JPH11344841A - Wet developer containing foaming inhibitor and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface rugged foamed body by forming a pattern of a foaming inhibitor on the surface of a foamable material through electrostatic recording or electrostatic transfer and then subjected to foaming. SOLUTION: Copolymerized resin particles comprising a copolymerized resin consisting of two or more monomeric units and contg. a foaming inhibitor are dispersed in an electric insulating dispersion medium to obtain the objective wet developer. The difference between the SP value δp<1> of a homopolymer comprising only the 1st monomeric unit of the copolymerized resin and the SP value δd of the dispersive medium is 1.0 or larger, the difference between the SP value δp<2> of a homopolymer comprising only the 2nd monomeric unit of the copolymerized resin and the SP value δd of the dispersive medium is 1.0 or smaller and the difference between δp<1> and δp<2> is 0.5 or larger. Each of the copolymerized resin particles consists of a core part which is insoluble in the dispersion medium and a peripheral part enveloping the core part and soluble or swellable in the dispersion medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet developer used for producing a foam having a three-dimensional surface pattern, for example, a foamed wallpaper or a foamed flooring, and a method for producing the same. More specifically, a foaming inhibitor (patterned preform) having a foaming resin composition is patterned with a foaming inhibitor on the surface thereof by a method such as electrostatic recording, electrostatic transfer, or electrostatic printing. The present invention relates to a wet developer containing a foaming inhibitor and a method for producing the same, which can be adhered to a developer.

[0002]

2. Description of the Related Art Printed materials or building materials having a three-dimensional pattern such as foamed wallpaper or foamed flooring are manufactured by a processing method called chemical embossing. On the surface of the foamed raw material made of the foamable resin composition, the foaming inhibitor is coated or infiltrated in a predetermined pattern, and then foamed by a method such as heating. It foams and rises, but remains unfoamed where the foam inhibitor is present. As a result, a foam having an uneven surface is formed. The unevenness formed on the surface of the foam becomes a three-dimensional pattern corresponding to the pattern of the foam inhibitor. In chemical embossing, printed materials or building materials having a three-dimensional pattern are manufactured by such a method. Such a method of chemical embossing is disclosed in JP-B-43-28636 and JP-B-47-29187.
No., etc.

As the foamable resin composition, for example, a composition containing a polyvinyl chloride resin, a foaming agent such as azodicarbonamide, and a foaming accelerator such as zinc naphthenate is used. A foaming agent such as azodicarbonamide decomposes when heated to generate a gas such as carbon dioxide, thereby forming bubbles in the foamable resin composition. Foaming promoters such as zinc naphthenate are catalysts that promote the decomposition of the blowing agent and lower the decomposition temperature. On the other hand, a benzotriazole-based compound that can hinder the action of the foaming accelerator is used as the foaming inhibitor. When such a foaming inhibitor is applied to the surface of a foamed raw material made of the foamable resin composition, the foaming temperature of the portion where the foaming inhibitor is applied is higher than the foaming temperature of the portion where the foaming inhibitor is not applied. Become. Therefore, by adjusting the heating temperature of the foamed raw material to be equal to or higher than the foaming temperature of the uncoated portion and lower than the foaming temperature of the coated portion, only the uncoated portion can be foamed.

Conventionally, a foaming inhibitor has been applied in a pattern to the surface of a foamed raw material by a printing method such as gravure printing or offset printing. However, in the case of using the printing method, it takes a relatively long time to create a printing plate, and the cost is high. For this reason, there was a problem that it was not possible to smoothly create and evaluate a prototype at the development stage.

Instead of creating a prototype, an image that reproduces the surface design of the prototype is synthesized by digital processing,
It is also worth considering the method of outputting it quickly using an on-demand printer such as an electrostatic plotter or an electrophotographic printer. For general printed materials, using various digital proofing presses, images similar to those of the final product or prototype can be synthesized and output in a short time. Evaluation can be performed flexibly. However, foams with irregularities on the surface can significantly change the design, including the impression and texture, due to the foaming process. It was impossible to synthesize and evaluate the images.

[0006] For this reason, in the development stage of a foamed product having a three-dimensional pattern such as a foamed wallpaper or a foamed flooring, a developer such as a designer is not allowed to frequently produce a prototype, and is exclusively used. It is difficult to evaluate the design of surface irregularities in detail because development has to proceed with reference to a composite image output by a digital proof printing machine etc. that can not be said to be reproduced very accurately. Met.

In order to present a foamed product to a customer, it is desirable to use a commercial product or a sample very similar to the commercial product to sufficiently appeal its design. However, for that purpose, it is necessary to prepare a printing plate in order to apply the foaming inhibitor, so that time and cost obstacles increase. Therefore, it was difficult to give a presentation flexibly.

[0008]

SUMMARY OF THE INVENTION The present inventors have proposed that, if a foaming inhibitor can be made into a toner, a coating or a penetrated portion of the foaming inhibitor having a desired pattern can be formed on the surface of the raw foam.
We thought that it would be possible to form easily and quickly using on-demand printers such as electrostatic plotters and electrophotographic printers, and to be able to flexibly create foams of various designs. However, in order to convert the foaming inhibitor into a toner, the foaming inhibitor must have excellent dispersibility and chargeability.

The present invention has been accomplished in view of the above situation, and a first object of the present invention is to provide a wet method in which toner particles containing a foaming inhibitor and having excellent chargeability are well dispersed. An object of the present invention is to provide a developer and a method for producing the same. Further, a second object of the present invention is to provide a wet type developer containing a foaming inhibitor and dispersing negatively charged toner particles in a favorable manner, and to reduce the chargeability of the toner particles containing the foaming inhibitor. It is an object of the present invention to provide a method for producing a wet developer which can be adjusted to an electric charge.

[0010]

SUMMARY OF THE INVENTION A wet developer according to the present invention is a copolymer comprising at least two monomer units including at least a first monomer unit and a second monomer unit in an electrically insulating dispersion medium. A wet developer in which copolymer resin particles containing a foaming inhibitor that can suppress foaming of the foamable resin composition, which is made of a resin, are dispersed,
(1) The electric insulating dispersion medium and the copolymer resin are as follows:
(I) The difference Δ (δp between the solubility parameter value δp ^{1 of} the homopolymer composed only of the first monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
¹⁻ δd) is 1.0 or more, and (ii) the difference between the solubility parameter value δp ^{2 of} the homopolymer composed only of the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium. Δ (δp ² −δd) is 1.0
And (iii) the difference Δ (δp ¹ −δp) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
² ) has a relationship of not less than 0.5, and (2) the copolymer resin particles have a core portion insoluble in the electric insulating dispersion medium and an electric insulating dispersion medium surrounding the core portion. And (3) a phospholipid, a neutral or basic metal petronate as a charge control agent,
Alternatively, it is characterized by containing a metal salt compound of an organic acid.

The first preferred method for producing the above-mentioned wet developer (hereinafter referred to as "solvent replacement method") includes at least the following steps. Then, at any stage of a series of manufacturing processes including the following process group, a raw material, a material other than the raw material or an intermediate product, is characterized by adding lecithin and basic calcium petronate as a charge control agent. .

Step group: (1) at least a first monomer unit and a second monomer unit
Copolymer tree composed of two or more monomer units containing
And the solubility parameter below.
A step of preparing an electrically insulating dispersion medium having a characteristic of the electrical insulation;
Homopolymer composed only of the first monomer unit
Solubility parameter value δp¹ And the solubility of the dispersion medium
Difference Δ (δp from parameter value δd¹ −δd) is 1.0
And (ii) the second monomer unit
Of solubility parameter of homopolymer composed only of
δp^Two And the solubility parameter value δd of the dispersion medium
Δ (δp ^Two -Δd) is 1.0 or less, and (ii)
i) solubility parameter values δ of the two homopolymers
p¹ , Δp^Two Δ (δp¹ −δp^Two ) Is 0.5 or more
Have the relationship

(2) a step of mixing the prepared copolymer resin solution and the electrically insulating dispersion medium in the presence of a foaming inhibitor capable of suppressing foaming of the foamable resin composition; and (3) Removing the solvent after granulation.

Here, the SP value (solubility parameter value) δd of the electrically insulating dispersion medium used in the present invention is represented by δ
The difference Δ (δp ¹ −δd) between d and the SP value δp ¹ of the homopolymer composed only of the first monomer unit of the copolymer resin becomes 1.0 or more, and the difference Δd and the second value of the copolymer resin
SP value δ of homopolymer composed only of monomer units
The difference Δ (δp ² −δd) from p ² has a relationship of 1.0 or less. That is, the dispersion medium used in the present invention has low affinity for the first monomer unit portion of the copolymer resin, and has high affinity for the second monomer unit portion of the copolymer resin. Moreover, the difference Δ (δp ¹ −δp) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers described above.
^{Since 2} ) is 0.5 or more, there is a considerable difference between the affinity of the dispersion medium for the portion of the first monomer unit and the affinity of the dispersion medium for the portion of the second monomer unit.

Therefore, a solution of a copolymer resin composed of at least a first monomer unit and a second monomer unit,
When mixed with an electrically insulating dispersion medium having the SP value characteristic as described above under conditions in which a foaming inhibitor having an originally low affinity for the electrically insulating dispersion medium is present, the first monomer of the copolymer resin is obtained. The unit part repels the dispersion medium and is adsorbed on the surface of the foaming inhibitor. As a result, the copolymer resin microscopically aggregates around the foaming inhibitor. Thus, copolymer resin particles containing the foaming inhibitor are formed.

The formed copolymer resin particles comprise a core portion insoluble in the dispersion medium and an outer edge portion surrounding the core portion and dissolving or swelling in the dispersion medium. Here, the core portion is composed of a foaming inhibitor and a portion having a high affinity for the foaming inhibitor in the molecule of the copolymer resin, particularly a portion of the first monomer unit. Further, the outer edge portion is composed of a portion having a high affinity for the electrically insulating dispersion medium in the molecule of the copolymer resin, particularly a portion of the second monomer unit. Since the copolymer resin particles have such a structure, the particles of the foaming inhibitor are prevented from directly contacting each other, are well dispersed in the dispersion medium, and are unlikely to cause precipitation or macroscopic aggregation. The chargeability of the copolymer resin particles is also well controlled by the addition of lecithin and basic calcium petronate. Therefore, by developing an electrostatic latent image using the wet developer of the present invention produced by the solvent replacement method, a pattern that matches the electrostatic latent image and contains a foaming inhibitor can be formed.

As described above, when the wet developer produced by the solvent replacement method is used, the pattern of the foaming inhibitor can be easily and quickly applied to the surface of the foamed material by electrostatic recording or electrostatic transfer. Can be formed. In the case of electrostatic recording or electrostatic transfer, a plate making process is not required. Therefore, the uneven foam can be manufactured without taking time and effort. In particular, it is suitable for applications such as repeated production of prototypes, rapid production of samples according to the presentation schedule, and construction of a custom-made system to supply small quantities of various types of uneven foams. In addition to electrostatic recording or electrostatic transfer, there is a method using an electrostatic action such as electrostatic printing, but the wet developer of the present invention is used for all such electrostatic methods. be able to.

In converting the foaming inhibitor into a toner,
It is important to appropriately adjust the charge amount, and it is also important to intentionally adjust the polarity of the charge to either positive or negative. According to the study of the present inventors, it was very difficult to intentionally negatively charge the toner of the foaming inhibitor, but by using a combination of lecithin and basic calcium petronate as a charge control agent, The toner particles of the foaming inhibitor can be negatively charged. In particular, when trimellitic anhydride is used as the foaming inhibitor or when a copolymer resin in which the first monomer unit has an acidic group is used, the toner particles are likely to be negatively charged.

The toner particles are negatively charged by adding each of lecithin and basic calcium petronate to 0.05 to 0.5 parts by weight with respect to 3.6 parts by weight of the foaming inhibitor. And a large amount of a foaming inhibitor can be attached to the electrostatic latent image.

