JP2000122350A - Printing system for forming pattern of foam suppressing agent and production of foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing system which is capable of adhering foam suppressing agents to a desired pattern form on the surface of a foamed raw sheet by electrostatic transfer using a wet process developer containing. the foam suppressing agents and lessens the deterioration of a dielectric substance. SOLUTION: An intermediate transfer body 22 is interposed between the dielectric substance 11 of the printing system based on an electrostatic transfer method and the body to be transferred. The wet process developer 19 prepared by dispersing copolymer resin particles containing the foam suppressing agents in an electrically insulative dispersion medium is used. This developer 19 has (1) the relations that the difference between the SP value δp1 of the homopolymer composed of the first monomer unit of a copolymer resin and the SP value δd of the dispersion medium is >=1.0, the difference between the SP value 6θp2 of the homopolymer composed of only the second monomer unit of the copolymer resin and the SP value δd of the dispersion medium is <=1.0 and the difference between δp1 and δp2 is >0.5 and (2) the copolymer resin particles consist of the core portions insoluble in the dispersion medium and the outer edge portions which dissolve or swell 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 method of applying an electrostatic transfer method such as an electrophotographic method or an electrostatic plotter to apply a foaming inhibitor to the surface of a foamed raw material (foamed preform). A printing system for coating or penetrating in a predetermined pattern,
Further, the present invention relates to a method for producing a foam having a three-dimensional pattern using such a printing system.

[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 impregnated 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 period of time. Evaluation can be performed flexibly. However, foams with irregularities on the surface have a significant change in design, including impression and texture, due to the foaming process, so even with a digital proofing press, etc., it is very similar to the surface design of the final product or prototype. 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.

Further, in order to present a foamed product to a customer, it is desirable to use a commercially available product or a sample very similar to the commercial product to sufficiently appeal its design. However, for this purpose, a printing plate needs to be prepared for applying the foaming inhibitor, so that time and cost obstacles increase. Therefore, it was difficult to give a presentation flexibly.

On the other hand, as an on-demand type printing method for forming and developing an electrostatic latent image, an electrostatic transfer method and an electrostatic recording method are known. In the electrostatic transfer method, an electrostatic latent image is formed on a dielectric, developed therein to form a visible image, and the obtained visible image is transferred to the surface of a printing medium. The visible image developed on the dielectric may be directly transferred from the dielectric to the printing medium, or may be transferred from the dielectric to the printing medium via the intermediate transfer body. Methods that allow electrostatic transfer include:
Examples include an electrophotographic method, an electrostatic plotter method, an ion printer method (JP-A-6-51591), and an electroplate printing method (JP-A-10-171171). On the other hand, in the electrostatic recording method, an electrostatic latent image is directly formed on the surface of a printing medium having a dielectric surface, and the printing medium is exposed to a developer to be visualized. Examples of methods capable of electrostatic recording include an electrostatic plotter method and an ion printer method.

In the system of the electrostatic transfer method, a dielectric for forming and carrying an electrostatic latent image for development is required, such as a constant dielectric in an electrostatic plotter or a photosensitive conductor in an electrophotographic printer. It is. Since this part is relatively expensive, it is desirable to minimize the deterioration due to the operation of the printer. However, when the developed image is transferred by directly pressing the surface of the dielectric against the surface of the print-receiving body, or when thermal transfer is performed to improve the transferability of the image or the fixability to the transfer-receiving body, In addition, the deterioration of the dielectric is accelerated and the life is shortened. In particular, most photosensitive conductors used in electrophotographic printers are made of organic materials, and thus easily deteriorate.

Therefore, for example, Japanese Patent Application Laid-Open No. Hei 4-502218.
No. of FIG. As shown in FIG. 1, when an intermediate transfer member is interposed between the photoconductive surface of the drum and a substrate which is a final printing medium, the contact pressure between the photoconductive surface and the intermediate transfer member becomes Since the photoconductive surface is weaker than when the photoconductive surface is directly pressed against the substrate and the intermediate transfer member is directly heated for thermal transfer, the photoconductive surface is not directly heated, so that deterioration can be reduced. However, in order to use the intermediate transfer member, it is necessary to appropriately transfer the image on the drum to the intermediate transfer member, and to transfer the image temporarily carried on the intermediate transfer member to the printing medium. Both sufficient thermal transfer properties that can be easily retransferred are required.

[0011]

SUMMARY OF THE INVENTION If the foaming inhibitor can be converted into a toner, the present inventors use an on-demand printer such as an electrostatic plotter or an electrophotographic printer on the surface of the foaming substrate. It was thought that it became possible to easily and quickly adhere to a desired pattern, and that foams of various designs could be flexibly produced. However, in order to convert the foaming inhibitor into a toner, the foaming inhibitor must have excellent dispersibility and chargeability.

Further, in order to use a foaming inhibitor toner in an electrostatic transfer type printer incorporating an intermediate transfer member, the toner has an excellent transferability from a dielectric to the intermediate transfer member. The fixability is not so strong, and it is necessary that it can be easily re-transferred to the foam by thermal transfer. The present invention has been achieved in view of the above situation, and a first object of the present invention is to provide a foaming inhibitor with a foaming inhibitor on the surface of a raw foam by electrostatic transfer using a wet developer containing the foaming inhibitor. It is another object of the present invention to provide a printing system which can be adhered in a pattern as described above, and in which the deterioration of the dielectric is small due to the interposition of the intermediate transfer member. A second object of the present invention is to provide a method for producing a high-design foam having a three-dimensional pattern using the system.

[0013]

According to the present invention, there is provided a printing system for forming a pattern of an antifoaming agent, comprising: (A) a latent image carrying means provided with a dielectric; and (B) a latent image carrying means provided on the surface of the dielectric. A latent image forming means for forming an electrostatic latent image, and (C) supplying the following foam suppressing wet developer to the surface of the dielectric to develop the electrostatic latent image to form a pattern of the foam suppressing agent. And (D) transferring the pattern of the foaming inhibitor from the surface of the dielectric and temporarily supporting the pattern, and then forming the foaming inhibitor pattern at least a part of the raw foam. In addition, an intermediate transfer member having a surface that can be thermally transferred to a surface of a foamable portion formed of a foamable resin composition, and the temporary transfer surface of the intermediate transfer member can be subjected to thermal transfer. Output means having a heating mechanism for heating to a temperature. And wherein the are.

(Foam-suppressing wet developer) A foamable resin comprising a copolymer resin comprising at least two types of 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 capable of suppressing foaming of the composition are dispersed, wherein (1) the electric insulating dispersion medium and the copolymer resin are as follows: i) When the difference Δ (δp ¹ −δd) 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 is 1.0 or more. (Ii) The difference Δ between the solubility parameter value δp ^{2 of} the homopolymer composed of only the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
(Δp ² −δd) is 1.0 or less, and (iii) solubility parameter values δp ¹ and δ of the two homopolymers.
The difference Δ (δp ¹ −δp ² ) of p ² has a relationship of 0.5 or more, and (2) the copolymer resin particles have a core portion insoluble in the electrically insulating dispersion medium. A foam-inhibiting wet developer, comprising: an outer edge portion surrounding the core portion, which dissolves or swells in the electrically insulating dispersion medium.

In a preferred aspect of the printing system, the dielectric of the latent image holding means has a cylindrical shape having a side surface serving as a surface for holding an electrostatic latent image, and is rotated around a central axis thereof. Developing means for supplying a wet developer to the electrostatic latent image carrying surface by electrostatic action while maintaining a non-contact positional relationship with the electrostatic latent image carrying surface of the dielectric. The intermediate transfer member of the output unit has a cylindrical shape whose side surface is a temporary supporting surface for a foaming inhibitor, and the intermediate transfer member of the dielectric member has an electrostatic latent image. The intermediate transfer body is arranged in parallel with the dielectric so that the support surface and the temporary support surface of the intermediate transfer body are in contact with each other, and rotated around its own central axis in synchronization with the dielectric. The pattern of the foaming inhibitor is transferred to the ink.

According to the printing system of the present invention, the foaming inhibitor can be adhered in a desired pattern on the surface of the raw foam by electrostatic transfer using the foaming-suppressing wet-type developer, and high designability can be obtained. A foam having a three-dimensional pattern is obtained.

