by weight and more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles in consideration of the addition effect and the adverse effect on the chargeability. .

Examples of charge control agents include benzoic acid metal salts, salicylic acid metal salts, alkyl salicylic acid metal salts, catechol metal salts, metal-containing bisazo dyes, tetraphenylborate derivatives, quaternary ammonium salts, alkylpyridinium salts, and the like. Can be mentioned.
The content of the charge control agent is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of the resin constituting the resin particles.

The resin emulsion is preferably 5 parts by weight or less, more preferably 0.1 to 3.5 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles, from the viewpoint of improving the emulsifiability of the resin. Parts, more preferably 0.1 to 3 parts by weight of surfactant is preferably present.
Examples of the surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type, and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene Nonionic surfactants such as glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based and the like can be mentioned. Although the said surfactant may be used individually by 1 type, you may use it in combination of 2 or more type.

Specific examples of the anionic surfactant include dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium alkyl ether sulfate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, and the like. Specific examples of the activator include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitan monostearate, polyoxyethylene alkylamine and the like.

The resin emulsion is preferably prepared by emulsifying the resin from the viewpoint of reducing the particle size of the resin particles and narrowing the particle size distribution of the obtained toner.
In this emulsification step, it is preferable to first add an alkaline aqueous solution to the resin and disperse the resin and the additive used as necessary.
The alkaline aqueous solution preferably has a concentration of 1 to 20% by weight, more preferably 1 to 10% by weight, and still more preferably 1.5 to 7.5% by weight. As for the alkali to be used, it is preferable to use an alkali that enhances the surface activity when the polyester becomes a salt. Specific examples thereof include monovalent alkali metal hydroxides such as potassium hydroxide and sodium hydroxide.

After dispersion, neutralize at a temperature equal to or higher than the glass transition point of the resin constituting the resin particles, and then add a water-based medium at a temperature equal to or higher than the glass transition point to produce a resin emulsion by phase inversion emulsification. can do.
Examples of the aqueous medium used for the production of the resin emulsion include the same as the aqueous medium described above.
The amount of the aqueous medium is preferably 100 to 2,000 parts by weight, and 150 to 1,500 parts by weight with respect to 100 parts by weight of the resin constituting the resin particles, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. More preferred.
Further, the temperature at this time is preferably in the range of not less than the glass transition point and not more than the softening point of the resin constituting the resin particles from the viewpoint of preparing a dispersion in which fine resin particles are dispersed. By carrying out the emulsification at a temperature within the above range, the emulsification is carried out smoothly and no special apparatus is required for heating. From this point, the temperature is preferably not less than (glass transition point + 10 ° C.) of the resin constituting the resin particles, and preferably not more than (softening point−5 ° C.).

The volume median particle size (D50) of the resin particles in the resin emulsion in which the resin particles thus obtained are dispersed is preferably 0.02 to perform uniform aggregation in the subsequent aggregation process. It is 2 μm, more preferably 0.05 to 1 μm, still more preferably 0.05 to 0.6 μm. Here, “volume median particle size (D50)” means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size. The measuring method is as described later.
The solid content concentration of the resin emulsion thus obtained is 5 to 50 from the viewpoint of causing stability of the emulsion and handling of the resin emulsion in the aggregation step to be performed later, and uniform aggregation. % By weight is preferred, 5 to 45% by weight is more preferred, and 10 to 40% by weight is even more preferred.

  Other methods for obtaining a dispersion containing resin particles include, for example, a method in which a polycondensable monomer is first emulsified and dispersed in an aqueous medium by mechanical shear or ultrasonic waves as a target resin particle raw material. It is done. At this time, if necessary, additives such as a polycondensation catalyst and a surfactant are also added to the water-soluble medium. And polycondensation is advanced by, for example, heating the solution. For example, when the resin is polyester, the above-mentioned polyester polycondensable monomer and polycondensation catalyst can be used, and the above-mentioned surfactants can be used similarly.