In the case where trimellitic anhydride is converted into a toner by the solvent substitution method, which is the first production method of the present invention, it is preferable to dissolve the copolymer resin with toluene. The copolymer resin particles have a structure in which the copolymer resin is adsorbed on the surface of the foaming inhibitor, but such a structure is formed when the solvent for dissolving the copolymer resin dissolves up to the foaming inhibitor. Cannot be successfully precipitated. Toluene has good solubility in copolymer resins, but is insoluble or poorly soluble in trimellitic anhydride,
When a toluene solution of a copolymer resin is mixed with an electrically insulating dispersion medium in the presence of trimellitic anhydride, copolymer resin particles containing trimellitic acid can be successfully precipitated.

Next, the second preferred method for producing the above-mentioned wet developer (hereinafter referred to as "slow cooling method") includes at least the following steps. Then, at any stage of a series of manufacturing processes including the following process group, in a raw material, a material other than the raw material or an intermediate product, as a charge control agent, a phospholipid, a neutral or basic metal petronate, or
It is characterized in that a metal salt compound of an organic acid is added.

Process group: (1) Electrical insulation having the following solubility parameter characteristics
Is heated to at least the first monomer unit and the second monomer unit.
Consists of two or more monomer units including two monomer units
While dissolving the copolymer resin to be used,
In the dispersion medium, the foaming resin may be simultaneously or separately with the copolymer resin.
A foaming inhibitor capable of suppressing foaming of the oil composition.
Dispersing to prepare a heated mixture, [Solubility parameter characteristics of electrically insulating dispersion medium] (i)
Homopolymer composed only of the first monomer unit
Solubility parameter value δp¹ And the solubility of the dispersion medium
Difference Δ (δp from parameter value δd¹ −δd) is 1.0
And (ii) the second monomer unit
Of solubility parameter of homopolymer composed only of
δp^Two And the solubility parameter value δd of the dispersion medium
Δ (δp ^Two -Δd) is 1.0 or less, and (ii)
i) solubility parameter values δ of the two homopolymers
p¹ , Δp^Two Δ (δp¹ −δp^Two ) Is 0.5 or more
Have the relationship

(2) Step of Slowly Cooling the Heated Mixture Here, only the SP value (solubility parameter value) δd of the electrically insulating dispersion medium used in the slow cooling method and the first monomer unit of the copolymer resin are used. SP value δp ^{1 of the} obtained homopolymer
(Δp ¹ −δd) and the difference Δ (δp ² −δd) between the δd and the SP value δp ² of the homopolymer composed only of the second monomer unit of the copolymer resin are as described above. It has the same relationship as the solvent replacement method. That is, the dispersion medium used in the slow cooling method also has a low affinity for the first monomer unit portion of the copolymer resin, and has a high affinity for the second monomer unit portion of the copolymer resin. In addition, the difference Δ (δp ¹ −δp ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers has the same relationship as in the above-mentioned solvent substitution method, so that the dispersion of the first monomer unit is There is considerable divergence between the affinity of the medium and the affinity of the dispersion medium for the portion of the second monomer unit.

Further, the electrically insulating dispersion medium is heated so that at least the first monomer unit and the second
It has the property of dissolving a copolymer resin composed of monomer units and then cooling it to precipitate the dissolved copolymer resin in the electrically insulating dispersion medium.

Therefore, the copolymer resin composed of at least the first monomer unit and the second monomer unit is dissolved in the electrically insulating dispersion medium having the SP characteristic as described above by heating the dispersion medium. You. This dissolution is
When the reaction is performed under the condition in which a foaming inhibitor having originally low affinity for the electrically insulating dispersion medium is present, the foaming inhibitor is dispersed in a solution in which the copolymer resin is dissolved in the electrically insulating dispersion medium. A hot mixture is obtained. Thereafter, when the mixture is cooled, a copolymer resin is precipitated. In this precipitation, the first monomer unit portion of the copolymer resin repels the dispersion medium and is adsorbed on the surface of the foam inhibitor, and as a result, the copolymer resin is microscopically aggregated around the foam inhibitor. It happens by things. Thus, copolymer resin particles containing the foaming inhibitor are formed. By gradually cooling from the temperature at which the precipitation of the copolymer resin starts to the temperature at which the precipitation of the copolymer resin is completed, the microscopic aggregation with the foaming inhibitor mixed in the above mixture as a nucleus is reduced. Can be raised uniformly.

The formed copolymer resin particles have the same constitution as those obtained by the above-mentioned solvent replacement method, and include a core portion insoluble in the dispersion medium and a core portion surrounding the core portion, which dissolves or swells in the dispersion medium. Consists of an outer edge. Here, the core portion is composed of a foaming inhibitor and a portion having a high affinity for the foaming inhibitor in the molecule of the copolymer resin, particularly a portion of the first monomer unit. Further, the outer edge portion is composed of a portion having a high affinity for the electrically insulating dispersion medium in the molecule of the copolymer resin, particularly a portion of the second monomer unit. Since the copolymer resin particles have such a structure, the particles of the foaming inhibitor are prevented from directly contacting each other, are well dispersed in the dispersion medium, and are unlikely to cause precipitation or macroscopic aggregation.

The chargeability of the copolymer resin particles is well controlled by adding a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid.
Therefore, by developing the electrostatic latent image using the wet developer manufactured by the slow cooling method, it is possible to form a pattern that matches the electrostatic latent image and contains a foaming inhibitor.

As described above, when the wet developer produced by the slow cooling method is used, the pattern of the foaming inhibitor is easily and quickly formed on the surface of the foamed raw material by using the method of electrostatic recording or electrostatic transfer. can do. In the case of electrostatic recording or electrostatic transfer, a plate making process is not required. Therefore, the uneven foam can be manufactured without taking time and effort. In particular, it is suitable for applications such as repeated production of prototypes, rapid production of samples according to the presentation schedule, and construction of a custom-made system to supply small quantities of various types of uneven foams. In addition to electrostatic recording or electrostatic transfer, there is a method using an electrostatic action such as electrostatic printing, but the wet developer of the present invention is used for all such electrostatic methods. be able to.

In converting the foaming inhibitor into a toner,
It is important to appropriately adjust the charge amount, and it is also important to intentionally adjust the polarity of the charge to either positive or negative. According to the present invention based on the slow cooling method, when trimellitic anhydride is used as a foaming inhibitor, and when a copolymer resin in which the first monomer unit has an acidic group is used, the toner particles are negatively charged. Easy to make. In particular, by using a combination of a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid as a charge control agent, the toner particles of the foaming inhibitor can be negatively charged.

It is preferable to add the above-mentioned charge controlling agent, a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid in the step of preparing the above heated mixture. The charge control agent added at this time is supposed to act as a dispersant to improve the dispersibility of the formed copolymer resin particles or to assist in adjusting the final charge amount. As a result, excellent dispersibility,
It is possible to manufacture a wet developer in which the charge amount can be easily adjusted.

The metals constituting the neutral or basic metal petronate include calcium, magnesium,
Any of barium and sodium can be used, lecithin can be preferably used as a phospholipid, and cobalt, manganese, zirconium, yttrium, nickel, calcium can be used as a metal constituting a metal salt compound of an organic acid. , Iron, lead, chromium, zinc, magnesium, barium and the like can be used.

When the amount of the phospholipid or the neutral or basic metal petronate is 0.1 to 30 parts by weight with respect to 60 parts by weight of the foaming inhibitor, the toner particles are easily negatively charged. In addition, a large amount of a foaming inhibitor can be deposited on the electrostatic latent image.

In the case of the slow cooling method, the reproducibility is higher than that in the case of the solvent replacement method. Under the same conditions, a wet developer having the same polarity and a constant charge amount can be easily obtained. In the case of employing the slow cooling method, copolymer resin particles having a higher content of the foaming inhibitor can be obtained than in the case of employing the solvent replacement method. In the case of the solvent replacement method, the content of the foaming inhibitor in the copolymer resin particles can be increased to a considerably high level of 50% by weight. It is particularly preferable because the content of the foaming inhibitor in the copolymer resin particles can be further increased to 50% by weight to 80% by weight.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(1) Foamable Resin Composition and Foaming Inhibitor The wet developer of the present invention is obtained by dispersing toner particles of a foaming inhibitor, and is used for electrostatic recording, electrostatic transfer and electrostatic printing. Utilizing electrostatic action, toner particles can be adhered in a predetermined pattern on the surface of a preform (foamed raw material) formed of a foamable resin composition. And
When the raw foam is foamed after the toner particles are attached, a foam having surface irregularities is obtained.

The foamable resin composition contains at least a resin, has the property of foaming by any processing method, for example, a method such as heating or a chemical reaction, and contains a large amount of air bubbles in the resin after foaming. Use a material which forms a structure and which can prevent or reduce the foaming property of the foamable resin composition by a foaming inhibitor appropriately selected.

As the resin composition which is usually used,
A mixture of a thermoplastic resin, a foaming agent that decomposes upon heating to generate gas, and a foaming accelerator that acts as a catalyst to lower the thermal decomposition temperature (foaming temperature) of the foaming agent is used. Further, as a foaming inhibitor used in combination with such a resin composition, one that inhibits the action of a foaming accelerator and increases the decomposition temperature of the foaming agent can be used. As the thermoplastic resin, for example, a polyvinyl chloride resin, particularly, a porous polyvinyl chloride resin is used. As the foaming agent, for example, azodicarbonamide, N, N-dinitrosopentamethylenetetramine, P-toluenesulfonyl semicarbazide and the like are used. As the foaming accelerator, for example,
For example, zinc naphthenate is used. In the foamable resin composition,
A coloring agent, a fluorescent agent, a deodorant, an ultraviolet ray-cutting agent, an antibacterial agent, and the like may be added as necessary for the purpose of enhancing the design properties after foaming.

As the foam inhibitor, trimellitic anhydride or benzotriazole is preferably used alone or in combination. In order to convert the foaming inhibitor into a toner, it is necessary to use a foaming inhibitor that is solid at room temperature. Many foam inhibitors are liquid at room temperature, while trimellitic anhydride and benzotriazole are solid at room temperature.

(2) Wet developer and method for producing the same The wet developer according to the present invention comprises a copolymer resin composed of at least two types of monomer units including at least a first monomer unit and a second monomer unit; Copolymer resin particles containing a foaming inhibitor such as trimellitic anhydride,
It is formed by dispersing in an electrically insulating dispersion medium. Also,
In the wet developer of the present invention, a phospholipid as a charge control agent,
Neutral or basic metal petronate or a metal salt compound of an organic acid is added.

The wet developer of the present invention is obtained, for example, by mixing a solution in which a copolymer resin is dissolved in a solvent and an electrically insulating dispersion medium in the presence of a foaming inhibitor such as trimellitic anhydride. After granulating the copolymer resin particles, it is manufactured by a solvent replacement method of removing the solvent, or the copolymer resin is heated and dissolved in an electrically insulating dispersion medium in the presence of a foaming inhibitor, and the obtained mixture is dispersed. It can be produced by a slow cooling method in which copolymer resin particles are precipitated by slow cooling. A phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid, which is a charge control agent, may be added at any stage during the production process by any method.

According to the present invention, by adjusting the SP value of an electrically insulating dispersion medium in which copolymer resin particles containing a foaming inhibitor are precipitated from a copolymer resin solution and dispersed.
A wet developer excellent in dispersibility of copolymer resin particles, that is, toner particles is provided.

[Solubility Parameter (SP Value)] In general, the SP value is known as an index indicating compatibility or incompatibility between substances. Taking the relationship between resin and solvent as an example,
The degree of solubility of the resin in the solvent can be indicated by the SP value. If the difference between the SP value of the resin and the SP value of the solvent is small, the solubility is high and the solubility is high. On the other hand, if the difference is large, the solubility is low and the solvent is insoluble.