Further, the printing system of the present invention is suitable for constructing an on-demand type printing system, and prints a pattern of a foaming inhibitor on a foamed raw material quickly and easily without going through a plate making process. can do. Therefore, by heating this foam, a highly-designed foam useful as a building interior material or the like can be obtained quickly and at low cost.

Further, according to the printing system of the present invention,
Since the intermediate transfer member is interposed so that the dielectric and the foamed material as the printing medium do not come into direct contact with each other, there is less damage due to the contact pressure as compared with the case where the dielectric and the foamed fabric are in direct contact. Further, even if thermal transfer is performed, the dielectric is not heated, so that it is not thermally damaged. Therefore, the life of the dielectric is long.

The copolymer resin used for dispersing the foaming inhibitor in the wet type developer has a melting point of 75 to 140 ° C.
Is preferably selected. When the pattern of the foaming inhibitor temporarily supported on the surface of the intermediate transfer member is retransferred to the foamed material, the surface of the intermediate transfer member is usually moved by 10%.
Heating is performed at about 0 to 160 ° C. for thermal transfer. At such a thermal transfer temperature, good transferability can be obtained by selecting a copolymer resin having a melting point within the above range.

In a preferred aspect of the printing system of the present invention, the latent image forming means and the latent image holding means form a negatively charged electrostatic latent image on the electrostatic latent image holding surface of the dielectric. The developer supply section of the developing means is capable of supplying a negatively charged foam-suppressing wet developer to reversely develop the electrostatic latent image of the negative charge, and the negative supply used therein. In the charged foaming suppressing wet developer, the first monomer unit is a monomer unit having an acidic group as a copolymer resin, and the second monomer unit is ethylene, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, Ethylhexyl methacrylate, lauryl methacrylate, and
While using a copolymer resin that is a monomer unit derived from at least one monomer selected from the group consisting of stearyl methacrylate, as a charge control agent phospholipid, neutral or basic metal petronate, or,
It is characterized by containing a metal salt compound of an organic acid.

The combination of the specific copolymer resin and the specific charge control agent makes it possible to almost certainly negatively charge the foam-suppressing toner particles, so that the negatively charged electrostatic latent image can be reversibly developed. . Reversal development has less "fogging" (a phenomenon in which a non-printed portion is stained with toner) as compared with normal image development, so that a printed matter with good image quality can be obtained.

When a system for reversal development of a negatively charged electrostatic latent image is to be constructed based on electrophotography, a charging mechanism capable of charging the surface of the dielectric material carrying the electrostatic latent image with negative charge. And a latent image forming means having an exposure mechanism capable of exposing the carrying surface of the electrostatic latent image in an image form, and a photosensitive conductor which temporarily exhibits conductivity only in an exposed portion. And a latent image carrying means provided with the dielectric material. It is preferable to use an organic photoreceptor for electrophotography, but many organic photoreceptors that form a negatively charged electrostatic latent image are known. Therefore, when it is desired to perform reversal development by electrophotography, negatively charged toner particles are required. According to the present invention, the foam-suppressing toner particles can be negatively charged almost certainly, so that a system for reversal development of a negatively charged electrostatic latent image can be constructed based on electrophotography.

The copolymer resin used for negatively charging the toner particles is a first monomer unit having an acidic group,
It preferably has a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and vinyl acetate. When acrylic acid, methacrylic acid or vinyl acetate is used as the first monomer unit, the thermal transferability of the foaming inhibitor from the intermediate transfer member to the raw foam is excellent. Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, and a resin composed of at least one copolymer selected from the group consisting of derivatives thereof as the copolymer resin. When used, the thermal transferability of the foaming inhibitor from the intermediate transfer member to the raw foam is particularly excellent.

The method for producing a foam having surface irregularities according to the present invention is characterized by including at least the following steps.

(A) a step of forming and carrying an electrostatic latent image on the surface of the dielectric; (B) developing the electrostatic latent image using the following foam-suppressing wet developing agent; A step of forming a pattern, (foam-suppressing wet developer) a copolymer resin composed of two or more 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 capable of suppressing foaming of the foamable resin composition are dispersed, wherein (1) the electric insulating dispersion medium and the copolymer resin Is the solubility parameter value δ of (i) the homopolymer composed of only the first monomer unit of the copolymer resin.
the difference Δ (δp ¹ −δd) between p ¹ and the solubility parameter value δd of the electrically insulating dispersion medium is 1.0 or more, and (ii)
Difference Δ (δp ² −δ) between the solubility parameter value δp ^{2 of} the homopolymer composed of only the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
d) is 1.0 or less, and (iii) the difference Δ (δ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
p ¹ −δp ² ) is equal to or greater than 0.5, and (2) the copolymer resin particles enclose the core portion insoluble in the electrically insulating dispersion medium and the core portion And an outer edge portion which dissolves or swells in the electrically insulating dispersion medium.

(C) a step of transferring the formed foam inhibitor pattern onto the surface of the intermediate transfer member and temporarily supporting the same;
(D) heating the surface of the intermediate transfer body to form a pattern of the foaming inhibitor carried thereon on at least a part of the foamed raw material and on the surface of the foamable portion formed of the foamable resin composition; A step of thermally transferring, and (E) a step of forming irregularities on the surface of the foamable portion by foaming the foamable portion after the thermal transfer.

According to this method, a highly-designed foam useful as a building interior material or the like 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.

[0028]

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

(1) Overall Configuration of Printing System The printing system for a foaming agent pattern according to the present invention employs an electrostatic transfer method. In the printing system, an electrostatic latent image is formed on the surface of a dielectric. And developing it with a wet developer containing a foaming inhibitor, transferring the resulting foaming inhibitor pattern onto the surface of the intermediate transfer body and temporarily supporting the same, and then supporting the foaming suppression The pattern of the agent is thermally transferred (re-transferred) to the surface of the raw foam. Here, the dielectric means a support member having a dielectric surface capable of forming and carrying an electrostatic latent image. The dielectric is
It is not limited to those that can always maintain dielectric properties as used in ion printers.For example, those whose dielectric properties change reversibly, such as photosensitive conductors of electrophotographic printers, and electrostatic lithography It may have an invariable conductive part like an electrostatic printing plate for printing.

FIGS. 1, 4 and 6 show a printing system according to the present invention, respectively. FIG. 1 shows one embodiment (1A) to which electrophotography is applied, FIG. 4 shows one embodiment (1B) to which an ion printer is applied, and FIG. 6 shows one embodiment (1C) to which electrostatic lithographic printing is applied. is there.

An electrophotographic method is applied to the printing system 1A shown in FIG. The latent image holding means 2 includes a cylindrical photosensitive drum 11 as a dielectric.
The photosensitive drum is formed of a photosensitive conductor, and usually has a dielectric property. However, only a portion irradiated with light such as laser light temporarily exhibits conductivity. The photosensitive drum can form and carry an electrostatic latent image on its side surface 11a, and rotates in the direction of arrow d around its own central axis 11b.

First, the side surface portion 11a of the photosensitive drum, that is, the surface on which the electrostatic latent image is held, is cleaned and made electrically neutral by the static elimination / cleaning means 3. The static elimination / cleaning means 3 includes at least a cleaning mechanism and a static elimination mechanism. As the cleaning mechanism, for example, a blade 12 as illustrated is used. The charge removal mechanism differs depending on the type of the latent image forming means and / or the type of the dielectric. When the electrophotographic method is applied, that is, when a photosensitive conductor is used, a large amount of the exposure device 13 is generally used as a charge elimination mechanism, and the entire surface 11a of the electrostatic latent image is exposed with a large amount of light, thereby obtaining an electric charge. Make it neutral.

The electrostatic latent image holding surface 11a reaches the latent image forming means 4 after passing through the charge removing / cleaning means 3, and
There, an electrostatic latent image is formed. When the electrophotographic method is applied, the latent image forming means has at least a charging mechanism and an exposure mechanism. The charging mechanism is a mechanism for uniformly charging the entire surface 11a of the electrostatic latent image, and uses, for example, a corona discharge device 14 such as a scorotron as the charging mechanism.
The exposure mechanism is a mechanism that can selectively irradiate a light beam having an appropriate wavelength and energy to the holding surface 11a of the electrostatic latent image in accordance with an image to be reproduced. A laser beam irradiation device 15 that can change the energy and the energy is used as an exposure device.