(Process (B))
Step (B) is a step of aggregating and coalescing the resin particles in the obtained resin emulsion.
In the aggregation step of the step (B), it is preferable to add an aggregating agent in order to aggregate the resin particles. As the aggregating agent, a quaternary salt cationic surfactant, an organic aggregating agent such as polyethyleneimine, an inorganic aggregating agent such as an inorganic metal salt, an ammonium salt or a divalent or higher metal complex is used. Examples of inorganic metal salts include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminum sulfate, polyaluminum chloride, polyaluminum hydroxide, Examples thereof include inorganic metal salt polymers such as calcium sulfide. From the viewpoint of achieving highly accurate toner particle size control and a sharp particle size distribution, it is preferable to use a monovalent salt. Here, the monovalent salt means that the valence of the metal ion or cation constituting the salt is 1. As monovalent salts, organic flocculants such as quaternary salt cationic surfactants, inorganic flocculants such as inorganic metal salts and ammonium salts are used. From the viewpoint of achieving a fine particle size distribution, a water-soluble nitrogen-containing compound having a molecular weight of 350 or less is used.

Examples of such water-soluble nitrogen-containing compounds include ammonium salts such as ammonium halide, ammonium sulfate, ammonium acetate, ammonium benzoate and ammonium salicylate, and quaternary ammonium salts such as tetraalkylammonium halides.
The amount of the flocculant used varies depending on the valence of the charge of the flocculant to be used, but when a monovalent flocculant is used, from the viewpoint of aggregability, 2 parts per 100 parts by weight of the resin constituting the resin particles. The weight is preferably from 50 parts by weight to 50 parts by weight, more preferably from 3.5 parts by weight to 40 parts by weight, and even more preferably from 3.5 parts by weight to 30 parts by weight.

The addition of the flocculant is performed after adjusting the pH in the system in order to perform uniform agglomeration and at a temperature not higher than the glass transition point of the resin constituting the resin particles, preferably not higher than (glass transition point−10 ° C.). It is desirable to carry out at the temperature of. The flocculant can be added as an aqueous medium solution. It is preferable to sufficiently stir at the time of adding the flocculant and after completion of the addition.
Further, the volume median particle size (D50) of the aggregated particles in the system in the step (B) is preferably 1 to 10 μm, more preferably 2 to 8 μm, from the viewpoint of improving the image quality. 3-8 micrometers is further more preferable. The obtained agglomerated particles are subjected to a step of coalescing the agglomerated particles (a coalescence step).

In the coalescence process, the temperature in the system is preferably equal to or higher than the temperature in the system in the aggregation process, but the target toner particle size, particle size distribution, shape control, and particle fusing property From the viewpoint of the above, the glass transition point or higher of the binder resin is preferable, (softening point + 20 ° C.) or lower is more preferable, (glass transition point + 5 ° C.) or higher, (softening point + 15 ° C.) or lower is more preferable, (glass transition point) + 10 ° C.) or higher and (softening point + 10 ° C.) or lower is more preferable. The stirring speed is preferably a speed at which the aggregated particles do not settle.
The coalescence process can be performed simultaneously with the aggregation process, for example, by continuously raising the temperature or by raising the temperature to a temperature at which aggregation and coalescence can be performed and then continuing stirring at that temperature.
From the viewpoint of high image quality, the volume-median particle size (D50) of the coalesced particles is preferably 1 to 10 μm, more preferably 2 to 10 μm, and even more preferably 3 to 9 μm.

The obtained coalesced particles are appropriately subjected to a solid-liquid separation process such as filtration, a washing process, and a drying process as necessary, whereby toner base particles can be obtained.
In the washing step, for the purpose of ensuring sufficient charging characteristics and reliability as a toner, it is preferable to use an acid to remove metal ions on the surface of the toner base particles, and washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner base particles is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, from the viewpoint of chargeability.

In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner particles is preferably adjusted to 1.5% by weight or less, more preferably 1.0% by weight or less, and still more preferably 0.5% by weight or less from the viewpoint of toner chargeability. Is preferred.
In the cleaning method of the present invention, the cleaning can be performed on any of the hard surfaces constituting the toner production line including the step (A), the step (B) and other steps, and the hard surface constituting the production line. It may be performed on at least one of the surfaces. However, from the viewpoint of the performance of the obtained toner, it is preferable that more parts are cleaned in the production line. The washing is preferably performed after completion of the entire toner production process and before the next toner production.