As a method of measuring the SP value of a resin, for example, (1) a method of dissolving, that is, a method of estimating from the SP value of a solvent in which the resin is dissolved (H. Burrell, Official
Digest, 27 (369), 726 (1950)), (2) Swelling method, that is, a method of estimating from the SP value of a solvent that maximizes the degree of swelling for a resin that is difficult to dissolve (same as above), (3) ) The method of obtaining from the intrinsic viscosity of the resin, that is, the intrinsic viscosity of the resin in the solvent shows the maximum value when the SP value of the resin coincides with the SP value of the solvent, so that the resin is dissolved in a solvent having various SP values. In each case, the intrinsic viscosity is measured, and the SP value of the resin is estimated from the SP value of the solvent that gives the maximum intrinsic viscosity (H. Ahmed, M. Yassen, J. Coat. Technol.,
50, 86 (1970), WR Song, DW Brownawell, Polym.
Eng. Sci., 10, 222 (1970)), (4) A method of obtaining from a molecular attraction constant, that is, a molecular attraction constant (G) and a molar volume (V) of each functional group or an atomic group constituting a resin molecule. From the equation SP value = ΣG / V (DA Sm
all, J. Appl. Chem., 3, 71 (1953), KL Hoy, J. Pa
int Technol., 42, 76 (1970)).

Hereinafter, in the present invention, a value determined by a molecular attraction constant is used as the SP value of the resin. As the SP value of the solvent, Hildebrand-Scatchard solution theory (JH Hildebrand, RL Scott, “The Solbi
lity of Nonelectrolytes '' 3rd Ed., Reinhold Publish
ing cop., New York (1949), G. Scatchard, Chem., Re.
v., 8, 321 (1931)) based on the attractive force between molecules.

SP value (δ) = (ΔE _V / ΔV ₁ ) ^1/2 [where ΔE _V : evaporation energy, V ₁ : molecular volume, ΔE
_V / ΔV ₁ : cohesive energy]. In the present invention, KL Hoy, J. Paint Technol., 42, 76 (1
970) at 25 ° C. are used.

The relationship between the SP value of the resin and that of the solvent will be described by taking as an example the case where the resin is dissolved in a solvent as performed by the solvent displacement method. Polystyrene having an SP value of 9.1 has a SP value of 9 0.1 is very soluble in tetrahydrofuran, is soluble in solvents having an SP value in the range of 8.5 to 9.3, and is not soluble in n-hexane having an SP value of 7.3. Thus, the state of the resin in the solvent can be estimated by looking at the difference between the SP values of the resin and the solvent.

After dissolving the resin in a relatively dilute state in a good solvent, adding the solution to a poor solvent and removing the good solvent, resin particles can be precipitated. However, it can be considered that in a good solvent, a resin that was present in a monomolecular state and a molecular chain was elongated, but in a poor solvent, the molecular chain was shrunk into particles and precipitated. . Therefore, a solvent having a difference in SP value such that the resin swells is used as the poor solvent.
The state of the resin particles in the solvent differs depending on whether a solvent in which the P value is large and the resin is completely insoluble is used. Generally, as the weight average molecular weight of the resin increases, the particle size of the formed resin particles increases.

[Copolymer Resin] The copolymer resin is used to enhance the dispersibility of a foaming inhibitor such as trimellitic acid. As such a copolymer resin, for example, styrene-butadiene copolymer resin, styrene-isoprene copolymer resin, styrene-acrylonitrile copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene- Acrylic acid copolymer resin, ethylene-
Thermoplastic resins such as methacrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, vinyl acetate-methyl methacrylate copolymer resin, acrylic acid-methyl methacrylate copolymer resin, and vinyl chloride-vinyl acetate copolymer resin can be used. . ASTM of copolymer resin
Melt flow rate (MF)
R) is usually 1 to 400 dg / min, preferably 2
To 150 dg / min. When this MFR value range is converted into a weight average molecular weight, 1 to 400 dg / min corresponds to about 60,000 to 250,000 in weight average molecular weight, and 2 to 150 dg / min.
dg / min corresponds to about 75,000 to 200,000 in weight average molecular weight.

The copolymer resin used in the present invention is composed of two or more types of monomer units, has a low affinity for an electrically insulating dispersion medium, and therefore forms a portion insoluble in the dispersion medium. A first monomer unit considered as having a high affinity for the electrically insulating dispersion medium, and therefore a second monomer unit considered to form a portion which dissolves or swells in the dispersion medium. In.
The ratio of the first monomer unit to the second monomer unit is 95/5 to 5/95 by weight, preferably 85/15 to 15 /.
85.

Examples of the first monomer unit include (meth) acrylic acid, methyl (meth) acrylate, (meth)
(Meth) acrylates having short-chain methylenes such as ethyl acrylate, butyl (meth) acrylate;
Nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; acrylamide, isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N-diacetoneacrylamide, N, N-
Acrylamide derivatives such as dimethylacrylamide; derived from other monomers such as (meth) acrylic acid-2-hydroxyethyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, methylstyrene, vinyl acetate, etc. A monomer unit can be exemplified. In particular, those derived from (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, methylstyrene, and vinyl acetate are preferred as the first monomer unit.

The second monomer unit effective for controlling the solubility and dispersibility in a solvent includes a vinyl monomer having a long-chain methylene as a side chain, more specifically (meth)
Monomer units derived from (meth) acrylates having long-chain methylenes such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and ethylene, isoprene, butadiene, propylene And a monomer unit derived from a vinyl monomer. In particular, 2-ethylhexyl (meth) acrylate or one derived from ethylene is preferred as the second monomer unit.

In the case of a copolymer resin having three or more monomer units, the one having the largest difference from the SP value of the dispersion medium is specified as the first monomer unit, and the difference from the SP value of the dispersion medium is determined. The smallest one may be specified as the second monomer unit, and its weight ratio may be the same as in the case of the above-mentioned two-component copolymer resin. Further, if the third monomer component has the same SP value as one of the first and second monomer units forming the insoluble portion or the dissolved portion in relation to the SP value of the dispersion medium, such a case is possible. It may be considered a component equivalent to a monomer unit having an approximate SP value.

[Foaming Inhibitor] As the foaming inhibitor contained in the copolymer resin particles, those capable of appropriately suppressing the foaming property of the foamable resin composition are used as described above. In the present invention, usually, a foaming inhibitor powder having an average particle size in a secondary aggregation state of 0.1 to 100 μm is used.

The wet developer of the present invention hardly causes problems such as agglomeration even when a large amount of copolymer resin particles containing a foam inhibitor is contained, so that the content of the foam inhibitor in the wet developer is increased can do.

[Charge Control Agent] In the present invention, a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid is used as the charge control agent to sufficiently charge the toner particles. It can be.

Here, examples of the phospholipid include lecithin and sekhalin, and for example, lecithin is represented by the following formula (1).

[0056]

Embedded image In the formula (1), R ¹ CO and R ² CO each represent a saturated or unsaturated acyl group, and the number of carbon atoms is not particularly limited.

Since lecithin has both a hydrophobic fatty acid glyceride group and a hydrophilic phosphate group or ethanolamino group in its molecule, it has a zwitterionic surfactant activity. . Lecithin has an acid value of about 2
At 0, it is a waxy substance, and at an acid value of about 30, it is a viscous liquid. Lecithin is insoluble in water, but swells with water. As lecithin, for example, soybean lecithin and egg yolk lecithin can be used. The constituent fatty acids of soy lecithin are palmitic acid 11.7%, stearic acid 4%, palmitooleic acid 8.6%, oleic acid 9.8%, linoleic acid 55%, and linolenic acid 4%. And an acid having 20 to 22 carbon atoms is 5.5%.

The neutral or basic metal petronate is
A neutral or basic mixture containing large amounts of metal sulfonates and mineral oil. As the metal constituting the neutral or basic metal petronate, petronates composed of any of calcium, magnesium, barium and sodium can be appropriately selected and used. For example, basic calcium petronate (BCP), basic magnesium petronate (BMP), basic barium petronate (BBP), basic sodium petronate, neutral (neutral) calcium petronate (NCP) and the like.

Of these, when a wet developer is produced by a solvent replacement method, it is preferable to use basic calcium petronate. Basic calcium petronate (BCP) is a basic mixture containing a large amount of calcium sulfonate represented by the following formula (2) and mineral oil.

[0060]

Embedded image [Wherein, n represents an integer of 20 or more. ]

Basic calcium petronate has been conventionally used as a rust inhibitor. The original basic calcium petronate was extracted from petroleum, but there are also synthetic products at present. In the present invention, both an extract and a synthetic product can be used.

As the basic calcium petronate,
It contains about 45% by weight of calcium sulfonate (average molecular weight measured by ASTM-D-3721 of about 880), about 3% of calcium derived from calcium hydroxide and calcium carbonate, and about 1% of water, with the balance being about 1%. Most are mineral oil. In this composition example, the basic alkali petronate has a total base number (total base number) of 21.
Is the alkali value of calcium inorganic salt (Free Alkalin
ity) is 25.

In converting the foaming inhibitor into a toner,
It is important to properly adjust the charge amount, but more importantly, it is more important to intentionally adjust the polarity of the charge to either positive or negative. According to our research,
Although it was very difficult to intentionally negatively charge the toner of the foaming inhibitor, particularly in the production of a wet developer by a solvent replacement method, a combination of lecithin and basic calcium petronate is used as a charge control agent. As a result, the toner particles of the foaming inhibitor can be negatively charged.

Depending on the type of foaming inhibitor, the type of copolymer resin, and the amount of charge control agent used, toner particles are not negatively charged even when lecithin and basic calcium petronate are used as charge control agents. There are cases. However, when trimellitic anhydride is used as the foaming inhibitor, the toner particles are likely to be negatively charged. Also, when the first monomer unit of the copolymer resin has an acidic group, for example, when the first monomer unit is a monomer unit derived from (meth) acrylic acid, the toner particles are easily negatively charged.

In the solvent replacement method, the content of each of lecithin and basic calcium petronate was 0.05 to 0.1 with respect to 3.6 parts by weight of the foaming inhibitor.
It is preferably 5 parts by weight, preferably 0.1 to 0.3 parts by weight. If the content is less than 0.05 parts by weight, positive charging is likely to occur. On the other hand, if the content is more than 0.5 part by weight, the amount of the foaming inhibitor adhering on the electrostatic latent image tends to be insufficient.

In the production of a wet developer by the solvent replacement method, it is preferable that both lecithin and basic calcium petronate are used at the above-mentioned contents.
If only one of them is used, the toner particles may not be sufficiently negatively charged. Even when printing is performed with a wet developer containing toner particles that are not sufficiently negatively charged, an image may not be formed on the obtained printed matter. Therefore, when a wet developer is produced by a solvent replacement method, it is particularly preferable to use both lecithin and basic calcium petronate.

In the solvent replacement method, the charge control agent exhibits a charge control effect when added in any of the production steps described below or after the solvent is removed, but is preferably used in the production step before the granulation step. Then, the solution of the copolymer resin and the electrically insulating dispersion medium are mixed in the presence of the foaming inhibitor and the charge control agent.

On the other hand, when the wet developer is produced by the slow cooling method, any of the above-mentioned phospholipids, neutral or basic metal petronates, and metal salt compounds of organic acids can be preferably used. Examples of the organic acid metal salt compound include, for example, dialkyl sulfosuccinate metal salts such as cobalt dialkyl sulfosuccinate, manganese dialkyl sulfosuccinate, zirconium dialkyl sulfosuccinate, yttrium dialkyl sulfosuccinate, nickel dialkyl sulfosuccinate; manganese naphthenate, naphthenate Calcium acid, zirconium naphthenate, cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, manganese octylate, calcium octylate, zirconium octylate,
Iron octylate, lead octylate, cobalt octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate,
Metal soaps such as cobalt dodecylate, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate; metal salts of alkylbenzenesulfonic acid such as calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate and barium dodecylbenzenesulfonate; Can be used.

As described above, it is important to properly adjust the charge amount in forming the foaming inhibitor into a toner, but more than that, the polarity of the charge is intentionally adjusted to either positive or negative. It is more important to do. According to the present invention, the toner particles of the foaming inhibitor can be negatively charged by using a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid as the charge controlling agent.