When the surface of a photosensitive conductor, which is a dielectric in electrophotography, is uniformly charged and then exposed, only a portion irradiated with light temporarily exhibits conductivity and becomes electrically neutral, As a result, an electrostatic latent image is formed. In an electrophotographic method using an organic photoreceptor, a negatively charged electrostatic latent image is usually formed. When a positive image is to be developed after the exposure, an electrostatic latent image of a positive pattern is formed by an exposure mechanism. When reversal development is to be performed after the exposure, a negative electrostatic image of a negative pattern is formed by the exposure mechanism. Generally, reversal development has a "fogging" (a phenomenon in which non-printed parts are stained with toner) compared to normal image development.
Less is. In this regard, there is an advantage of performing reversal development.

After the electrostatic latent image is formed and held on the electrostatic latent image holding surface 11a, the latent image forming section moves in accordance with the rotation of the photosensitive drum 11 and reaches the developing means 5, where the foaming suppressing wet development is performed. The developer is supplied to develop the electrostatic latent image. The developing means 5 is usually provided with a measuring mechanism for removing excess developer adhering to the developing surface and keeping the amount of adhering constant, together with the developer supply section.

Normally, while the non-contact positional relationship between the developer supply unit and the electrostatic latent image carrying surface is maintained, the electrostatic latent image is carried from the developer supply unit by electrostatic action. A foam-suppressing wet developer is supplied to the surface. In FIG.
A cylindrical developing roller 16 is used as a developer supply unit. The developing roller 16 has a lower portion of the side surface portion 16a immersed in the foam-suppressing wet developer 19 in the storage tank 18 and has a very narrow portion at the closest portion between the side surface portion 16a and the electrostatic latent image holding surface 11a. A gap is formed (usually about 100 μm), arranged so as to be parallel to the photosensitive drum 11, and rotated around its own central axis 16b. Since the foaming suppressing wet type developer is scraped up by the side portion 16a of the rotating developing roller, the thickness of the liquid film and the minute gap between the side portion 16a of the developing roller and the holding surface 11a of the electrostatic latent image are reduced. By adjusting the distance, the minute gap is filled with the foam-suppressing wet developer.

Then, the toner selectively adheres to the charged portion or the non-charged portion of the electrostatic latent image, and the pattern of the foaming inhibitor is developed. When performing normal image development, use a foam-suppressing wet developer charged to the opposite polarity to the electrostatic latent image, and draw the toner in the developer to the charged portion of the electrostatic latent image by electrophoresis. Attach. Therefore, the toner attachment portion is formed in the same pattern as the normal image of the latent image. On the other hand, when performing reversal development, a foam-suppressing wet developer charged to the same polarity as the electrostatic latent image is used, and an appropriate bias voltage is applied between the developing roller and the photosensitive drum to thereby cause the developer in the developer to have a different polarity. Toner adheres to the uncharged portions of the electrostatic latent image. In this case, the toner attachment portion is formed in the same pattern as the reverse image of the latent image.

For example, a reversing roller 17 can be used as a measuring mechanism for keeping the amount of the developer adhered after the development.

Instead of providing the developer storage tank 18, as shown in FIG. 2, on the side surface 16a of the developing roller, or on the side surface 16a of the developing roller and the side surface 1 of the photosensitive drum.
1a is filled with a foam-suppressing wet developer 19
May be forcibly supplied by a method such as injection, dropping, or spraying.

A developing roller 1 is used as a developer supply section.
Instead of providing the developing electrode 6, as shown in FIG. 3, a developing electrode 20 which maintains a non-contact positional relationship along the side surface 11a of the photosensitive drum may be provided. The developing electrode 20 is very narrow (typically 100 μm) between the developing electrode 20 and the side surface 11 a of the photosensitive drum.
Degree) are arranged to form the gap 21. By supplying and circulating the developer from the supply path 20a into the minute gap 21, the electrostatic latent image carried on the side surface 11a of the photosensitive drum can be developed. When performing development, particularly when performing reversal development, an appropriate bias voltage is applied between the development electrode 20 and the side surface 11a of the photosensitive drum.

The pattern of the foaming inhibitor formed on the side surface of the photosensitive drum 11 moves according to the rotation of the photosensitive drum and reaches the output means 6, where it is transferred to the intermediate transfer member 22 and temporarily carried thereon. Then, it is thermally transferred to the raw foam 25. If an appropriate intermediate transfer member is interposed between the dielectric material such as the photosensitive drum and the foam, the pattern of the foam inhibitor can be transferred even when the contact pressure between the dielectric material and the intermediate transfer member is relatively weak. Therefore, mechanical damage to the dielectric can be reduced. In addition, by interposing the intermediate transfer member, the pattern of the foaming inhibitor can be thermally transferred (re-transferred) to the raw foam without directly heating the dielectric, so that thermal damage to the dielectric can be reduced. Therefore, the dielectric hardly deteriorates. Since the organic photoreceptor usually used in electrophotography is easily damaged by heat, an intermediate transfer member is extremely effective.

The output means 6 is provided with at least a heating mechanism for heating the intermediate transfer member 22 and the temporary supporting surface of the intermediate transfer member to a temperature at which thermal transfer can be performed. Impression cylinder 2 to obtain appropriate contact pressure
4 is provided.

In FIG. 1, the intermediate transfer member 22 has a cylindrical shape, and its side surface 22a functions as a support surface for receiving and temporarily holding the pattern of the foaming inhibitor. The intermediate transfer body 22 has a side surface 22a and a side surface 1 of the photosensitive drum.
1a is arranged in parallel with the photosensitive drum so as to be in contact with the photosensitive drum,
The photosensitive drum rotates around its own central axis 22b in synchronization with the rotation of the photosensitive drum. The impression cylinder 24 is arranged close to or in contact with the intermediate transfer member 22 and in parallel with the intermediate transfer member 22 so as to sandwich the raw foam 25 in cooperation with the intermediate transfer member 22 at the position where the thermal transfer is performed. In the system 1A,
Although a heater is provided inside the intermediate transfer member as a heating mechanism, it is not shown.

Temporary support surface 22a for foam inhibitor
In order to receive the pattern of the foaming inhibitor from the dielectric material such as the photosensitive drum, the toner particles (copolymer resin particles) have appropriate wettability, and melt to re-transfer the glittering image to the raw foam. It is required that the toner particles have appropriate release properties and heat resistance enough to withstand the thermal transfer process. Further, in order to improve the transferability from the dielectric to the intermediate transfer member and the transferability from the intermediate transfer member to the raw foam, the intermediate transfer member is preferably made of a material having a soft rubber-like elasticity. For this reason, silicone oil and fluorine-based surfactants are contained in rubber-based materials with low surface energy such as silicone rubber and fluorine rubber, or in flexible resins such as acrylic rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, and chloroprene rubber. It is preferable to form the whole or surface of the intermediate transfer member using a material having low surface energy and flexibility by adding an additive such as

In order to secure flexibility with low surface energy, a low energy interface layer made of a material such as silicone is formed on the surface, and an adhesion improving layer made of a flexible material such as urethane rubber is formed on the base. An intermediate transfer member having a two-layer structure or an intermediate transfer member having a structure of three or more layers by adding other functional layers as necessary may be used.

The pattern of the foam suppressing agent developed on the side surface 11a of the photosensitive drum is transferred onto the side surface 22a of the intermediate transfer body by the contact rotation between the photosensitive drum and the intermediate transfer body. In order to cope with image disturbance at the time of transfer due to a potential difference between an image portion and a non-image portion on the side surface portion 11a of the photosensitive drum, the photosensitive drum may be exposed before transfer. Further, when an appropriate bias voltage is applied between the side surface portion 11a of the photosensitive drum and the side surface portion 22a of the intermediate transfer body, the transfer is facilitated. Then, the pattern of the foaming inhibitor temporarily supported on the intermediate transfer body is retransferred onto the foaming raw material 25 by thermal transfer. During thermal transfer, the temporary support surface of the intermediate transfer member is usually heated to a temperature higher than the melting point of the toner resin used, for example, about 100 to 160 ° C. The toner resin is ethylene-
In the case of an acrylic, ethylene-methacrylic or ethylene-vinyl acetate copolymer, the temporary support surface of the intermediate transfer member is usually heated to about 120 to 140 ° C.

In this way, a foam inhibitor pattern is formed on the surface of the foam. When this foam is heated under appropriate conditions, an uneven pattern is formed. On the other hand, the side surface portion 11a of the photosensitive drum returns to the position of the charge removing / cleaning means 3 after releasing the pattern of the foaming inhibitor, and shifts to the next printing cycle.