[Electrophotographic toner]
The electrophotographic toner of the present invention is obtained by the toner production method including the cleaning method of the present invention, and the content of the volatile organic compound in the toner thus obtained is preferably 1000 ppm or less. More preferably, it is 800 ppm or less, More preferably, it is 500 ppm or less. Such a toner has a small particle size suitable for high definition and high image quality, has excellent charging characteristics and fixing properties, and contains almost no organic solvent. And in-machine fusion such as copying machines and the like, and does not adversely affect the environment.

  The softening point of the electrophotographic toner thus formed is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and further preferably 60 to 120 ° C. from the viewpoint of low-temperature fixability. . Moreover, 30-80 degreeC is preferable from a durable viewpoint, and, as for a glass transition point, 40-70 degreeC is more preferable. In addition, the measuring method of a softening point and a glass transition point is based on these measuring methods in resin.

In the toner of the present invention, an auxiliary agent such as a fluidizing agent can be added to the toner particle surface as an external additive. External additives include known fine particles such as silica fine particles, titanium fine particles, alumina fine particles, cerium oxide fine particles, carbon black and other inorganic fine particles, and polymer fine particles such as polycarbonate, polymethyl methacrylate and silicone resin. Can be used.
The amount of the external additive is preferably 1 to 5 parts by weight and more preferably 1.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner before processing with the external additive.

From the viewpoint of high image quality, the volume median particle size (D50) of the toner particles is preferably 1 to 10 μm, more preferably 2 to 8 μm, and even more preferably 3 to 8 μm.
The toner for electrophotography obtained by the present invention can be used as a one-component developer or a two-component developer mixed with a carrier.

Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4
5 g of polyester 1 (prepared by the method described below) fluidized by heating to 200 ° C. was dropped on a test piece (width 70 mm, length 100 mm, thickness 1 mm) made of SUS304, and the Teflon (registered trademark) type Use a spatula to spread over the entire surface of one side of the test piece and cover 100%. Polyester 1 is solidified at room temperature to prepare a test piece for a cleaning test. In a 1000 mL beaker, 3.0 g of tetrasodium ethylenediaminetetraacetate and 946.3 g of ion-exchanged water are added and stirred to dissolve. Thereto was added 3.0 g of each surfactant shown in Table 1, 5.0 g of disodium 2-ethylhexylaminodipropionate, 1.0 g of potassium octoate, and 41.7 g of a 48 wt% potassium hydroxide aqueous solution, followed by stirring. Mixed. A washing solution was prepared by heating to each temperature. The pH of the cleaning liquids of Examples 1-1 to 1-5 was 13.5. Each surfactant shown in Table 1 was prepared by a method according to “Synthesis of nonionic surfactant” described later.

Using two blades made of SUS304 (width 10 mm, length 30 mm), stirring the cleaning liquid at the cleaning temperature shown in the table at a rotation speed of 200 rpm, the test piece was suspended and immersed so that the resin was completely immersed in the cleaning liquid, The sample was taken out after 30 minutes, immersed in a 1000 mL beaker containing 1000 g of ion-exchanged water at 25 ° C. for 1 minute to rinse the cleaning solution, and the state of the test piece surface was visually observed to evaluate the cleaning property. The results are shown in Table 1. Judgment criteria are as follows.
◎ There is no residual resin, and the entire test piece surface is covered with water.
○ Resin does not remain, but part of the test piece surface is not covered with water.
Δ Resin remains, but the coated area of the test piece surface is less than S / 2.
X Resin remains and the coating area on the surface of the test piece is S / 2 or more.

In the following examples and the like, each property value was measured and evaluated by the following method.
[Acid value of resin]
Measured according to JIS K0070. However, the measurement solvent was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point and glass transition point of resin and toner]
(1) Softening point Using a flow tester (Shimadzu Corporation, “CFT-500D”), a 1 g sample was heated at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, Extrude from a 1 mm long nozzle. Plot the flow tester drop by the flow tester against the temperature, and let the softening point be the temperature at which half the sample flowed out.
(2) Maximum endothermic peak temperature Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C., and the temperature of the sample cooled to 0 ° C. at a temperature drop rate of 10 ° C./min was raised. Measure at a rate of 10 ° C / min. Among the observed endothermic peaks, the peak temperature on the highest temperature side is defined as the highest endothermic peak temperature. When the maximum peak temperature is within 20 ° C. from the softening point, the peak temperature is taken as the melting point, and when it is 20 ° C. or more lower than the softening point, the peak is caused by the glass transition.