In the slow cooling method, the type of the foaming inhibitor,
Depending on the type of copolymer resin and the amount of charge control agent used, toner particles can be negatively charged even if phospholipid, neutral or basic metal petronate, or metal salt compound of organic acid is used as the charge control agent. May not be charged. However, when trimellitic anhydride is used as the foaming inhibitor, the toner particles are likely to be negatively charged. Further, when the first monomer unit of the copolymer resin has an acidic group, for example, when the monomer unit is derived from (meth) acrylic acid or vinyl acetate, the toner particles are easily negatively charged.

When lecithin or neutral or basic metal petronate is used, the preferred content is 0.1 to 30 parts by weight with respect to 60 parts by weight of the foam inhibitor.
More preferably, it is 1 to 10 parts by weight. Content is 0.1
When the amount is less than the weight part, positive charging is apt to occur. On the other hand, when the content is more than 30 parts by weight, the amount of the foaming inhibitor adhering on the electrostatic latent image tends to be insufficient. In addition, when a metal salt compound of an organic acid is used, the preferable content is the foaming inhibitor 6
It is 30 to 300 parts by weight with respect to 0 parts by weight. If the content is less than 30 parts by weight, positive charging is likely to occur. On the other hand, if the content is more than 300 parts by weight, the amount of the foaming inhibitor adhering on the electrostatic latent image tends to be insufficient.

The charge control agent exhibits a charge control effect when added at any stage in the production process of the later-described slow cooling method. It is preferable to add simultaneously or separately in the step of dispersing the foaming inhibitor and preparing a heated mixture. It is presumed that the charge control agent added during this step acts as a dispersant to improve the dispersibility of the formed copolymer resin particles, or acts as an auxiliary to make it easier to adjust the final charge amount. . As a result, it is possible to manufacture a wet type developer having excellent dispersibility and capable of easily adjusting the charge amount.

[Additives] Other additives such as a dispersant and a fixing agent may be added to the wet developer of the present invention, if necessary. The copolymer resin in the present invention itself has excellent affinity with the dispersion medium, so a dispersant is not necessarily required. In addition, since the entanglement of molecular chains during granulation is controlled, the particle size of toner particles can be reduced to a submicron unit.
In addition, the particle size distribution can be narrowed.

As such a dispersant, for example, a polymer dispersant such as a polyhydroxycarboxylic acid ester can be used. The polyhydroxycarboxylic acid ester is a polymer of an ester derivative of hydroxycarboxylic acid represented by the following formula.

[0075]

HO-X-COOH wherein, in the above formula, X is a divalent saturated or unsaturated aliphatic hydrocarbon having 12 or more carbon atoms, and at least 4 There are carbon atoms. ]

Preferred ester derivatives of hydroxycarboxylic acids include, for example, hydroxycarboxylic acid alkyl esters such as methyl 12-hydroxystearate and ethyl 12-hydroxystearate; lithium 12-hydroxycarboxylate, 12-hydroxycarboxylic acid Examples thereof include metal salts of hydroxycarboxylic acids such as aluminum; amides of hydroxycarboxylic acids; and hardened castor oil.

The polyhydroxycarboxylic acid ester is a light gray brown wax-like substance obtained by polymerizing the hydroxycarboxylic acid ester by partially saponifying it in the presence of a small amount of amines or a catalyst. It contains various forms such as those esterified between molecules and those esterified in the molecule.

The polyhydroxycarboxylic acid ester is preferably a 3- to 10-mer hydroxycarboxylic acid ester. When the degree of polymerization of the polyhydroxycarboxylic acid ester is smaller than 3 or larger than 10, there is no compatibility with a dispersion medium such as n-hexane, and the effect as a dispersant cannot be obtained. The amount of the polyhydroxycarboxylic acid ester to be added is not particularly limited.
To 200% by weight. Polyhydroxycarboxylic acid ester may be added at any time during the manufacturing process before the granulation step in the solvent replacement method, or even in the slow cooling method, it may be added at any time, It is preferably added during the manufacturing process before the slow cooling process.

As the fixing agent, for example, various resins soluble in a dispersion medium such as n-hexane can be used. More specifically, modified or unmodified alkyd resins, ordinary alkyl resins, synthetic resins, Rubber, polyalkylene oxide,
Examples thereof include polyvinyl acetal (for example, polyvinyl butyral) and vinyl acetate resin.

[Solvent] The solvent is used when producing a wet developer by a solvent replacement method. The copolymer resin particles are granulated by utilizing the difference in SP value between the solvent capable of dissolving or swelling the copolymer resin and the electrically insulating dispersion medium. The solvent may not completely dissolve the copolymer resin, but may be capable of dissolving and swelling the copolymer resin at room temperature (25 ° C.), or may be in an insoluble state. It must be able to satisfactorily disperse the partial homopolymer chains present in the copolymer resin.

The solvent must be insoluble or hardly soluble in the foaming inhibitor constituting the core of the copolymer resin particles. The copolymer resin particles have a structure in which the copolymer resin is adsorbed on the surface of the foaming inhibitor, but such a structure is formed when the solvent for dissolving the copolymer resin dissolves up to the foaming inhibitor. Cannot be successfully precipitated.

In order to have good solubility in the copolymer resin, the SP value of the solvent must be the same as the SP value δ of the homopolymer composed only of the first monomer unit in the copolymer resin molecule.
p ^1, and, must approximate to either the SP value .delta.p ² homopolymers made up of only the second monomer units in the copolymer resin molecules, approximation to both .delta.p ¹ and .delta.p ² Preferably.

For example, in the case of a styrene-isoprene copolymer resin, polystyrene (first monomer unit) SP
Value of 9.1, S of polyisoprene (second monomer unit)
The P value is 8.15. Therefore, toluene (SP value:
8.9) or cyclohexane (SP value: 8.2).

As a solvent for dissolving the copolymer resin, for example, cyclohexane (SP value: 8.2), cellosolve acetate (SP value: 9.4), toluene (SP value: 8.9), tetrahydrofuran (SP value: 9.1) ), Methyl ethyl ketone (SP value 9.5), cyclohexanone (SP value 10.
4), acetone (SP value 9.6), dioxane (SP value 10.1), ethyl cellosolve (SP value 10.7), cyclohexanol (SP value 11.4), methyl cellosolve (SP value 11.7) , Isopropyl alcohol (SP
Value 11.4), ethanol (SP value 12.8), methanol (SP value 14.5) and the like.

When the foaming inhibitor is trimellitic anhydride, the copolymer resin is preferably dissolved in toluene. Toluene has good solubility in copolymer resins, but is insoluble or poorly soluble in trimellitic anhydride, so a toluene solution of copolymer resins is electrically insulated in the presence of trimellitic anhydride. When mixed with an aqueous dispersion medium, copolymer resin particles containing trimellitic acid can be successfully precipitated.

[Electrically Insulating Dispersion Medium] As the electrically insulating dispersion medium, it is preferable to use a liquid aliphatic hydrocarbon. Among them, those having a volume resistance of 10 ¹⁰ Ω · cm or more are particularly preferable. As a liquid aliphatic hydrocarbon,
Examples thereof include n-paraffinic hydrocarbons, iso-paraffinic hydrocarbons, mixtures of these paraffinic hydrocarbons, halogenated aliphatic hydrocarbons, and branched-chain aliphatic hydrocarbons. Particularly preferred are branched chain aliphatic hydrocarbons. Branched-chain aliphatic hydrocarbons are supplied by Exxon under the trade name Isopar. In Isopar,
There are grades such as Isopar E, Isopar G, Isopar H, Isopar L and Isopar M, and an appropriate one is selected according to the type of copolymer resin.

In the present invention, it is necessary to use an electrically insulating dispersion medium having the following SP value characteristics.

(I) SP of a homopolymer composed of only the first monomer unit as a part of the copolymer resin molecule
Δ (δp ¹⁾ between the value δp ¹ and the SP value δd of the dispersion medium.
-Δd) is 1.0 or more.

(Ii) S of a homopolymer composed of only the second monomer unit as a part of the copolymer resin molecule
The difference Δ (δp between the P value δp ² and the SP value δd of the dispersion medium
^2- δd) is 1.0 or less.

(Iii) The difference Δ (δp ¹ −δ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers described above.
p ² ) is 0.5 or more.

For example, in the solvent replacement method, a solution of a styrene-isoprene copolymer resin is mixed with n-hexane in the presence of a foam inhibitor to form a styrene-isoprene copolymer resin containing a foam inhibitor. Particles can be deposited. In this case, polystyrene (first
SP value .delta.p ¹ 9.1 monomeric units), SP value .delta.p ² polyisoprene (second monomer unit) is 8.15, and n- hexane (from SP value δd of the dispersion medium) is 7.3 As shown in the following calculation formula, the above condition is satisfied.

[0092]

Δp ¹ −δd = 9.1−7.3 = 1.8∴Δ (δp ¹ −δd) ≧ 1 δp ² −δd = 8.15−7.3 = 0.85∴Δ (δp ²⁻ δd) ≦ 1 δp ¹ −δp ² = 9.1-8.15 = 0.95∴Δ (δp ¹ −δp ² ) ≧ 0.5

The particles of the styrene-isoprene copolymer resin are formed such that, in n-hexane as a dispersion medium, a portion derived from the isoprene unit forms an outer edge portion in a dissolved or swollen state, and a portion derived from the styrene unit is formed. Is adsorbed on the surface of the foaming inhibitor to form an insoluble core together with the foaming inhibitor.

Here, the homopolymers which can serve as indices when specifying the SP value of the homopolymer composed of only the first monomer unit or the second monomer unit of the copolymer resin and the SP value of each homopolymer are listed as follows. become that way. Polyethylene (8.1), polybutadiene (8.
4), polyisoprene (8.15), polyisobutylene (7.7), polylauryl methacrylate (8.2),
Polystearyl methacrylate (8.2), polyisobonyl methacrylate (8.2), poly-t-butyl methacrylate (8.2), polystyrene (9.1), polyethyl methacrylate (9.1), polymethyl methacrylate (9.3), polymethyl acrylate (9.
7), polyethyl acrylate (9.2), polyacrylonitrile (12.8).

The following is a list of usable electrically insulating dispersion media and SP values of the respective dispersion media. n-hexane (7.3), n-heptane (7.5), n-octane (7.5), nonane (7.6), decane (7.7),
Dodecane (7.9), cyclohexane (8.2), perchlorethylene (9.3), trichloroethane (9.
9). The SP value of the Isopar series (trade name) supplied by Exxon is 7.0 to 7.3.

Preferred combinations of the copolymer resin and the electrically insulating dispersion medium include the following combinations.

First, in the case of using n-hexane (δd = 7.3) as a dispersion medium, preferred copolymer resins are listed, and a homopolymer SP composed only of the first monomer unit of the copolymer resin is listed. Difference Δ (δp ¹ −δd) between the value δp ¹ and the SP value δd of the dispersion medium, and the difference between the SP value δp ^{2 of the} homopolymer composed of only the second monomer unit of the copolymer resin and the SP value δd of the dispersion medium. Δ (δp ² −δ
d) and the difference Δ (δp ¹ −δp between δp ¹ and δp ^2
2 ) is also described. However, the numerical value in parentheses is the SP value of the homopolymer composed only of the monomer unit.