FIG. 4 shows an embodiment (1B) of a printing system to which a so-called ion printer is applied, which is provided with a cylindrical dielectric drum 26 as a dielectric of the latent image holding means 2. The dielectric drum can form and carry an electrostatic latent image on its side surface portion 26a, and rotates around its own central axis 26b in the direction of arrow d. As the dielectric drum, for example, a drum in which a dielectric sheet such as Alpet (polyethylene terephthalate vapor-deposited with aluminum) is wound around a cylindrical plate cylinder as a support can be used.

The side surface portion 26a of the dielectric drum, that is, the surface on which the electrostatic latent image is held, is first cleaned and neutralized electrically by at least the discharging / cleaning means 3 having a cleaning mechanism and a discharging mechanism. You.

After the electrostatic latent image holding surface 26a is cleaned and neutralized, the latent image forming means 4 is rotated by the rotation of the dielectric drum 26.
Transported to The latent image forming means of the system 1B includes at least an ion head 27. By supplying ions to the surface of the dielectric drum while controlling the ion flow with an ion head, an electrostatic latent image can be formed. Solid discharge type recording head 2 as an example of an ion head
8 is shown in FIG. A high frequency voltage applied between the line electrode 29 and the finger electrode 30 of the recording head 28 causes a discharge around the finger electrode to generate positive and negative ions 31, which are formed between the finger electrode 30 and the dielectric drum 26. An ion flow 32 is formed by the generated electric field, and ions are supplied imagewise to the surface of the dielectric drum to form an electrostatic latent image. At the same time, a voltage is applied to the screen electrode 33 to isolate the finger electrode 30 from the electrostatic latent image on the dielectric drum.

In the system 1B of FIG. 4, a negatively charged electrostatic latent image is formed on the electrostatic latent image holding surface 26a. Thereafter, development and indirect transfer are performed by the same developing means 5 and output means 6 as in the system 1A of FIG. 1 to form a predetermined pattern of the foaming inhibitor on the surface of the raw foam.

FIG. 6 shows an embodiment (1C) of a printing system to which so-called electrostatic lithographic printing is applied. The printing system 1C includes a cylindrical plate cylinder 34 around which an electrostatic printing plate 35 is wound as a dielectric of the latent image holding means 2. The plate cylinder 34 rotates in the direction of arrow d around its own central axis 34b. The electrostatic printing plate 35 in this example has a multilayer structure in which a conductive layer is covered with a dielectric layer that is degraded by light irradiation and can be removed.

In the printing system 1C, first, the surface 35a of the electrostatic printing plate is irradiated with laser light imagewise by the laser light irradiation device 36 of the conductive portion forming means 7,
A conductive portion having a pattern of an image to be reproduced or a reverse image thereof is formed. That is, plate making is performed. The electrostatic printing plate 35 is made only once, and can be used continuously thereafter.

The portion of the electrostatic printing plate 35 where the conductive portion is formed is carried to the cleaning means 3 having a cleaning mechanism by the rotation of the plate cylinder 34, where it is cleaned.

The portion of the electrostatic printing plate 35 where the conductive portions are formed is cleaned, and then carried to the latent image forming means 4. The latent image forming means of the system 1C includes at least a charging mechanism capable of uniformly supplying charges to the entire surface of the electrostatic printing plate.
As such a charging mechanism, for example, a corona discharge device 14 such as a scorotron can be used. When electric charges are uniformly supplied to the surface of the electrostatic printing plate, the electric charges in the conductive portions disappear by energization, and only the electric charges on the dielectric layer remain, so that an electrostatic latent image is formed.

In the system 1C of FIG. 6, a negatively charged electrostatic latent image is formed on the electrostatic latent image holding surface 35a. Thereafter, development and indirect transfer are performed by the same developing means 5 and output means 6 as in the system 1A of FIG. 1 to form a predetermined pattern of the foaming inhibitor on the surface of the raw foam. In the system 1C, by controlling the potential of the surface 35a of the electrostatic printing plate and the potentials of the plate cylinder 34 and the developing roller 16,
Electrostatic development or reversal development can be performed arbitrarily.

(2) 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 and has a property of foaming by any processing method, for example, a method such as heating or a chemical reaction, and after foaming, contains a large amount of air bubbles in the resin. 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 selected appropriately.

As the resin composition that is usually used,
A mixture of a thermoplastic resin, a foaming agent that decomposes by 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 needed for the purpose of enhancing the design properties after foaming.

As the foaming 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.

(3) Foam Controlling Wet Developer and Method for Producing the Same The wet developer according to the present invention is a copolymer resin comprising at least two types of monomer units including at least a first monomer unit and a second monomer unit. Copolymer resin particles comprising a foaming inhibitor such as trimellitic anhydride,
It is formed by dispersing in an electrically insulating dispersion medium.

The wet developer of the present invention is prepared, for example, by mixing a solution obtained by dissolving a copolymer resin 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 was produced by a solvent replacement method of removing the solvent, or was heated and dissolved in an electrically insulating dispersion medium in the presence of a foaming inhibitor to obtain a copolymer resin. It can be produced by a slow cooling method in which the mixture is gradually cooled to precipitate copolymer resin particles.

According to the present invention, copolymer resin particles containing a foaming inhibitor are precipitated from a varnish or solution of the copolymer resin, and the SP value of an electrically insulating dispersion medium for dispersing the resin particles is adjusted, whereby the copolymer resin is dispersed. A wet developer having excellent dispersibility of 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. When the difference between the SP value of the resin and the SP value of the solvent is small, the solubility is large and the solvent becomes easily soluble. On the other hand, when the difference is large, the solubility is small and the solvent becomes insoluble.

As a method of measuring the SP value of a resin, for example, (1) a method by a dissolution method, that is, a method of estimating from the SP value of a solvent in which a 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) A) 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 matches the SP value of the solvent. Therefore, the resin is dissolved in a solvent having various SP values, and the respective intrinsic viscosities are measured.
From the SP value of the solvent that gives the maximum value of the intrinsic viscosity, the SP of the resin
Method for estimating values (H. Ahmed, M, Yassen, J. Coat. Tec
hnol., 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) of each functional group or an atomic group constituting a resin molecule, and a molar volume ( V), a method of obtaining SP value = ΣG / V (DA Small, J. Appl. Chem., 3, 71 (1953), KL H
oy, J. Paint Technol., 42, 76 (1970)).

Hereinafter, in the present invention, as the SP value of the resin, a value obtained from the molecular attraction constant is used. 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)), which is obtained by considering 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], and 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 the case where the resin is dissolved in a solvent as an example. Polystyrene having an SP value of 9.1 is very soluble in tetrahydrofuran having an SP value of 9.1. Easy, SP value is 8.5-
Solvents in the 9.3 range are soluble and have SP values of 7.3.
Does not dissolve in n-hexane. 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 having a large P value and a completely insoluble resin is used. Generally, as the weight average molecular weight of the resin increases, the particle size of the formed resin particles increases.

[Copolymer Resin] A 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. .

The melt flow rate (MFR) of the copolymer resin specified by ASTM D-1238 is usually 1
~ 400 dg / min, preferably 2-150 dg / m
in. When the range of this MFR value is converted into a weight average molecular weight, 1 to 400 dg / min is equivalent to about 60,000 to 250,000 in weight average molecular weight, and 2 to 150 dg / min is about 75,000 to 20 in weight average molecular weight. Equivalent to ten thousand.

0-8 relative to the thermal transfer temperature of the printing system
Good transferability can be obtained by using a copolymer resin having a melting point as low as 0 ° C, preferably about 20 to 50 ° C. When the pattern of the foaming inhibitor temporarily supported on the surface of the intermediate transfer member is re-transferred to the raw foam, the surface of the intermediate transfer member is usually heated to about 100 to 160 ° C. for thermal transfer. At this level of thermal transfer temperature, the lower limit of the melting point of the copolymer resin is set to 75 ° C. or higher, as the melting point determined based on the endothermic peak at the time of temperature rise using a differential scanning calorimeter (DSC). And more preferably 80 ° C. or higher. On the other hand, the upper limit is preferably 140 ° C. or lower, more preferably 110 ° C. or lower. If the melting point is too low, the adhesion between the toner particles and the intermediate transfer member becomes too high, so that when the intermediate transfer member separates from the printing medium, the toner layer undergoes cohesive failure, resulting in poor transfer. On the other hand, if the melting point is too high, the copolymer resin is not easily melted, so that the toner particles do not bind to each other. As a result, a toner layer is not formed on the printing medium, resulting in poor transfer. If the transfer temperature is 160 ° C. or lower, most of the heat-sensitive foamable resin composition does not foam, so that an undesirable foaming phenomenon during thermal transfer can be avoided.