[Number average molecular weight of resin]
The molecular weight distribution is measured by gel permeation chromatography and the number average molecular weight is calculated by the following method.
(1) Preparation of sample solution The resin is dissolved in chloroform so that the concentration is 0.5 g / 100 ml. Subsequently, this solution is filtered using a fluororesin filter having a pore size of 2 μm [manufactured by Sumitomo Electric Industries, Ltd., “FP-200”] to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Using the following apparatus, chloroform is flowed at a flow rate of 1 ml per minute, and the column is stabilized in a constant temperature bath at 40 ° C. 100 μl of the sample solution is injected therein and measurement is performed. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. In this calibration curve, several types of monodisperse polystyrene (2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ manufactured by Tosoh Corporation), 2.10 × manufactured by GL Sciences Inc. 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) are used as standard samples.
Measuring device: CO-8010 (manufactured by Tosoh Corporation)
Analysis column: GMHLX + G3000HXL (manufactured by Tosoh Corporation)

[Particle size of resin particles]
(1) Measuring apparatus: Laser scattering type particle size measuring machine (LA-920, manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water is added to the measurement cell, and the volume average particle diameter (D ₄ ) is measured at a temperature where the absorbance falls within an appropriate range.

[Solid concentration of emulsion]
Using an infrared moisture meter (Ketto Science Laboratory Co., Ltd .: FD-230), 5 g of the emulsion was wet at a drying temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). Measure the moisture content of the base. The solid content was calculated according to the following formula.
Solid content (%) = 100-M
M: wet base moisture (%) = [(W−W0) / W] × 100
W: Sample weight before measurement (initial sample weight)
W0: Sample weight after measurement (absolute dry weight)

[Toner particle size]
・ Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
・ Electrolyte: Isoton II (Beckman Coulter)
-Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by weight to obtain a dispersion.
-Dispersion condition: 10 mg of a measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of an electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion is prepared.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. To determine the volume-median particle size (D50).

[Amount of deposit in the hook before and after cleaning]
The amount of the pot accumulated matter (the pot deposit) was determined by measuring the weight of the 2L kettle with the deposit and the weight of the original 2L kettle before and after washing, and obtaining the difference.

[Total amount of volatile organic substances (TVOC)]
10 mg of toner as a measurement sample was weighed in a glass tube dedicated to a solid sample, stoppered with glass wool, and measured by ATD-GC / MS (automatic heat desorption-gas chromatograph / mass spectrometry) as follows.
(ATD condition)
Equipment: Turbo Matrix ATD (automatic thermal desorption (ATD) equipment) manufactured by Perkin Elmer
Analysis mode; 2-stage desorption injection: Desorption conditions from the tube once: 180 ° C., 30 min
Adsorption condition to trap tube: -30 ° C
Desorption conditions from the trap tube: GC cycle time from -30 ° C to 300 ° C by raising the temperature at 40 ° C per minute: 105 minutes Purge time: 1 minute Valve temperature: 250 ° C
Transfer temperature: 260 ° C
Column pressure: 150 kPa
Inlet split: Not used Outlet split: 5 ml
Desorption: 50ml

(GC condition)
GC device: 6890N made by Agilent Technologies
Oven: 40 ° C (hold for 3 minutes)
The temperature is raised at a rate of 5 ° C. per minute to 200 ° C., further raised at a rate of 10 ° C. per minute, held at 280 ° C. for 22 minutes, then heated at a rate of 10 ° C. per minute and held at 300 ° C. for 30 minutes. did.
Column: DB-5MS (60m * 50um * 0.25um)
Pressure: 150 kPa constant (controlled from ATD)
(MS condition)
MS equipment: 5973N manufactured by Agilent Technologies
Scan range: m / z = 40-460
Integration condition: initial area reject: 0
initial peak width: 0.097
shoulder detection: off
initial threshold: 11

Under the above conditions, TVOC and specific components (such as benzene) were quantified by ATD-GC / MS. Quantification was performed in terms of toluene, and the component detected between hexane and hexadecane was defined as TVOC.
The correction coefficient of each component is as follows.
Benzene 1.2, toluene 1.0, ethylbenzene 0.8, mp-xylene 1.1, styrene 1.2, o-xylene 1.0, butyl acrylate 1.9, benzaldehyde 2.9, phenol 1.6, Acetophenone 1.3, 2-ethylhexanoic acid 41.1