Ethylene (8.1) -vinyl acetate (9.
4) copolymer resin, Δ (δp ¹ −δd) = 2.1, Δ (δ
(p ² −δd) = 0.8, Δ (δp ¹ −δp ² ) = 1.3 Ethylene (8.1) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2. 4, Δ (δp ² −
δd) = 0.8, Δ (δp ¹ −δp ² ) = 1.6 Ethylene (8.1) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.9, Δ (Δp ² −
δd) = 0.8, Δ (δp ¹ −δp ² ) = 1.1 Styrene (9.1) -isoprene (8.15) copolymer resin, Δ (δp ¹ −δd) = 1.8, Δ ( δp ² -δd)
= 0.9, Δ (δp ¹ −δp ² ) = 0.9 Lauryl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) = 2.
0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp
² ) = 1.1 Lauryl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) = 1.
8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 0.9 Lauryl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.5 Lauryl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.0 Lauryl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) = 1.
7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 0.8 Stearyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 1.1 Stearyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 0.9 Stearyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.5 Stearyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.0 Stearyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 0.8 Isobonyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 1.1 Isobornyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 0.9 Isobonyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.5 Isobonyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
9, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δp)
² ) = 1.0 Isobonyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.7, Δ (δp ² −δd) = 0.9, Δ (δp ¹ −δ
p ² ) = 0.8 t-butyl methacrylate (8.3) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
2.0, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δ
p ² ) = 1.0 t-butyl methacrylate (8.3) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.8, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δ
p ² ) = 0.8 t-butyl methacrylate (8.3) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 2.
4, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp)
² ) = 1.4 t-butyl methacrylate (8.3) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
9, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δp)
² ) = 0.9 t-butyl methacrylate (8.3) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.7, Δ (δp ² −δd) = 1.0, Δ (δp ¹ −δ
p ² ) = 0.7 A combination of the above copolymer resin with n-heptane, n-octane, nonane, decane, dodecane, cyclohexane or the like is also preferable.

Preferred copolymer resins when perchloroethylene (δd = 9.3) is used as a dispersion medium include:
For example, there is the following.

Ethylene (8.1) -vinyl acetate (9.
4) copolymer resin, Δ (δp¹ −δd) = 1.2, Δ (δ
p^Two −δd) = 0.1, Δ (δp¹ −δp^Two ) = 1.3 Ethylene (8.1) -methyl acrylate (9.7)
Polymerized resin, Δ (δp¹ −δd) = 1.2, Δ (δp^Two −
δd) = 0.4, Δ (δp¹ −δp^Two ) = 1.6 Ethylene (8.1) -ethyl acrylate (9.2)
Polymerized resin, Δ (δp¹ −δd) = 1.2, Δ (δp^Two −
δd) = 0.1, Δ (δp¹ −δp^Two ) = 1.1 Styrene (9.1) -isoprene (8.15) copolymer tree
Fat, Δ (δp¹ −δd) = 1.15, Δ (δp^Two −δ
d) = 0.2, Δ (δp¹ −δp^Two ) = 0.95 lauryl methacrylate (8.2) -methyl methacrylate
(9.3) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0, Δ (δp¹ −δp ^Two ) =
1.1 Lauryl methacrylate (8.2) -ethyl methacrylate
(9.1) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.2, Δ (δp¹ −δp
^Two ) = 0.9 lauryl methacrylate (8.2) -methyl acrylate
G (9.7) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.4, Δ (δp¹ −δp
^Two ) = 1.5 lauryl methacrylate (8.2) -ethyl acrylate
G (9.2) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.1, Δ (δp¹ −δp
^Two ) = 1.0 lauryl methacrylate (8.2) -propyl acryle
(9.0) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.3, Δ (δp¹ −δp
^Two ) = 0.8 stearyl methacrylate (8.2) -methyl methacrylate
Rate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0, Δ (δp¹ −δp
^Two ) = 1.1 stearyl methacrylate (8.2) -ethyl methacrylate
Rate (9.1) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0.2, Δ (δp¹−δ
p^Two ) = 0.9 stearyl methacrylate (8.2) -methyl acryle
(9.7) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.4, Δ (δp¹ −δp
^Two ) = 1.5 stearyl methacrylate (8.2) -ethyl acryle
(9.2) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.1, Δ (δp¹ −δp
^Two ) = 1.0 stearyl methacrylate (8.2) -propylacrylic
Rate (9.0) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0.3, Δ (δp¹−δ
p^Two ) = 0.8 Isobonyl methacrylate (8.2) -methyl methacrylate
Rate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0, Δ (δp¹ −δp
^Two ) = 1.1 Isobonyl methacrylate (8.2) -ethyl methacrylate
Rate (9.1) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0.2, Δ (δp¹−δ
p^Two ) = 0.9 Isobonyl methacrylate (8.2) -methyl acryle
(9.7) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.4, Δ (δp¹ −δp
^Two ) = 1.5 Isobonyl methacrylate (8.2) -ethyl acryle
(9.2) copolymer resin, Δ (δp¹ -Δd) = 1.
1, Δ (δp^Two −δd) = 0.1, Δ (δp¹ −δp
^Two ) = 1.0 Isobonyl methacrylate (8.2) -propylacrylic
Rate (9.0) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0.3, Δ (δp¹−δ
p^Two ) = 0.8 t-butyl methacrylate (8.3) -methyl methacrylate
Rate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.0, Δ (δp^Two −δd) = 0, Δ (δp¹ −δp
^Two ) = 1.0 t-butyl methacrylate (8.3) -ethyl methacrylate
Rate (9.1) copolymer resin, Δ (δp¹ −δd) =
1.0, Δ (δp^Two −δd) = 0.2, Δ (δp¹−δ
p^Two ) = 0.8 t-butyl methacrylate (8.3) -methyl acryle
(9.7) copolymer resin, Δ (δp¹ -Δd) = 1.
0, Δ (δp^Two −δd) = 0.4, Δ (δp¹ −δp
^Two ) = 1.4 t-butyl methacrylate (8.3) -ethyl acryle
(9.2) copolymer resin, Δ (δp¹ -Δd) = 1.
0, Δ (δp^Two −δd) = 0.1, Δ (δp¹ −δp
^Two ) = 0.9 t-butyl methacrylate (8.3) -propylacrylic
Rate (9.0) copolymer resin, Δ (δp¹ −δd) =
1.0, Δ (δp^Two −δd) = 0.3, Δ (δp¹−δ
p^Two ) = 0.7 using trichloroethane (δd = 9.9) as the dispersion medium
Examples of preferred copolymer resins in the case where
There are things.

N-Propyl methacrylate (8.8)-
Methyl acrylate (9.7) copolymer resin, Δ (δp¹ 
−δd) = 1.1, Δ (δp^Two −δd) = 0.2, Δ
(Δp¹−δp^Two ) = 0.9 n-propyl methacrylate (8.8) -methyl methacrylate
Relate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.1, Δ (δp^Two −δd) = 0.6, Δ (δp ¹ −δ
p^Two ) = 0.5 n-butyl methacrylate (8.7) -methyl acryle
(9.7) copolymer resin, Δ (δp¹ -Δd) = 1.
2, Δ (δp^Two −δd) = 0.2, Δ (δp¹ −δp
^Two ) = 1.0 n-butyl methacrylate (8.7) -ethyl acryle
(9.2) copolymer resin, Δ (δp¹ -Δd) = 1.
2, Δ (δp^Two −δd) = 0.7, Δ (δp¹ −δp
^Two ) = 0.5 n-butyl methacrylate (8.7) -methyl methacrylate
Rate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.2, Δ (δp^Two −δd) = 0.6, Δ (δp¹−δ
p^Two ) = 0.6 n-hexyl methacrylate (8.6) -methylacrylic
Rate (9.7) copolymer resin, Δ (δp¹ −δd) =
1.3, Δ (δp^Two −δd) = 0.2, Δ (δp¹−δ
p^Two ) = 1.1 n-hexyl methacrylate (8.6) -ethylacryl
Rate (9.2) copolymer resin, Δ (δp¹ −δd) =
1.3, Δ (δp^Two −δd) = 0.7, Δ (δp¹−δ
p^Two ) = 0.6 n-hexyl methacrylate (8.6) -methyl methacrylate
Relate (9.3) copolymer resin, Δ (δp¹ −δd) =
1.3, Δ (δp^Two −δd) = 0.6, Δ (δp ¹ −δ
p^Two ) = 0.7 n-hexyl methacrylate (8.6) -ethyl methacrylate
Relate (9.1) copolymer resin, Δ (δp¹ −δd) =
1.3, Δ (δp^Two −δd) = 0.8, Δ (δp ¹ −δ
p^Two ) = 0.5 On the other hand, also in the slow cooling method, the above (i) to (iii)
It is necessary to use an electrically insulating dispersion medium with SP value characteristics
is there.

Further, in the slow cooling method, the heated electrically insulating dispersion medium contains at least the first monomer unit and the second monomer unit.
It must have the property of dissolving a copolymer resin composed of monomer units and then cooling the dissolved solution to precipitate the copolymer resin dissolved in the electrically insulating dispersion medium. is there. Since the above-mentioned electrically insulating dispersion medium satisfies such properties, any of them can be preferably used.

The copolymer resin particles precipitated by cooling are:
The portion of the first monomer unit of the copolymer resin repels the dispersion medium and is adsorbed on the surface of the foaming inhibitor. As a result, the copolymer resin is microscopically aggregated around the foaming inhibitor. Thus, copolymer resin particles containing the foaming inhibitor are formed. The formed copolymer resin particles have the same configuration as those obtained by the above-described solvent replacement method, and include a core portion insoluble in the dispersion medium, and an outer edge portion that surrounds the core portion and dissolves or swells in the dispersion medium. Become.

[First Method for Producing Wet Developer (Solvent Replacement Method)] To produce the wet developer of the present invention by the solvent replacement method, (1) a copolymer resin is dissolved in a solvent, and (2) The solution in which the copolymer resin is dissolved is mixed with the electrically insulating dispersion medium in the presence of the foaming inhibitor, and then (3) the solvent may be removed. The copolymer resin particles are precipitated (granulated) in at least one of the step (2) of mixing the electrically insulating dispersion medium or the step (3) of removing the solvent. Lecithin and basic calcium petronate, which are charge control agents, may be added to raw materials such as copolymer resins and foam inhibitors at any stage of the manufacturing process, or may be added to materials other than the raw materials, such as solvents. Is added to the intermediate product after granulation or solvent removal.

First, in the step (1), the copolymer resin is dissolved using an appropriate solvent. The copolymer resin is preferably completely dissolved in the solution, but may be in a swollen state or a partial homopolymer chain present in the copolymer resin even if it is in an insoluble state. Should be satisfactorily dispersed. In addition, the solvent is preferably one that can dissolve and swell the copolymer resin at room temperature (25 ° C.) or can disperse a partial homopolymer chain well. Further, the solvent must be insoluble or poorly soluble in the foam inhibitor.

The dispersant is added to the copolymer resin solution in an amount of from 0.3 to 0.3.
If it is contained in the range of 0.5% by weight, the state of dispersion of the resin can be improved. The amount of the copolymer resin dissolved in the solvent is arbitrary, but if the ratio of the resin is too high, the resin particles may come into contact with each other in the granulation step and form a gel-like mass, and thus usually 1 to 80 weight. %, A solution containing a copolymer resin in a ratio of 5% is prepared.
Prepare a 溶液 10% by weight dilute solution.

Next, in the step (2) of mixing the electrically insulating dispersion medium, the solution prepared in the step (1) and the electrically insulating dispersion medium are mixed with a foaming inhibitor such as trimellitic acid. Mix below to precipitate the copolymer resin particles.

For example, when a solution of a styrene-isoprene copolymer resin dissolved in toluene at a ratio of 10% by weight of toluene is mixed with n-hexane, the mixture becomes cloudy, and the precipitation of styrene-isoprene copolymer resin particles is clearly observed. it can. Further, when the above resin solution is mixed with n-hexane in the presence of trimellitic acid as a foaming inhibitor, it is difficult to confirm cloudiness because trimellitic acid is dispersed, but it contains trimellitic acid. It can be observed that the resin particles adhere to the wall surface of the glass bottle.

In order to allow a foaming inhibitor such as trimellitic acid to coexist at the time of mixing, the foaming inhibitor powder may be added to either the resin solution or the electrically insulating dispersion medium. When a resin solution and a dispersion medium are mixed together in the presence of a foaming inhibitor, the resin molecular chains that have been dissolved, swelled, or dispersed at the molecular level in the solution are filled with an electrically insulating dispersion medium that is a poor solvent. Will be added to the environment. As a result, the molecular chain of the copolymer resin is adsorbed on the surface of the foaming inhibitor via the first monomer unit having a higher affinity for the foaming inhibitor than for the dispersion medium, and the particles of the foaming inhibitor are removed. Entangling in a wrapping manner, resin particles are formed. Since the surface of the copolymer resin particles thus formed is rich in the second monomer unit having a high affinity for the dispersion medium and is a dissolved or swelled part in the dispersion medium, Even if a large amount of a foaming inhibitor is contained, contact between the foaming inhibitors is avoided, and excellent dispersion stability is exhibited.