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 second monomer unit which has a high affinity for an electrically insulating dispersion medium and is therefore 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 15/95.
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 comprising 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 powder of a foaming inhibitor having an average particle diameter 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 charge control agent may be used to control the charge amount and / or the polarity of the charge of the copolymer resin particles as the toner particles.
In converting the foaming inhibitor into a toner, it is important to appropriately adjust the charge amount of the toner particles. However, it is more important to intentionally control the polarity of the charge to be either positive or negative. is there. The polarity of the toner particles must be intentionally controlled depending on whether a positive or negative polarity electrostatic latent image is to be formed in the printing system to be employed, or whether the electrostatic latent image is to be developed positively or reversely. No.

This is particularly important when reversal development is to be performed by electrophotography. As described above, the reversal development has an advantage that the fogging is smaller than that of the normal image development and an accurate print pattern can be formed. on the other hand,
As photoreceptor materials used for electrophotography, inorganic photoreceptor materials such as amorphous selenium, amorphous silicon, and zinc oxide, and organic photoreceptor materials represented by polyvinyl carbazole are known. In the present invention,
Either photoreceptor can be used, but the organic photoreceptor has many advantages compared to the inorganic photoreceptor in terms of variety of shapes, lightness, and mass productivity. In addition, as a photosensitive conductor used for an organic photosensitive member, there are many materials that form a negative electrostatic latent image by moving a charge on a photosensitive member surface by utilizing a change in electron conductivity of the photosensitive member. Are known. Therefore, in order to develop an electrophotographic printing system that is excellent in mass productivity as a system and capable of reversal development, it is necessary to enable reversal development on an electron conductive organic photoreceptor. Charged toner particles are required.

By combining a specific copolymer resin and a specific charge control agent, the polarity of charging of the toner particles including the foaming inhibitor can be controlled almost certainly.

When it is desired to positively charge the copolymer resin particles in the foam-suppressing wet developer, a first monomer unit having a basic group and 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate are used. , Lauryl methacrylate, and a second monomer unit derived from at least one monomer selected from the group consisting of stearyl methacrylate, and a foam control agent containing at least a foaming inhibitor, and a charge control agent. As metal soap. By doing so, the copolymer resin particles can usually be positively charged.

The copolymer resin used for positively charging the toner particles includes, as the first monomer unit having a basic group, dimethylaminoethyl acrylate, dimethylacrylamide acrylate, diacetone acrylamide, isopropylacrylamide, dimethylamino methacrylate. It preferably has a monomer unit derived from at least one monomer selected from the group consisting of ethyl and methacrylic acid dimethylacrylamide. As the metal soap, a metal salt of naphthenic acid or octylic acid, particularly, zirconium naphthenate or zirconium octylate can be preferably used.

When it is desired to negatively charge the copolymer resin particles in the foam-suppressing wet developer, the first resin having an acidic group may be used.
A monomer unit and a second monomer unit derived from at least one monomer selected from the group consisting of ethylene, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate. While including a foaming inhibitor using at least a copolymer resin constituted, a phospholipid as a charge control agent, neutral or basic metal petronate,
And one or more suitable metal salts of organic acids.
Select and add more than seeds. By doing so, the copolymer resin particles can usually be negatively charged.

The copolymer resin used to negatively charge the toner particles is a first monomer unit having an acidic group,
It preferably has a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and vinyl acetate. When acrylic acid, methacrylic acid or vinyl acetate is used as the first monomer unit, not only can the copolymer resin particles be negatively charged, but also the thermal transferability of the foaming inhibitor from the intermediate transfer body to the raw foam is excellent. I have. Ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer as a copolymer resin,
Ethylene-vinyl acetate copolymer, and, when using a resin consisting of at least one copolymer selected from the group consisting of derivatives thereof, particularly the thermal transferability of the foaming inhibitor from the intermediate transfer body to the foam raw material Are better.

Examples of the phospholipid include lecithin and sekhalin. Preferred is lecithin. Lecithin is represented by the following formula (1).

[0086]

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. Original petronates were extracted from petroleum, but there are also synthetic products now. In the present invention, either an extract or a synthetic product may be used.

As the metal salt compound of an organic acid, 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, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, naphthenate Iron, 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, dodecylate Metal soaps such as sodium dodecylate, 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.

Depending on conditions such as the type of the foaming inhibitor, the type of the copolymer resin, and the amount of the charge control agent used, the toner particles may not be easily negatively charged. Even in such a case, when trimellitic anhydride is used as the foaming inhibitor, the toner particles are likely to be negatively charged.

In the case where a wet developer is produced by the solvent replacement method, when a combination of basic magnesium petronate or basic calcium petronate is used with lecithin, the copolymer resin particles are likely to be negatively charged. Basic magnesium petronate and basic calcium petronate have been conventionally used as a dispersant used for lubricating oils and the like, a rust preventive, and the like.

Basic magnesium petronate (BM
Examples of P) include a basic mixture containing a large amount of magnesium sulfonate represented by the following formula and a mineral oil.

[0094]

Embedded image (C ₂₂ H ₄₅ C ₆ H ₄ SO ₃ ) ₂ Mg

Basic calcium petronate (BCP)
Examples thereof include a calcium sulfonate represented by the following formula and a basic mixture containing a large amount of mineral oil.

[0096]

_{Embedded image} (C _n H _(2n-10) SO ₃ ) ₂ Ca [wherein, n represents an integer of 20 or more. The specific composition of the basic calcium petronate includes calcium sulfonate (ASTM D-3721).
Of about 880), about 3% of calcium derived from calcium hydroxide and calcium carbonate, and about 1% of water, with the majority of the remainder being mineral oil. Can be exemplified. In this composition example,
Total alkali number of basic calcium petronate (Total
Base Number) is 21, and the alkali value (Free Alkalinity) of the calcium inorganic salt is 25.

In the solvent replacement method, the content of each of lecithin and basic magnesium petronate or basic calcium petronate is 0.05 to 0.5 parts by weight with respect to 3.6 parts by weight of the foaming inhibitor. , 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 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, the above-mentioned specific copolymer resin and the above-mentioned phospholipid, neutral or basic metal petronate,
Alternatively, when any one of the organic acid metal salt compounds is used in combination, the copolymer resin particles are likely to be negatively charged.

In the slow cooling method, when lecithin or neutral or basic metal petronate is used, the preferable content is 0.1% with respect to 60 parts by weight of the foaming inhibitor.
It is 1 to 30 parts by weight, more preferably 1 to 10 parts by weight. If the content is less than 0.1 part by weight, positive charging is likely 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. When the metal salt compound of the organic acid is used, the content is preferably 30 to 300 parts by weight with respect to 60 parts by weight of the foaming inhibitor. 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 slow cooling method described later. In particular, the step of preparing a heated mixture, that is, the step of preparing a copolymer with the copolymer resin in an electrically insulating dispersion medium. 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 produce a wet developer which has excellent dispersibility and can easily adjust the charge amount.

[Additives] If necessary, other additives such as a dispersant and a fixing agent may be added to the wet developer of the present invention. 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 the 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.

[0104]

HO-X-COOH wherein X is a divalent saturated or unsaturated aliphatic hydrocarbon having 12 or more carbon atoms, and at least 4 hydrocarbons are present between the hydroxy group and the carboxy group. There are carbon atoms. Preferred ester derivatives of hydroxycarboxylic acid include, for example, hydroxycarboxylic acid alkyl esters such as methyl 12-hydroxystearate and ethyl 12-hydroxystearate; lithium 12-hydroxycarboxylate, aluminum 12-hydroxycarboxylate and the like. And hydroxycarboxylic acid amides; hydrogenated castor oil and the like.

The polyhydroxycarboxylic acid ester is a light gray brown wax-like substance obtained by polymerizing a hydroxycarboxylic acid ester by partially saponifying it in the presence of a small amount of an amine 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 of 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 a difference in SP value between a solvent capable of dissolving or swelling the copolymer resin and an 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 even if the solvent is 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 obtained 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 equal to the SP value δ of the homopolymer composed only of the first monomer unit in the copolymer resin molecule.
p1 and the SP value δp2 of the homopolymer composed of only the second monomer unit in the copolymer resin molecule must be close to one of the two, and it is close to both δp1 and δp2. Is preferred.