Synthesis of nonionic surfactant Ethoxy with 3 moles of ethylene oxide added to a secondary alcohol with an average carbon number of 12 in a 5 liter rotary stirring autoclave with two measuring tanks for ethylene oxide and propylene oxide 1012 g of a rate compound (trade name “Softanol 30”, manufactured by Nippon Shokubai Co., Ltd.) and 3.0 g of potassium hydroxide were charged, and after nitrogen substitution, the temperature was raised to 110 ° C. and dehydrated at 5.33 kPa for 1 hour. Went. Next, the temperature was raised to 150 ° C., ethylene oxide was introduced into the 267 g autoclave at a pressure of 343 kPa, and the reaction was continued until the pressure decreased and became constant, then cooled to 120 ° C. and 352 g of propylene oxide was placed in the autoclave. It was introduced at a pressure of 343 kPa, and the reaction was continued until the pressure dropped and became constant as in the case of ethylene oxide. Thereafter, the temperature was raised again to 150 ° C., 668 g of ethylene oxide was introduced, and the reaction was continued until the pressure decreased and became constant. After completion of the reaction, a sample synthesized at a reduced temperature was taken out, and the catalyst was neutralized with acetic acid to obtain about 2.3 kg of a nonionic surfactant (average molecular weight: 760). Nonionic surface active agent obtained has the general formula _{RO- (EO) l - (PO} ) m - in (EO) _n -H, 2 alkyl group R is a total carbon number of 12, l is the 5, m 2, n is a compound of 5, and HLB is 6.2.

Example 2 (Preparation of cleaning agent 1)
Stir until 4 kg of ethylenediaminetetraacetic acid 3.5 kg of water is completely dissolved in 48.7 kg of water. Thereafter, 2.6 kg of the nonionic surfactant is added and stirred for 5 minutes or more. Thereafter, 40.0 kg of 48% by weight potassium hydroxide is added and mixed with stirring. Thereafter, the cleaning agent 1 was obtained through a mesh having an opening of 150 μm. The pH was 13.4.

Comparative Example 2 (Preparation of cleaning agent 2)
Stir until 8 kg of ethylenediaminetetraacetic acid tetrasodium is completely dissolved in 88.7 kg of water. Thereafter, 2.6 kg of the nonionic surfactant is added and stirred for 5 minutes or more. Thereafter, the cleaning agent 2 was obtained through a mesh having an opening of 150 μm.

Production example of polyester 1 Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 17500 g, Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane 16250 g , 11450 g of terephthalic acid, 4800 g of trimellitic anhydride, 1600 g of dodecenyl succinic anhydride and 15 g of tin 2-ethylhexanoate were placed in a four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer and a thermocouple, The mixture was stirred at 230 ° C. and reacted until the softening point measured according to ASTM D36-86 reached 125 ° C. to obtain polyester 1. Polyester 1 had a softening point of 125 ° C., a maximum endothermic peak temperature of 69 ° C., an acid value of 21.0 mgKOH / g, and a number average molecular weight of 3390.

Production Example of Polyester 2 33750 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 325 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane , 6960 g of fumaric acid, 6723 g of terephthalic acid and 15 g of tin 2-ethylhexanoate were placed in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and stirred at 230 ° C. in a nitrogen atmosphere. Reaction was carried out until the softening point measured according to D36-86 reached 110 ° C. to obtain polyester 2. Polyester 2 had a softening point of 111 ° C., a maximum endothermic peak temperature of 70 ° C., an acid value of 24.0 mgKOH / g, and a number average molecular weight of 4090.

Production Example of Resin Dispersion In a 5 liter stainless steel kettle, 210 g of polyester 1, 390 g of polyester 2, 30 g of copper phthalocyanine pigment (ECB-301: manufactured by Dainichi Seikagaku) and non-ionic surfactant “Emulgen 430 (Kao) ) "Polyoxyethylene (30 mol) oleyl ether 6.0 g, anionic surfactant" Neopelex G-15 (manufactured by Kao) "sodium dodecylbenzenesulfonate 40.0 g, and potassium hydroxide as neutralizer 252 g of an aqueous solution (concentration: 5% by weight) was added and dispersed at 95 ° C. with stirring at 250 r / min with a chi-type stirrer. The contents were stirred for 2 hours after reaching 95 ° C., and then 1118 g of deionized water was added dropwise with stirring at 200 r / min with a chi-type stirrer, and the mixture was atomized through a 200 mesh (mesh opening: 105 μm) wire mesh. A resin dispersion was obtained. The resin particles in the obtained resin dispersion had a volume-median particle size of 0.172 μm, a solid concentration of 31.1% by weight, and no resin component remained on the wire mesh.