As described above, the charge controlling agents lecithin and basic calcium petronate may be added at any stage during the production. It is preferable to add it to either the resin solution or the electrically insulating dispersion medium in advance so that it can be performed.

In the step (3), the solvent is removed from the liquid mixture containing the copolymer resin particles, the dispersion medium and the good solvent. From the viewpoint of granulation properties, it is preferable to remove the solvent by a method such as decantation or evaporation. In addition, in order to adjust the particle size of the resin particles, ball mill, attritor, sand grinder,
Fine particles may be further formed using a Keddy mill, a three-roll mill, or the like.

Thus, a wet developer in which the copolymer resin particles containing the foaming inhibitor are dispersed in the electrically insulating dispersion medium is obtained. The core portion of the copolymer resin particles is mainly formed by the foaming inhibitor and the portion of the first monomer unit adsorbed on the surface of the foaming inhibitor, and is insoluble in the dispersion medium. An outer edge portion rich in the second monomer unit having a high affinity for the hydrophilic dispersion medium is formed. Accordingly, the copolymer resin particles are well dispersed in the wet developer, and even if the particle concentration is increased, gelation, macroscopic aggregation, precipitation, and the like do not occur, and the dispersion stability is excellent. The solid content concentration in the wet developer may be 1 to 5% by weight, and the content ratio of the copolymer resin particles to the solid content in the wet developer is usually 0.01 to 80% by weight, preferably 0%. 0.1 to 50% by weight.

In the wet developer produced by the solvent displacement method, the foaming inhibitor can be incorporated in the copolymer resin particles in an amount of up to 80% by weight, preferably up to 75% by weight. However, when the polarity and chargeability of the copolymer resin particles are adjusted so that they can be particularly preferably used for practical use, it is possible to incorporate up to about 50% by weight of the foaming inhibitor in the copolymer resin particles. it can.

[Second Production Method of Wet Developer (Slow Cooling Method)] To produce the wet developer of the present invention by the slow cooling method, (1) the electric insulating dispersion medium is heated to dissolve the copolymer resin and A foaming inhibitor may be dispersed in the electrically insulating dispersion medium simultaneously or separately with the copolymer resin to prepare a heated mixture, and (2) the heated mixture may be gradually cooled. The copolymer resin particles are precipitated (granulated) in the slow cooling step (2) and the dilution and dispersion step that is performed as necessary.
A phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid, which is a charge control agent, can be added at any stage of the production process. For example, it may be added to a raw material such as a copolymer resin or a foaming inhibitor, may be added to a material other than the raw material such as an electrically insulating dispersion medium, or may be added to an intermediate product after precipitation (granulation) or after a dispersion step. Can be added.

First, in the step (1), the electrically insulating dispersion medium having the above-mentioned solubility parameter characteristics is heated to dissolve the copolymer resin, and the foaming is suppressed in the electrically insulating dispersion medium. The heating mixture is prepared by dispersing the agent. The foaming inhibitor may be added and dispersed simultaneously with the copolymer resin in the electrically insulating dispersion medium, or may be separately added and dispersed. In the mixture in the high temperature state, it is preferable that the copolymer resin is completely dissolved,
It may be in a swollen state. Further, even if it is in an insoluble state, it is sufficient that partial homopolymer chains present in the copolymer resin are well dispersed. The temperature of the electrically insulating dispersion medium for dissolving the copolymer resin is preferably equal to or lower than the decomposition temperature of the foaming inhibitor, and the temperature is not particularly limited, but is usually preferably about 70C to 150C. Further, the electrically insulating dispersion medium must be a solvent that is insoluble or hardly soluble in the foam inhibitor.

In the slow cooling method, the dispersant is added to the solution in which the copolymer resin is dissolved in an amount of 0.3 to 0.5 as in the solvent replacement method.
When the content is contained in the range of weight%, the dispersion state of the resin can be improved.

Next, in the step (2) of gradually cooling the heated mixture, the heated mixture prepared in the step (1) is gradually cooled to precipitate (granulate) the copolymer resin particles.

For example, a styrene-isoprene copolymer resin is dissolved in n-hexane heated to a predetermined temperature, and then the precipitation of the copolymer resin is stopped at a temperature at which the styrene-isoprene copolymer resin in the solution starts to precipitate. When the temperature is gradually cooled to a predetermined temperature, precipitation of the styrene-isoprene copolymer resin particles can be clearly observed. Also, in the above solution,
A mixture obtained by mixing trimellitic acid, which is a foam inhibitor,
When gradually cooled from the temperature at which the styrene-isoprene copolymer resin starts to precipitate in the solution to the temperature at which the precipitation of the copolymer resin stops, it becomes difficult to confirm white turbidity because trimellitic acid is dispersed. It can be observed that the copolymer resin particles containing the inhibitor adhere to the wall surface of the glass bottle.

The gradual cooling may be performed at least between the temperature at which the precipitation of the copolymer in the solution starts to precipitate and the temperature at which the precipitation of the copolymer is stopped. When the temperature is lower than the temperature at which the precipitation of ceases, it is not always necessary to gradually cool. The slow cooling rate varies depending on the electric insulating dispersion medium, the copolymer resin and the like to be used, but it is preferable that the slow cooling rate is generally in the range of 30 ° C./hour to 0.1 ° C./hour. The slow cooling speed affects the particle size of the copolymer resin particles and the aggregation between the toner particles, and the larger the slow cooling speed, the larger the particle size, and the lower the slow cooling speed, the smaller the particle size.

The mixture in which the foaming inhibitor such as trimellitic acid is mixed is added to either the powder of the foaming inhibitor in the electric insulating dispersion medium or the solution in which the copolymer resin is dissolved in the electric insulating dispersion medium. Can be obtained. When the foaming inhibitor is mixed in the electrically insulating dispersion medium, the electrically insulating dispersion medium is subsequently heated to dissolve the copolymer resin to form a heated mixture.

In this mixture, at least one of the first monomer unit and the second monomer unit, which are the molecular chains of the copolymer resin, is dissolved in a heated electrically insulating dispersion medium.
It is swollen or dispersed at the molecular level, and is in a state of being dissolved as a resin. Then, by cooling the mixture, at least one of the molecular chains of the copolymer resin is
The copolymer resin is precipitated by dissolving, swelling, or changing from a state dispersed at a molecular level to an insoluble state in the electrically insulating dispersion medium. Specifically, the precipitation of the copolymer resin is caused by the fact that the molecular chain of the copolymer resin is formed through the first monomer unit having a higher affinity for the foam inhibitor than for the electrically insulating dispersion medium. This is caused by being adsorbed on the surface of the resin and entangled in such a manner as to enclose the particles of the foaming inhibitor, thereby forming copolymer resin particles. The surface of the copolymer resin particles thus precipitated is rich in a portion of the second monomer unit having a high affinity for the electrically insulating dispersion medium, and is dissolved and swelled in the electrically insulating dispersion medium. Thus, even if a large amount of the foaming inhibitor is contained, contact between the foaming inhibitors is avoided, and excellent dispersion stability is exhibited.

As described above, the phospholipid, neutral or basic metal petronate, or metal salt compound of an organic acid, which is a charge controlling agent, may be added at any stage during the production. It is preferably added in the step (1) of preparing. The charge control agent added at this time is supposed to act as a dispersant to improve the dispersibility of the formed copolymer resin particles or to assist in adjusting the final charge amount. As a result, excellent dispersibility,
It is possible to manufacture a wet developer in which the charge amount can be easily adjusted.

The amount of the copolymer resin dissolved in the electrically insulating dispersion medium is optional depending on the type of the dispersion medium and the heating temperature.
Therefore, when the copolymer resin particles precipitate (granulate) in the subsequent cooling step, a concentrated dispersion of the copolymer resin particles may be directly obtained, but usually, the copolymer resin particles come into contact with each other. This gives a clay-like mixture that is not dispersed. If such a clay-like mixture is obtained,
After slow cooling, the clay-like mixture is added to the same electrically insulating dispersion medium as described above, or the electrically-insulating dispersion medium is added to the clay-like mixture to form and disperse the copolymer resin particles. The concentrated dispersion obtained by adding the electrically insulating dispersion medium to the concentrated dispersion obtained by the slow cooling step (2) or the clay-like mixture obtained by the slow cooling step (2). By further adding an electrically insulating dispersion medium, the copolymer resin particles can be adjusted to a desired concentration while maintaining the dispersion stability of the copolymer resin particles.

Thus, a wet developer in which the copolymer resin particles containing the foaming inhibitor are dispersed in the electrically insulating dispersion medium is obtained. The core portion of the copolymer resin particles is mainly formed by the foaming inhibitor and the portion of the first monomer unit adsorbed on the surface of the foaming inhibitor, and is insoluble in the electrically insulating dispersion medium. Has an outer edge portion rich in the second monomer unit having a high affinity for the electrically insulating dispersion medium. Therefore, the copolymer resin particles are well dispersed in the wet developer, and even if the particle concentration is increased,
It does not cause gelation, macroscopic aggregation, precipitation, etc., and has excellent dispersion stability. The solid content concentration in the wet developer may be 1 to 5% by weight, and the content ratio of the copolymer resin particles to the solid content in the wet developer is usually 0.01 to 80% by weight, preferably 0%. 0.1 to 50% by weight.

In the case of the slow cooling method, the reproducibility is higher than in the case of the solvent replacement method. Under the same conditions, a wet developer having the same polarity and a constant charge amount can be easily obtained. In the case of employing the slow cooling method, copolymer resin particles having a higher content of the foaming inhibitor can be obtained than in the case of employing the solvent replacement method. In the case of using the solvent replacement method, the content of the foaming inhibitor in the copolymer resin particles can be increased to as high as 50% by weight. However, the solvent replacement method has a practical limit. However, in the case of the slow cooling method, while maintaining the polarity and charge amount suitable for practical use,
The content of the foaming inhibitor in the copolymer resin particles is from 50% by weight to
It is particularly preferable because it can be further increased to 80% by weight.

In any case, the wet developer of the present invention obtained by the solvent replacement method and the slow cooling method hardly causes problems such as aggregation even when a large amount of copolymer resin particles containing a foaming inhibitor is contained. The content of the foaming inhibitor in the wet developer can be increased.

(3) Method for Producing a Foam Having Surface Irregularities and an Intermediate Product
Using the above-mentioned wet developer, electrostatic recording, electrostatic transfer, by a method utilizing an electrostatic action such as electrostatic printing, after covering or penetrating the foam inhibitor in a predetermined pattern, and then By foaming, a foam having an uneven pattern with high design properties can be produced.

The wet developing agent of the present invention and the wet developing agent manufactured by the manufacturing method of the present invention are particularly suitable for an on-demand type printing system using electrostatic recording or electrostatic transfer among electrostatic printing systems. It is suitable and can easily and quickly form a pattern of the foam inhibitor without using a printing plate.

Here, according to the electrostatic recording method, an electrostatic latent image is formed directly on the surface of the foamed raw material, and the foamed raw material is exposed to a wet developer to develop the electrostatic latent image. On the other hand, according to the electrostatic transfer method, an electrostatic latent image is formed on the surface of a dielectric material that is not a foam, and the dielectric material is exposed to a wet developer to develop the electrostatic latent image. The pattern of the foaming inhibitor formed thereon is transferred directly or indirectly to the surface of the raw foam. In electrostatic transfer, a toner pattern on a dielectric can be directly transferred onto a transfer target by electrostatic force. Alternatively, the toner pattern on the dielectric is transferred to the intermediate receiver once, and the toner pattern on the intermediate receiver is transferred onto the receiver by a method such as thermal transfer. It may be transcribed.