For example, in the case of a styrene-isoprene copolymer resin, the 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).

Examples of solvents for dissolving the copolymer resin include cyclohexane (SP value: 8.2), cellosolve acetate (SP value: 9.4), toluene (SP value: 8.9), and 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 the 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 homopolymer composed of only the second monomer unit as a part of 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 prepare 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.

[0120]

## EQU2 ## 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 an isoprene unit forms an outer edge portion in a dissolved or swollen state, and a portion derived from a 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), perchloroethylene (9.3), trichloroethane (9.
9). An electrically insulating solvent having an SP value of 7.0 to 7.3 supplied from Exxon under the trade name of Isopar, more specifically Isopar G, Isopar H, Isopar L, Isopar C, Isopar E, Isopar M or the like may be used as the dispersion medium.

The following combinations can be exemplified as preferred combinations of the copolymer resin and the electrically insulating dispersion medium.

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 ² ) between δp ¹ and δp 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 −δ
d) = 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 −δ
d) = 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 −δp
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 −δp
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 −δp)
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 −δp
² ) = 1.1 Isobonyl 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 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 −δp)
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 −δp)
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 −δp)
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 −δp)
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.

When perchlorethylene (δd = 9.3) is used as a dispersion medium, preferred copolymer resins include:
For example, there is the following.

Ethylene (8.1) -vinyl acetate (9.
4) copolymer resin, Δ (δp ¹ −δd) = 1.2, Δ (δ
p ² −δd) = 0.1, Δ (δp ¹ −δp ² ) = 1.3 Ethylene (8.1) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1. 2, Δ (δp ² −δ
d) = 0.4, Δ (δp ¹ −δp ² ) = 1.6 Ethylene (8.1) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.2, Δ (Δp ² −δ
d) = 0.1, Δ (δp ¹ −δp ² ) = 1.1 Styrene (9.1) -isoprene (8.15) copolymer resin, Δ (δp ¹ −δd) = 1.15, Δ ( δp ² -δd)
= 0.2, Δ (δp ¹ −δp ² ) = 0.95 Lauryl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² ) =
1.1 Lauryl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp ² )
= 0.9 lauryl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 lauryl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 lauryl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp ² )
= 0.8 stearyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.1 Stearyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.9 Stearyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 Stearyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 Stearyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.8 Isobonyl methacrylate (8.2) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.1 Isobonyl methacrylate (8.2) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.9 Isobonyl methacrylate (8.2) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
1, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.5 Isobonyl methacrylate (8.2) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ -δd) = 1.
1, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 1.0 Isobonyl methacrylate (8.2) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ -δd) =
1.1, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0, Δ (δp ¹ −δp ² )
= 1.0 t-butyl methacrylate (8.3) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 0.8 t-butyl methacrylate (8.3) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
0, Δ (δp ² −δd) = 0.4, Δ (δp ¹ −δp ² )
= 1.4 t-butyl methacrylate (8.3) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
0, Δ (δp ² −δd) = 0.1, Δ (δp ¹ −δp ² )
= 0.9 t-butyl methacrylate (8.3) -propyl acrylate (9.0) copolymer resin, Δ (δp ¹ −δd) =
1.0, Δ (δp ² −δd) = 0.3, Δ (δp ¹ −δp)
² ) = 0.7 Preferable copolymer resins when trichloroethane (δd = 9.9) is used as the dispersion medium include, for example, the following.

N-Propyl methacrylate (8.8)-
Methyl acrylate (9.7) copolymer resin, Δ (δp ¹
−δd) = 1.1, Δ (δp ² −δd) = 0.2, Δ
(Δp ¹ −δp ² ) = 0.9 n-propyl methacrylate (8.8) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.1, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.5 n-butyl methacrylate (8.7) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) = 1.
2, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp ² )
= 1.0 n-butyl methacrylate (8.7) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) = 1.
2, Δ (δp ² −δd) = 0.7, Δ (δp ¹ −δp ² )
= 0.5 n-butyl methacrylate (8.7) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.2, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.6 n-hexyl methacrylate (8.6) -methyl acrylate (9.7) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.2, Δ (δp ¹ −δp)
² ) = 1.1 n-hexyl methacrylate (8.6) -ethyl acrylate (9.2) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.7, Δ (δp ¹ −δp)
² ) = 0.6 n-hexyl methacrylate (8.6) -methyl methacrylate (9.3) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.6, Δ (δp ¹ −δp)
² ) = 0.7 n-hexyl methacrylate (8.6) -ethyl methacrylate (9.1) copolymer resin, Δ (δp ¹ −δd) =
1.3, Δ (δp ² −δd) = 0.8, Δ (δp ¹ −δp
² ) = 0.5 On the other hand, also in the slow cooling method, it is necessary to use an electrically insulating dispersion medium having the above-mentioned SP value characteristics (i) to (iii).

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 that 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 Type Developer (Solvent Substitution Method)] To produce the wet type developer of the present invention by the solvent substitution 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. Charge control agents such as lecithin and basic calcium petronate 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, for example, solvents. ,
It is added to the intermediate product after granulation or after removing the solvent.

First, in the step (1), the copolymer resin is dissolved using an appropriate solvent. It is preferable that the copolymer resin is completely dissolved in the solution, but it 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 well dispersed. The solvent is preferably one that can dissolve and swell the copolymer resin at room temperature (25 ° C.), or one that 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 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 proportion of
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 the toluene weight is mixed with n-hexane, the mixture becomes cloudy, and the precipitation of the styrene-isoprene copolymer resin particles is clearly observed. it can. Further, when the above resin solution is mixed with n-hexane in the coexistence of trimellitic acid as a foaming inhibitor, it becomes 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 the resin solution and the dispersion medium are mixed in the presence of the foaming inhibitor, the resin molecular chains that have been dissolved, swelled, or dispersed at the molecular level in the solution are filled with the electrically insulating dispersion medium, which 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. 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 control agent such as lecithin and basic calcium petronate may be added at any stage during the production, but granulation is performed in the presence of both the foam inhibitor and the charge control agent. Preferably, it is added 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. Also, in order to adjust the particle size of the resin particles, ball mill, attritor, sand grinder,
Fine particles may be 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 a foaming inhibitor and a 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. Therefore, the copolymer resin particles are well dispersed in the wet developer, and do not cause gelation, macroscopic aggregation, sedimentation, and the like even when the particle concentration is increased, and are excellent in 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 a 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 practically, the upper limit is usually about 50% by weight.

[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 electrically 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 charge controlling agent such as a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid 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 solubility parameter characteristics as described above 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 starts to precipitate in the solution. 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 resin in the solution starts to precipitate and the temperature at which the precipitation of the copolymer resin 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 rate affects the particle size of the copolymer resin particles and the aggregation between the toner particles. When the slow cooling rate is increased, the particle diameter tends to be large, and when the slow cooling rate is reduced, the particle diameter tends to be small.

The mixture in which the foaming inhibitor such as trimellitic acid is mixed is prepared by adding the foaming inhibitor powder to 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 electric 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 a foaming inhibitor and a 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, and a wet developer having the same polarity and a constant charge amount can be easily obtained under the same conditions. 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.

(4) Method for Producing a Foam Having Surface Irregularities Using the above-described electrostatic transfer printing system, a foam inhibitor is applied to the surface of various sheet-like or three-dimensional foam raw materials in a predetermined manner. By foaming after coating or infiltrating in a pattern, a foam having an uneven pattern with high design properties can be produced. The printing system of the present invention is suitable for constructing an on-demand type printing system. When an on-demand type printing method is constructed based on the printing system of the present invention, the pattern of the foaming inhibitor is designed and input to the system by digital processing without going through a complicated plate making process. The pattern of the foam inhibitor can be output on the surface of the raw foam. Therefore, it is possible to form the foam easily and quickly.

The pattern of the foaming inhibitor to be output may be an artificial pattern such as an array of letters, symbols, or figures, or a pattern imitating a natural object such as wood grain, stone grain, and clouds. There may be. Before or after forming the foam inhibitor pattern on the surface of the raw foam, other processing may be performed as necessary. For example, surface heating using a melamine paint or the like is performed after heating and foaming of the foam. Alternatively, a glossy image may be attached to a raw material of a foamed product such as a foamed wallpaper or a foamed flooring material, a pattern of a foaming inhibitor may be successively provided, and the pattern may be heated and foamed.