Toner Production Example 400 g of the obtained resin dispersion was mixed in a 2 liter container made of SUS (hereinafter referred to as a 2 L kettle) at room temperature. Next, under stirring at 100 r / min with a Kai-type stirrer, 1.12 g of calcium chloride dissolved in deionized water as an aggregating agent was added dropwise to this mixture at room temperature over 15 minutes. Thereafter, the mixed dispersion was heated at 1 ° C./5 min to form aggregated particles. When the temperature reached 85 ° C., the mixture was fixed at 85 ° C. and stirred for 1.5 hours, and then the heating was stopped.
The toner was gradually cooled to room temperature, and a toner was obtained through a suction filtration step, a washing step, and a drying step. The volume median particle size (D50) of the toner was 4.9 μm. In the 2 L kettle used, the kettle staying matter (kettle deposit) was observed at the gas-liquid interface. The main component of the pot
ICP emission analysis using infrared absorption spectrum (IR) and inductively coupled radio frequency plasma discharge identified the polyester used or a polymer in which the terminal carboxylic acid was converted to a calcium salt.

Example 3
110 g of the cleaning agent 1 was added to the 2 L kettle made of SUS having the above-mentioned kettle deposit (5.10 g of kettle deposit), and then 1540 g of deionized water was added to prepare a diluted washing solution in the 2 L kettle. Thereafter, a reflux tube and a chi-type stirrer used in the production of the toner were attached, and the temperature was raised to 95 ° C. and stirred for 2 hours. After stirring, the temperature was returned to room temperature, and the used cleaning solution was removed from the 2 L kettle and stored in another container. No pot deposits that were present at the gas-liquid interface portion of the 2 L kettle were observed. Then, it was lightly washed with water, and the amount of the remaining kettle deposits was measured and found to be 0.0 g.
Further, when the used cleaning liquid stored in another container was observed using a laser scattering type particle size measuring instrument (Horiba LA-920), the pot deposit was removed as 17 μm polymer fine particles. Turned out to be.

Comparative Example 3
In the same manner as in Example 3, the above-mentioned toner was produced in an unused reaction tank (2 L kettle), and a cleaning test for the adhering matter adhering to the 2 L kettle was performed by replacing the cleaning agent.
That is, 46 kg of 48% sodium hydroxide was added to the 2 L kettle having the above-mentioned kettle deposit (4.92 g kettle deposit), and then 1567.5 g of deionized water was added to prepare a diluted washing solution in the 2 L kettle. Thereafter, a reflux tube and a chi-type stirrer used in the production of the toner particles were attached, and the temperature was raised to 95 ° C. and stirred for 2 hours. After stirring, the temperature was returned to room temperature and the washing solution was removed. A portion of the pot deposit remaining at the gas-liquid interface portion of the 2 L pot remained. Thereafter, the residue was lightly washed with water, and the amount of deposits on the remaining kettle was measured and found to be 0.90 g.

Comparative Example 4
In the same manner as in Example 3, the above-mentioned toner was produced in an unused reaction tank (2 L kettle), and a cleaning test for the adhering matter adhering to the 2 L kettle was performed by replacing the cleaning agent.
That is, 110 g of the cleaning agent 2 was added to the 2 L kettle having the above-mentioned kettle deposit (5.12 g of the kettle deposit), and then 1540 g of deionized water was added to prepare a diluted cleaning solution in the 2 L kettle. Thereafter, a reflux tube and a chi-type stirrer used in the production of the toner particles were attached, and the temperature was raised to 95 ° C. and stirred for 2 hours. After stirring, the temperature was returned to room temperature and the washing solution was removed. A portion of the pot deposit remaining at the gas-liquid interface portion of the 2 L pot remained. Thereafter, the residue was lightly washed with water, and the amount of deposits on the remaining kettle was measured and found to be 2.97 g.