FIGS. 1 to 7 illustrate steps for producing a pseudo-tile foam, that is, a foam having an appearance surface such as a tile, by using an electrostatic recording technique. is there. FIG. 1 is a partial plan view of an example (1) of a foam raw material used in the present invention, and FIG.
It is a schematic diagram of the cross section cut along the A line. As shown in FIG. 2, the raw foam 1 is provided with a foamable portion 2 formed of a foamable resin on one surface side of a support 3, and further provided with a dielectric layer 4 on the foamable portion 2. It is. The dielectric layer 4 is formed of a resin or a resin composition having excellent chargeability in order to impart appropriate chargeability to the surface of the foamable portion. When the foamable portion 2 is formed of a resin having a poor chargeability such as a polyvinyl chloride resin, a good electrostatic latent image cannot be formed unless a dielectric layer is provided. It is necessary to form an electrostatic latent image when the foaming resin is excellent in chargeability, or by providing a foaming inhibitor pattern on the foaming raw material by thermal transfer or electrostatic transfer. When not provided, it may be formed only of the foamable resin portion provided with the conductive layer.

The resin composition for the foamable portion, the support, and the like may be formed using a material conventionally used in performing chemical embossing. As the support 3, for example, paper, woven fabric, knitted fabric, felt, nonwoven fabric, and the like can be used. The foamable portion 2 can be formed on a support using the foamable resin composition as described above.

The dielectric layer 4 may be formed using a material conventionally used for performing electrostatic recording. Dielectric layer 4
Is an acrylic resin, styrene resin, polyester, polyolefin, polyamide, polyether, polyimide,
Polyamide imide, polyetherester, poly-p-
Phenylene sulfide, polyvinyl chloride, fluororesin,
It is preferable to use a polycarbonate resin or the like. When the foamable portion is formed of a resin composition mainly composed of polyvinyl chloride, the dielectric layer 4 is made of an acrylic resin; a polyester; an ethylene-vinyl acetate copolymer resin or an ethylene- (meth) acrylic acid copolymer resin. It is preferable to use an ethylene copolymer resin as described above. These resins are excellent not only in chargeability, but also in adhesion to polyvinyl chloride and heat resistance.

The raw foam 1 is prepared, and an electrostatic latent image 5 is formed on the surface of the foamable portion 2. In FIG. 3, since the joint portion of the tile pattern is intended to be a non-foamed concave portion, the electrostatic latent image 5 in which the charged portion has a lattice pattern is formed. Next, when the surface of the foamable portion 2 having the electrostatic latent image 5 is exposed to the wet developer of the present invention and developed, the copolymer resin particles dispersed in the developer are charged with the electrostatic latent image 5. Attaches to parts. As a result, as shown in FIGS. 4 and 5, a coating 7 having a lattice pattern containing a foaming inhibitor is formed on the surface of the foamable portion 2. Thus, the foamable intermediate product 6 having the pattern of the foam inhibitor is obtained.

Thereafter, the foamable intermediate product 6 is heated at an appropriate temperature to obtain a pseudo tile foam in which the unfoamed concave portions 10 are formed in a lattice as shown in FIGS. When the foamable intermediate product 6 is heated, the foaming inhibitor existing on the surface of the foamable portion 2 diffuses into the foamable portion, and the catalytic action of the foaming accelerator immediately below the foaming inhibitor pattern. Inhibited, the foaming temperature rises.
Therefore, the foamable intermediate product 6 is heated to a temperature at which the area outside the pattern of the foaming inhibitor becomes foamable or higher, and the temperature immediately below the foaming inhibitor pattern is below the foamable temperature, so that foaming is performed. Protrusions 9 with increased bulk
And a foam 8 having an unfoamed concave portion 10 corresponding to the pattern portion of the foam inhibitor or the pattern of the electrostatic latent image.

[0135]

EXAMPLES The wet developer according to the present invention will be described in more detail through examples. In the following, Examples 1 to 17
Is a wet developer manufactured by a solvent displacement method, and Examples 18 to 31 are wet developers manufactured by a slow cooling method.

Example 1 Production of Wet Developer 1 by Solvent Replacement Method: First, 7.35 g of a mixture having the following composition was added to 80 g of toluene.
It was dissolved and dispersed at room temperature using a paint shaker. The obtained dissolved / dispersed liquid was washed with Isopar L (S
(P value: 7.3, manufactured by Exxon Co.) was added to 360 g while irradiating ultrasonic waves, then only toluene was removed using an evaporator, and then further supersonicated using an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Seisaku-sho, Ltd.). Irradiation of a sound wave gave a master toner. The obtained master toner was diluted with Isopar L to adjust the toner concentration to 4% by weight to obtain a wet developer 1 by a solvent replacement method. Here, the toner concentration is a ratio of the total amount of the foaming inhibitor and the copolymer resin to the total amount of the wet developer.

<Composition for Wet Developer 1> Trimellitic anhydride (Mitsubishi Gas Chemical): 3.6 parts by weight Ethylene (SP value: 8.1) / methacrylic acid copolymer resin (SP value: 9) .4) (Nucrel N035, manufactured by DuPont Mitsui): 3.6 parts by weight ・ Soybean lecithin (manufactured by Junsei Chemical): 0.1 parts by weight ・ Basic calcium petronate (manufactured by Witco): 0.05 parts by weight (total) [Examples 2 to 9] Wet developer by solvent replacement method in the same manner as in Example 1 except that the added amounts of lecithin and basic calcium petronate as charge control agents were changed. 2
To 9 were produced. Table 1 shows the amount of addition in each example.

[Example 10] A mixture 7.35 having the following composition:
g was added to 80 g of toluene, and thereafter the same procedure as in Example 1 was carried out to prepare a wet developer 10 by a solvent replacement method.

<Composition for Wet Developer 10> Trimellitic anhydride (manufactured by Mitsubishi Gas Chemical): 3.6 parts by weight Ethylene (SP value: 8.1) / vinyl acetate copolymer resin (SP value: 9) .4) (El vax 4310, manufactured by Dupont Mitsui): 3.6 parts by weight ・ Soybean lecithin (manufactured by Junsei Chemical): 0.05 parts by weight ・ Basic calcium petronate (manufactured by Witco): 0.1 parts by weight ( [Total: 7.35 parts by weight] [Examples 11 to 17] Wet development by a solvent displacement method was carried out in the same manner as in Example 10 except that the amounts of the charge control agents lecithin and basic calcium petronate were changed. Agents 11 to 17 were prepared. Table 2 shows the addition amount of each example.

Example 18 Production of Wet Developer 18 by Slow Cooling Method: First, 463.54 g of a mixture having the following composition was added to Isopar L (SP value: 7.0).
3, exxon) and dissolved and stirred at 120 ° C. using a double planetary mixer (manufactured by Aikosha) and an oil bath. The stirring speed at this time was 5 on the mechanical scale of the planetary mixer.

In order to sufficiently dissolve the mixture, the mixture was kept at 120 ° C. for 1 hour, and then the temperature was lowered to 110 ° C. and kept for 2 hours. Then, at a rate of 10 ° C./0.5 hour, 80
Quenched to 60 ° C at a rate of 2 ° C / 0.5 hour.
The temperature was gradually cooled to ° C. Next, the oil bath was removed and the mixture was allowed to cool to room temperature to obtain a clay-like conc. Toner (concentrated toner). The stirring was continuously performed during a series of cooling and cooling.

Further, the obtained conc. Toner 763.5
150 g of 4 g was added to 250 g of Isopar L and dispersed at room temperature using a paint shaker. 400 g of the obtained dispersion is put into Isopar L3100
g, and adjusted so that the toner concentration became 2.6% by weight, to obtain 3500 g of a master toner. Lecithin and basic calcium petronate were added at a ratio of 2.5 g to 3500 g of the obtained master toner, and these were gently stirred to obtain a wet developer 18. Here, the toner concentration is a ratio of the total amount of the foaming inhibitor and the copolymer resin to the total amount of the wet developer. Also,
The total amount of lecithin and basic calcium petronate in the toner is the sum of what is previously contained in the composition for wet developer 18 and what is added later, and the content of each is trimellitic anhydride The amount is 3.85 parts by weight for 60 parts by weight.

<Composition for Wet Developer 18> Trimellitic anhydride (Mitsubishi Gas Chemical): 300 parts by weight Ethylene (SP value: 8.1) / methacrylic acid copolymer resin (SP value: 9.4) ) (Nucrel N1050H, manufactured by DuPont Mitsui): 150 parts by weight ・ Lecithin made by soybean (manufactured by Junsei Chemical): 6.77 parts by weight ・ Basic calcium petronate (manufactured by Witco): 6.77 parts by weight (total: 463. [Examples 19 to 21] The same procedure as in Example 18 was carried out except that the addition amount of the ethylene / methacrylic acid copolymer resin was changed as shown in Table 3, and the wet developers 19 to 2 by the slow cooling method were used.
1 was produced.

Examples 22 to 31 Production of wet developers 22 to 31 by slow cooling method: First, 450 g of a mixture having the following composition to which no charge control agent was added was added to Isopar L (SP value: 7.3, manufactured by Exxon Corporation). ) 300
g, and then added in the same manner as in Example 18.
A clay-like conc toner (thick toner) was obtained.

[0145] Of the 750 g of the obtained toner, 15
0 g was added to 250 g of Isopar L and dispersed at room temperature using a paint shaker. 400 g of the obtained dispersion was diluted with 3100 g of Isopar L and adjusted to have a solid content (toner concentration) of 2.6% by weight to obtain 3500 g of a master toner. Various charge control agents shown in Table 4 were added to 3500 g of the obtained master toner at the ratios shown in Table 4, and these were gently stirred to obtain wet developers 22 to 31.

<Composition for Wet Developers 22 to 31> Trimellitic anhydride (manufactured by Mitsubishi Gas Chemical): 300 parts by weight Ethylene (SP value: 8.1) / methacrylic acid copolymer resin (SP value: 9) .4) (Nucrel N1050H, manufactured by Mitsui Dupont): 150 parts by weight (total: 450.00 parts by weight) [Evaluation] For the wet developer obtained in each example, the charge amount and negative chargeability of the copolymer resin particles were evaluated. Are shown in Tables 1 to 4.

(1) Evaluation method of charge amount The charge amount of the copolymer resin particles was measured by the following method.
A wet developer is filled between a brass electrode plate having an interval of 1.0 cm, a length of 5.0 cm, and a width of 4.5 cm, and a high voltage generator (type 237 manufactured by KEITHLEY) is used to fill the space between the two electrodes.
A voltage of 00 V was applied, and a current value was measured over time until 60 seconds had elapsed from the start of energization. Based on the measured value, first, the current value (I ₆₀ ) after the lapse of 60 seconds from the initial current amount (I ₀ ) at the start of energization is integrated, and 6 hours after the start of energization.
The initial total charge amount Q ₀ spent until 0 seconds had elapsed was calculated. Next, based on the current value 60 seconds after the start of energization,
The amount of charge Q ₆₀ spent in 60 seconds in the steady state was calculated. Then, to calculate the total charge Q _t of the copolymer resin particles by calculating the difference between the two charge amount. The equation for the above calculation is expressed as follows.

[0148]

[Equation 3] Q _t = Q ₀ −Q ₆₀ = Q ₀ −I ₆₀ × 60 seconds

Thereafter, the electrode plate on which the wet type developer was adhered was taken out of the current value measuring cell, dried, and the toner adhesion amount (M) on the electrode plate was measured. On the basis of the adhesion amount (M) and the total amount of charge Q _t, toner specific charge i.e. toner 1g
Per charge Q _t / M (μC / g) was calculated.

(2) Evaluation method of negative chargeability The adhesion state of the toner to the electrode plate used when measuring the charge amount was observed. The evaluation criteria are as follows.

<Evaluation Criteria for Charging Polarity> A (excellent): The toner adhered only to the positive electrode plate. In addition, the fixability was good, and the toner did not run off when the positive electrode plate was taken out of the cell.