A preferred embodiment of the method for producing a foam will be described below. 7 to 16 show a pseudo-tile foam, i.e., a foam having a tile-like appearance surface,
FIG. 3 illustrates each process for manufacturing using an electrostatic transfer technique. That is, according to this aspect, first,
On the surface of the foamed raw material, that is, the surface of the preformed body having foaming properties,
Electrostatic transfer is performed using a wet type developer containing a brilliant pigment to output a predetermined brilliant pattern. Next, the foaming inhibitor is adhered to the surface of the foamed raw material in a predetermined pattern by the electrostatic transfer printing system according to the present invention. Finally, the foam is foamed. According to this method, having a glitter image and a three-dimensional surface pattern,
It is possible to produce a foam having extremely high designability.

FIG. 7 is a partial plan view of an example (40) of a raw foam, and FIG. 8 is a schematic cross-sectional view taken along the line AA. As shown in FIG.
Numeral 0 indicates that a foamable portion 41 formed of a foamable resin composition is provided on one surface side of the support 42. The raw foam may be formed of only the foamable resin composition. The support 42 may be formed using a material conventionally used when performing chemical embossing. As the support, for example, paper, woven fabric, knitted fabric, felt, nonwoven fabric, and the like can be used.

In order to improve the transferability when transferring the pattern of the foam inhibitor or the glittering image from the intermediate transfer body to the raw foam, a suitable primer layer may be provided on the surface of the raw foam. As a primer coated on the surface of the foamed raw material for such a purpose, a material having an appropriate adhesiveness to both the foamed raw material and the wet developer may be used, and a thermoplastic resin having an appropriate melting point may be used. used. For example,
Synthetic rubber such as isoprene rubber, isobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile, acrylic resin, methacrylic resin, polyvinyl ether resin,
Vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, styrene resin, polyester resin,
Examples thereof include a polyamide resin, a polyacrylamide resin, and a polyvinyl butyral resin.

One or more of these primers are dissolved or dispersed in a suitable aqueous or non-aqueous solvent that does not destroy the surface of the foamed foam, and are coated by a known coating method such as a blade coater or a wire bar coater. Coat the foam. The coating amount (thickness) of the primer layer is
The dry weight is suitably about 0.1 to 20 g / m ² , preferably about 0.5 to 5 g / m ² . The coating amount is 0.
If it is less than 1 g / m ² , sufficient adhesiveness cannot be obtained in many cases, and if it exceeds 20 g / m ² , the original surface properties of the raw foam are impaired.

When such a foam raw material 40 is prepared and electrostatic transfer is performed on the surface of the foamable portion 41 by using a brilliant wet type developer, squares are arranged as shown in FIG. 9 and FIG. A bright pattern 44 is formed. Thus, the foamable intermediate product 43 provided with the glitter image is obtained. The printing system for electrostatically transferring glittering images is
The system for forming the pattern of the foam inhibitor may be the same or different.

The brilliant wet developer used here is composed of a copolymer resin composed of at least two types of monomer units including a first monomer unit and a second monomer unit in an electrically insulating dispersion medium. And a wet developer in which copolymer resin particles containing a brilliant pigment are dispersed,
(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 of only 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 ² ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
Is 0.5 or more, and (2)
The copolymer resin particles are composed of a core portion insoluble in the dispersion medium, and an outer edge portion surrounding the core portion that dissolves or swells in the dispersion medium.

As the brilliant pigment, a pigment having a pearly luster or interference luster, preferably a scaly foil piece is used. Known inks used for glittering inks can be used. For example, (1) a so-called pearl pigment, more specifically, a scale-like foil piece (titanium dioxide-coated mica) obtained by baking titanium oxide or iron oxide on the inner part of a shell, crushed pearl, or mica fine particles )etc;
(2) metal powder, more specifically, aluminum, brass,
Powder of bronze, gold, silver, etc., preferably in the form of fine particles or scaly foil of 1 to 120 μm; (3) fragments of a plastic film deposited, more specifically, a polyethylene terephthalate film; Silver powder, which is obtained by evaporating and crushing a metal such as aluminum, usually aluminum,
Golden powder crushed after coating with transparent yellow after deposition;
(4) Two or more resin layers having different refractive indices, for example, a polyester resin layer and an acrylic resin layer, each having a thickness of several μm or less, are laminated to form an iris color due to light interference. Examples thereof include foil powder obtained by finely cutting the resulting composite film.

The glittering wet developer can be produced by a solvent replacement method which is one of the methods for producing a foam-suppressing wet developer. That is, after mixing a good solvent solution or varnish of the copolymer resin and the electrically insulating dispersion medium in the coexistence of the glittering pigment, if necessary, removing the solvent,
A brilliant wet developer is obtained. The solvent for dissolving the copolymer resin, the varnish of the copolymer resin, the electrically insulating dispersion medium, and the like may be selected from those usable for producing a foam-suppressing wet developer. However, in a specific combination of the foam suppressing wet developer and the glittering wet developer, the electrically insulating dispersion medium and the copolymer resin used in each of the two developers may be the same or different. .

Next, as shown in FIGS. 11, 12 and 13, the surface of the foamable portion 41 of the foamable intermediate product 43 is
The printing system of the present invention performs electrostatic transfer using a foam-suppressing wet developer to adhere the foam-suppressing toner in a predetermined pattern. In FIG. 11, since the joint portion of the tile pattern is intended to be a non-foamed concave portion, the attachment portion 46 of the foam inhibitor is formed in a lattice pattern. In this way, a foamable intermediate product 45 having the glitter image 44 and the attachment portion 46 of the foam inhibitor is obtained.

After the pattern of the foaming inhibitor is formed on the surface of the raw fabric, the foamable intermediate product 45 is heated at an appropriate temperature to form unfoamed concave portions in a lattice shape. When the foamable intermediate product 45 is heated, the foaming inhibitor present on the surface of the foamable portion 41 diffuses into the foamable portion, and immediately below the foaming inhibitor pattern, the catalytic action of the foaming accelerator is activated. Inhibited, the foaming temperature rises. Therefore, by heating the foamable intermediate product 45 to a temperature that is equal to or higher than the foaming temperature in a region deviating from the foam inhibitor pattern and lower than the foaming temperature immediately below the foam inhibitor pattern, FIG.
4. As shown in FIGS. 15 and 16, a foam 47 having a convex portion 48 whose bulk is increased by foaming and an unfoamed concave portion 49 corresponding to the pattern portion of the foaming inhibitor is obtained. In this manner, a pseudo tile foam 47 having the glitter image 44 is obtained.

In the above method, the glittering image is formed first, and then the pattern of the antifoaming agent is formed. However, even if the pattern of the foaming inhibitor is formed first, then the glittering image is formed. Good. Further, in the above method, both the glitter image and the pattern of the foaming inhibitor are formed by electrostatic transfer, but the glitter image is formed by forming a dielectric layer on the surface of the foamed raw material. May be formed. Of course, a color image may be formed by developing using a color wet developer such as Y, M, C, K before and after developing with the foam suppressing wet developer.

[0168]

Hereinafter, a printing system according to the present invention will be described in more detail with reference to examples.

[Production of Wet Developer] (1) Wet Developer 1 A solvent replacement method was performed. First, a mixture 7.35 having the following composition
g was added to 80 g of toluene, and then dissolved and dispersed at room temperature using a paint shaker. The obtained dissolved / dispersed liquid was added to 360 g of Isopar L (δd = 7.3, exxon) at room temperature while irradiating ultrasonic waves,
Next, only toluene was removed using an evaporator, and an ultrasonic homogenizer (Nippon Seiki Seisakusho U
S-300T) to irradiate ultrasonic waves to obtain a master toner. The obtained master toner was diluted with Isopar L to adjust the toner concentration to 4% by weight, and a negatively charged wet developer 1 was obtained. 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 (ETH) / methacrylic acid copolymer resin (M
A) (first monomer unit: MA (δp ¹ = 9.4), second monomer unit: ETH (δp ² = 8.1), melting point: 8
8 ° C, trade name Nucrel N0200H, manufactured by Mitsui Dupont): 3.
6 parts by weight ・ Soybean lecithin (manufactured by Junsei Chemical): 0.1 part by weight ・ Basic calcium petronate (manufactured by Witco):
0.05 parts by weight (total: 7.35 parts by weight) [Wet developer 2 to 4] In the case of wet developer 1 except that the ethylene / methacrylic acid copolymer resin is changed to another copolymer resin of the same amount. In the same manner as in the above, wet developers 2 to 4 were obtained.
Table 1 shows the copolymer resins used for each wet developer.