Example 4
Using the cleaning liquid stored after use in Example 3, the production of the toner and the cleaning operation performed in Example 3 were repeated 10 times, and the cleaning performance of the kettle was evaluated for each number of times. That is, in the same manner as in Example 3, the amount of the 2L kettle deposit and the remaining kettle deposit were used. The results are shown in Table 2.
In addition, when the toner particles manufactured by the above-described toner manufacturing method were subjected to a quantitative analysis of the total amount of volatile organic substances (TVOC amount) in a kettle after the above-described toner manufacturing and cleaning operations were performed 10 times, 128 ppm was obtained. Met.

Comparative Example 5
1650 g of methyl ethyl ketone was added to the 2 L kettle (5.02 g of the kettle deposit) having the aforementioned kettle deposit. Thereafter, a reflux tube and a chi-type stirrer used in the production of the toner were attached, and the temperature was raised to 95 ° C. and stirred for 2 hours. After stirring, the temperature was returned to room temperature, and the washing solution was removed and stored in another container. No pot deposits that were present at the gas-liquid interface portion of the 2 L kettle were observed. Thereafter, the residue was lightly washed with water, and the amount of the remaining kettle deposits was measured to be 0.0 g.
In the same manner as in Example 4, the above-described toner production and washing operations were repeated 10 times using methyl ethyl ketone stored in a separate container, and the pot washability was evaluated each time. In the same manner as in Example 3, the amount of 2L kettle deposits and the amount of residual kettle deposits used were confirmed. The results are shown in Table 3.
In addition, when the toner particles manufactured by the above-described toner manufacturing method were quantitatively analyzed for the amount of total volatile organic matter (TVOC amount) in a kettle after the toner was manufactured and washed 10 times, 203 ppm was obtained. Met.

比較例５で製造されたトナーには、実施例４で製造されたトナーの１．５倍以上の全揮発性有機物量が含まれることが判明した。

It was found that the toner produced in Comparative Example 5 contained a total volatile organic matter amount 1.5 times or more that of the toner produced in Example 4.

  Since the cleaning method and the cleaning agent of the present invention have sufficient cleaning properties for the hard surface to which the resin is adhered, they are suitable for cleaning hard surfaces that use various polymers or constitute a production line for manufacturing various polymers. Can be used. In particular, the cleaning method and the cleaning agent of the present invention have sufficient cleaning properties for the toner production line and do not adversely affect the produced toner. It can be suitably used for cleaning in a production line of an electrophotographic toner used in a printing method or the like.

Claims (8)

A hard surface cleaning method for cleaning a hard surface to which a resin is adhered with an aqueous cleaning agent having a cleaning temperature of 85 ° C. or more, wherein the aqueous cleaning agent comprises: (a) an alkaline agent; and (b) the following general formula (1): A method for cleaning a hard surface, which comprises a nonionic surfactant represented by formula (II) and water and has a pH ≧ 13.

(In the formula, R represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and l, m, and n represent average addition mole numbers of oxyethylene group, oxypropylene group, and oxyethylene group, respectively. 0-15, l and n are not 0 at the same time, and m ≦ l + n ≦ 30.)   The method for cleaning a hard surface according to claim 1, wherein the hard surface is a member in contact with a polymer.   The method for cleaning a hard surface according to claim 1, wherein the hard surface is a metal.   The method for cleaning a hard surface according to claim 2 or 3, wherein the member in contact with the polymer constitutes a production line used in the step of granulating the raw material component containing the binder resin for toner in an aqueous medium.   The hard surface cleaning method according to claim 1, wherein the aqueous cleaning agent is used repeatedly.   In a production line of toner including a hard surface, a method for producing an electrophotographic toner comprising a step of forming a raw material component containing a binder resin into an aqueous medium, wherein at least the hard surface comprises at least the hard surface. 6. A method for producing an electrophotographic toner, wherein the toner is produced after being washed by the washing method according to any one of 5 above.   An electrophotographic toner obtained by the production method according to claim 6. (A) An alkali agent, (b) a nonionic surfactant represented by the following general formula (1), and water, and having a pH of ≧ 13: Cleaning agent for cleaning.

(In the formula, R represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, l, m, and n represent the average number of moles of oxyethylene group, oxypropylene group, and oxyethylene group, respectively. Each is 0-15, l and n are not 0 at the same time, and m ≦ l + n ≦ 30.)