（(Good): The toner adhered to the positive electrode plate with good fixability, and only a small amount of toner adhered to the negative electrode plate.

Δ (Slightly poor): No fixability of toner to positive electrode plate. Alternatively, a relatively large amount of toner adhered to the negative electrode plate.

X (poor): More adhered to the negative electrode plate than to the positive electrode plate.

(3) Printed matter evaluation method Using each of the wet developers obtained in the examples, a printed matter having ON / OFF binary values shown in FIG. 4 was formed by an electrophotographic method which is an on-demand type electrostatic printing method. Produced. The device for obtaining the printed matter may be a device generally used as an electrophotographic device.

FIG. 8 is a schematic diagram showing an example of a printing apparatus using an electrophotographic method. The printing apparatus 101A used was a photoconductor drum 111 made of a photosensitive dielectric material.
02, a cleaning device for cleaning the surface of the photosensitive drum 111 to make it electrically neutral, for example, a blade 112 and a charging device, for example, a mass exposure device 113.
A latent image forming unit on the photosensitive drum 111 is provided with a charging device for forming an electrostatic latent image to be printed, such as a scorotron 114, and an exposing device, for example, a laser beam irradiation device 115, as the cleaning unit 103. The developing roller 116 for supplying the wet developer 119 obtained in the above-described embodiment and the like and the storage tank 118 are connected to the developing unit 105.
An intermediate transfer, which is a pressing member for moving the developed image in accordance with the rotation of the photosensitive drum 111 and printing the developed image on the foam web 125. Body 122 and impression cylinder 12
4 is provided as output means 106. Then, printing was performed under the following electrical and thermal conditions.

<Electrical and Thermal Conditions> Scorotron 114 voltage: -6 kV Surface charge of uniformly charged photosensitive drum 111: -700
V, surface potential of the exposed portion of the laser beam irradiation device 115: -1
00 B, bias voltage of developing roller 116: -300V (at this time, reversal development was performed using negatively charged wet developer 119), bias voltage of reverse roller 117: -200V
(At this time, the excess solvent was removed.) Bias voltage of the intermediate transfer member 122: +400 V (temperature: 120 ° C., at this time, the foaming inhibitor pattern was transferred by contact, and then the impression cylinder 124 was used. Raw foam 1
25 was brought into contact with the intermediate transfer member 122 to form a foaming inhibitor pattern on the foamed raw material 125. <Evaluation Criteria for Printed Material> ◎ (excellent): A high-density printed material without image deletion was obtained.

（(Good): Although some image deletion was observed, a printed matter of high density was obtained.

Δ (Slightly poor): A printed matter with remarkable image deletion or a printed matter with low print density was obtained.

X (bad): No image was formed.

[0161]

[Table 1]

[0162]

[Table 2]

[0163]

[Table 3]

[0164]

[Table 4]

The obtained printed matter was heated in an oven (22
(0 ° C., 1 minute), the portion where the wet developer containing the foaming inhibitor was printed did not foam, and the portion where no printing was performed foamed, thereby obtaining a foam having irregularities. As shown in the printed matter evaluation results of Tables 1 to 4,
Since the printed matter printed with the copolymer resin particles having a high content of the foaming inhibitor could be printed with the foaming inhibitor at a high concentration, a foam having sufficient unevenness was obtained by heating. On the other hand, the printed matter printed with the copolymer resin particles having a not so high content of the foaming inhibitor cannot print the foaming inhibitor at a high concentration. I couldn't get my body.

[0166]

As described above, according to the present invention,
A wet developer containing a foaming inhibitor and excellently dispersing toner particles having excellent chargeability is provided. When such a wet developer is used, a pattern of a foam inhibitor can be formed on a foam base by a method utilizing an electrostatic action such as electrostatic recording, electrostatic transfer, or electrostatic printing. In particular, according to the method of electrostatic recording or electrostatic transfer, a printing plate is not required, and a foamed material having a desired pattern of a foaming inhibitor can be quickly and easily formed.

Therefore, by heating this foam,
A foam having surface irregularities can be obtained quickly and at low cost. In particular, it can respond promptly to requests and orders, such as trial production at the development stage, preparation of samples for presentations, and launch of products of various types and small quantities.

Further, according to the present invention, toner particles containing a foaming inhibitor can be negatively charged.

[Brief description of the drawings]

FIG. 1 is a partial plan view showing an example of an original foam.

FIG. 2 is a diagram schematically showing a cross section taken along the line AA of the raw foam of FIG.

FIG. 3 is a plan view showing a state where an electrostatic latent image is formed on the surface of the foamed raw material.

FIG. 4 is a partial plan view showing a foamable intermediate product created by developing an electrostatic latent image on the surface of a raw foam with a wet developer containing a foam inhibitor.

FIG. 5 is a diagram schematically showing a BB cross section of the intermediate product of FIG. 4;

FIG. 6 is a partial plan view showing an example of a surface uneven foam according to the present invention.

FIG. 7 is a view schematically showing a cross section taken along the line CC of the uneven foam of FIG. 6;

FIG. 8 is a schematic diagram illustrating an example of a printing apparatus using an electrophotographic method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Raw foam 2 ... Foaming part 3 ... Support 4 ... Dielectric layer 5 ... Electrostatic latent image 6 ... Foaming intermediate product 7 ... Foaming inhibitor pattern 8 ... Surface irregularity foam 9 ... Convex part 10 ... Concave part

Claims (26)

[Claims] 1. The method according to claim 1, wherein at least
Copolymer resin particles comprising a copolymer resin composed of two or more types of monomer units including a monomer unit and a second monomer unit and including a foaming inhibitor capable of suppressing foaming of the foamable resin composition Wherein (1) the electrically insulating dispersion medium and the copolymer resin are:
(I) The difference Δ (δp between the solubility parameter value δp ^{1 of} the homopolymer composed only of the first monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
¹⁻ δd) is 1.0 or more, and (ii) the difference between the solubility parameter value δp ^{2 of} the homopolymer composed only of the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium. Δ (δp ² −δd) is 1.0
And (iii) the difference Δ (δp ¹ −δp) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
² ) has a relationship of 0.5 or more; (2) a core portion in which the copolymer resin particles are insoluble in the electric insulating dispersion medium; And (3) a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid as a charge controlling agent. Developer. 2. The wet developer according to claim 1, wherein the charge control agent contains lecithin and basic calcium petronate. 3. The content of each of the lecithin and the basic calcium petronate is 0.05 to 0.5 part by weight, based on 3.6 parts by weight of the foaming inhibitor. The wet developer according to claim 2. 4. The wet developer according to claim 1, wherein the metal constituting the neutral or basic metal petronate is any one of calcium, magnesium, barium and sodium. 5. The wet developer according to claim 4, wherein the phospholipid is lecithin. 6. The method according to claim 5, wherein the content of the lecithin or the neutral or basic metal petronate is 0.1 to 30 parts by weight based on 60 parts by weight of the foam inhibitor. 4. The wet developer according to item 1. 7. The wet method according to claim 4, wherein the content of the foaming inhibitor in the copolymer resin particles is from 50% by weight to 80% by weight. Developer. 8. The wet developer according to claim 1, wherein the foaming inhibitor is trimellitic anhydride. 9. The method according to claim 9, wherein the first monomer unit of the copolymer resin is
The wet developer according to any one of claims 1 to 8, wherein the developer has an acidic group. 10. The wet developer according to claim 1, wherein the copolymer resin particles are negatively charged. 11. A series of manufacturing processes including the following process groups:
In any stage, raw materials, materials other than raw materials or
In the intermediate product, lecithin as a charge control agent and basic
Wet, characterized by the addition of calcium petronate
A method for producing a developer. Step group: (1) at least a first monomer unit and a second monomer unit
Copolymer tree composed of two or more monomer units containing
And the solubility parameter below.
A step of preparing an electrically insulating dispersion medium having a characteristic of the electrical insulation;
Homopolymer composed only of the first monomer unit
Solubility parameter value δp¹ And the solubility of the dispersion medium
Difference Δ (δp from parameter value δd¹ −δd) is 1.0
And (ii) the second monomer unit
Of solubility parameter of homopolymer composed only of
δp^Two And the solubility parameter value δd of the dispersion medium
Δ (δp ^Two -Δd) is 1.0 or less, and (ii)
i) solubility parameter values δ of the two homopolymers
p¹ , Δp^Two Δ (δp¹ −δp^Two ) Is 0.5 or more
Have the relationship (2) Prepared copolymer resin solution and electrically insulating dispersion medium
Is capable of suppressing foaming of the foamable resin composition.
Mixing in the presence of a foam inhibitor; and (3) removing the solvent after mixing the electrically insulating dispersion medium.
Process. 12. The method according to claim 11, wherein the foaming inhibitor is trimellitic anhydride. 13. The method for producing a wet developer according to claim 11, wherein a toluene solution of the copolymer resin is prepared. 14. The method for producing a wet developer according to claim 11, wherein the first monomer unit of the copolymer resin has an acidic group. 15. The amount of each of the lecithin and the basic calcium petronate is 0.05 to 0.5 part by weight with respect to 3.6 parts by weight of the foaming inhibitor. A method for producing a wet developer according to any one of claims 11 to 14. 16. A solution of a copolymer resin and an electrically insulating dispersion medium are mixed in the presence of a foaming inhibitor, a charge control agent, lecithin and basic calcium petronate. A method for producing a wet developer according to claim 15. 17. A series of manufacturing processes including the following steps:
In any stage, raw materials, materials other than raw materials or
In the intermediate product, phospholipids, neutral or
Is basic metal petronate or metal chloride of organic acid
Method for producing wet developer, characterized by adding a compound
Law. Process group: (1) Electrical insulation having the following solubility parameter characteristics
Is heated to at least the first monomer unit and the second monomer unit.
Consists of two or more monomer units including two monomer units
While dissolving the copolymer resin to be used,
In the dispersion medium, the foaming resin may be simultaneously or separately with the copolymer resin.
A foaming inhibitor capable of suppressing foaming of the oil composition.
Dispersing to prepare a heated mixture, [Solubility parameter characteristics of electrically insulating dispersion medium] (i)
Homopolymer composed only of the first monomer unit
Solubility parameter value δp¹ And the solubility of the dispersion medium
Difference Δ (δp from parameter value δd¹ −δd) is 1.0
And (ii) the second monomer unit
Of solubility parameter of homopolymer composed only of
δp^Two And the solubility parameter value δd of the dispersion medium
Δ (δp ^Two -Δd) is 1.0 or less, and (ii)
i) solubility parameter values δ of the two homopolymers
p¹ , Δp^Two Δ (δp¹ −δp^Two ) Is 0.5 or more
Have the relationship (2) a step of gradually cooling the heated mixture. 18. The method according to claim 17, further comprising a step of adding a dispersion medium to disperse the copolymer resin particles after the slow cooling. 19. The wet development according to claim 17, wherein the metal constituting the neutral or basic metal petronate is any one of calcium, magnesium, barium and sodium. Method of manufacturing the agent. 20. The method according to claim 19, wherein the phospholipid is lecithin. 21. The method according to claim 20, wherein the content of the lecithin or the neutral or basic metal petronate is 0.1 to 30 parts by weight based on 60 parts by weight of the foam inhibitor. 3. The method for producing a wet developer according to item 1. 22. The method according to claim 17, wherein the foaming inhibitor is trimellitic anhydride.
2. The method for producing a wet developer according to claim 1. 23. The wet method according to claim 16, wherein the content of the foaming inhibitor in the copolymer resin particles is 50% by weight to 80% by weight. A method for producing a developer. 24. The method for producing a wet developer according to claim 17, wherein the first monomer unit of the copolymer resin has an acidic group. 25. The method according to claim 1, wherein the charge control agent is added in the step of preparing the heated mixture.
A method for producing a wet developer according to any one of claims 7 to 24. 26. The method for producing a wet developer according to claim 11, wherein the copolymer resin particles are negatively charged.