[Wet developer 5] A slow cooling method was performed. First,
463.54 g of a mixture having the following composition was mixed with Isopar L (δd
= 7.3, manufactured by Exxon Co.) 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 another 2 hours. Then, at a rate of 10 ° C./0.5 hour,
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 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 5. 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. The total amount of lecithin and basic calcium petronate in the toner is the sum of those previously contained in the composition for the wet developer 5 and those added later. Each amount is 3.85 parts by weight based on 60 parts by weight of melic acid.

<Composition for wet developer 5> Trimellitic anhydride (manufactured by Mitsubishi Gas Chemical): 300 parts by weight Ethylene (ETH) / methacrylic acid copolymer resin (M
A) (first monomer unit: MA (δp ¹ = 9.4), second monomer unit: ETH (δp ² = 8.1), melting point 95
° C, trade name Nuclel N1050H, manufactured by Mitsui Dupont): 150
Parts by weight ・ Soybean lecithin (manufactured by Junsei Chemical): 6.77 parts by weight ・ Basic calcium petronate (manufactured by Witco): 6.
77 parts by weight (total: 463.54 parts by weight) [Wet developer 6] Ethylene / methacrylic acid copolymer resin is mixed with the same amount of another ethylene (ETH) / methacrylic acid copolymer resin (MA) (first monomer unit). : MA (δp ¹ =
9.4), second monomer unit: ETH (δp ² = 8.
1), melting point: 72 ° C., trade name: Nucrel AN4311, manufactured by Du Pont-Mitsui Co., Ltd.), except that wet developer 6 was obtained.

[Comparative Developer 1] Ethylene / methacrylic acid copolymer resin was mixed with the same amount of polystyrene resin (melting point 190
Comparative Developer 1 was obtained in the same manner as in Example 1 except that the temperature was changed to (C.C., manufactured by Junsei Chemical Co., Ltd.).

[Preparation of foamed raw material for wallpaper] A primer having the following composition was dried on the surface of the foamed raw material, and then coated with a miller bar so as to have an application amount of 1 g / m ^2, and dried. Was prepared.

<Primer composition> Polyamide (trade name) DPX238 (manufactured by Henkel):
10 parts by weight Solvent n-propyl alcohol: 90 parts by weight [Examples 1 to 11, Comparative Example 1] Using each of the prepared wet developers, by any one of the following image forming methods 1, 2 and 3, A foam inhibitor pattern was formed on the surface of the foam foam for wallpaper. Then, the raw foam is placed in an oven for 22 minutes.
Heating was performed at 0 ° C. for 1 minute to selectively foam a portion to which the foaming inhibitor was not attached, to obtain a wallpaper having an uneven pattern on the surface. The combination of the wet developer and the image forming method in each of Examples 1 to 11 and Comparative Example 1 was the second.
It is as shown in the table.

<Image Forming Method 1> Using the electrophotographic printing system 1A shown in FIG. 1 together with a negatively charged wet developer, reverse development is performed to form a foam inhibitor pattern, and the reverse roller is used to form a pattern on the photosensitive drum. The excess solvent was removed, and the photosensitive drum was brought into contact with the intermediate transfer member to transfer the foaming inhibitor pattern to the intermediate transfer member. Thereafter, the raw foam was brought into contact with the intermediate transfer member using an impression cylinder, and the pattern of the foam inhibitor was thermally transferred onto the raw foam. In this way, the foaming inhibitor was attached to the surface of the raw foam in a pattern of ON / OFF binary values shown in FIG. The electrical and thermal conditions of the system 1A were set as follows.

Scorotron voltage: -6 kv Surface potential of uniformly charged photosensitive drum: -700 V Surface potential of exposed portion by laser exposure: -100 V Bias potential of developing roller: -300 V Bias potential of reverse roller:- 200V ・ Bias potential and temperature of intermediate transfer member: + 400V, 1
20 ° C. <Image forming method 2> Inverse development is performed using the printing system 1B of the ion printer shown in FIG. 4 together with the negatively charged wet developer to form a foaming inhibitor pattern, and the reverse roller is used to form a pattern on the dielectric drum. The excess solvent was removed, and the dielectric drum was brought into contact with the intermediate transfer member to transfer the foam inhibitor pattern to the intermediate transfer member. Thereafter, the raw foam was brought into contact with the intermediate transfer member using an impression cylinder, and the pattern of the foam inhibitor was thermally transferred onto the raw foam. In this way, the foaming inhibitor was attached to the surface of the raw foam in a pattern of ON / OFF binary values shown in FIG. The electrical and thermal conditions of the system 1B were set as follows.

Surface potential of the removed dielectric: 0 V Bias potential of the back surface of the dielectric: 0 V Surface potential of the dielectric written by the ion head:-
300V ・ Bias potential of developing roller: -200V ・ Bias potential of reverse roller: -50V ・ Bias potential and temperature of intermediate transfer member: + 500V, 1
40 ° C. <Image forming method 3> Using an electrolithographic printing system 1C shown in FIG. 6 together with a negatively charged wet developer, form a pattern of conductive portions on an electrostatic printing plate by laser exposure, and perform reverse development. To form a foam inhibitor pattern,
Excess solvent on the dielectric drum was removed with a reverse roller, and the dielectric drum was brought into contact with the intermediate transfer member to transfer the foam inhibitor pattern to the intermediate transfer member. Thereafter, the raw foam was brought into contact with the intermediate transfer member using an impression cylinder, and the pattern of the foam inhibitor was thermally transferred onto the raw foam. In this way,
A foaming inhibitor was attached to the surface of the foamed material in a pattern of ON / OFF binary values shown in FIG. The electrical and thermal conditions of the system 1C were set as follows.

Scorotron voltage: -8 kv Surface potential of dielectric part: -300 V Bias potential of conductive part (bias potential of plate cylinder):
0V ・ Bias potential of developing roller: -100V ・ Bias potential of reverse roller: -50V ・ Bias potential and temperature of intermediate transfer member: + 700V, 1
10 ° C. [Evaluation method] (1) Evaluation of electrical characteristics A wet-type 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 (KEITHLEY) 237) between the two electrodes.
A voltage of 00 V was applied, and an initial current value (I ₀ ) at the start of energization was measured. Further, the weight (M1) of the negatively charged toner particles attached to the positive electrode plate and the weight (M2) of the positively charged toner particles attached to the negative electrode plate at the time of measuring the initial current value were measured.
The negative charging rate was determined by the following equation. Table 1 shows the electrical characteristics of each wet developer.

[0182]

(Negative charging rate) = M1 / (M1 + M2) × 100 (%)

(2) Evaluation of Image Based on the following criteria, the state of the pattern of the foaming inhibitor output to the raw foam and the state of the surface irregularities after heating the foam were evaluated. Table 2 shows the evaluation results.

◎ (excellent): No transfer residue of the toner particles on the dielectric was observed, and a pattern of a foam inhibitor having a high concentration was formed on the raw foam. When the raw foam was heated, the surface irregularities were sufficient.

（(Good): There was some transfer residue of the toner particles on the dielectric, but a dense foam inhibitor pattern was formed on the original foam. After heating the raw foam,
Surface irregularities were also sufficient.

Δ (Slightly poor): A large amount of the toner particles remained on the dielectric material, and the foam inhibitor pattern formed on the original foam had a somewhat low density. When the foam was heated, the surface irregularities were somewhat insufficient.

X: (Poor): The transfer residue of the toner particles on the dielectric was large, and the pattern of the foaming inhibitor formed on the foamed foam was low in density. When the foam was heated, the surface irregularities were insufficient.

[0188]

[Table 1] * 1 ETH: ethylene * 2 MA: methacrylic acid * 3 VA: vinyl acetate

[Table 2]

[0189]

According to the printing system of the present invention, the foaming inhibitor can be attached in a desired pattern to the surface of the raw foam by electrostatic transfer using the foaming suppressing wet developer. A foam having a three-dimensional design can be obtained.

Further, the printing system of the present invention is suitable for constructing an on-demand type printing system, and prints a pattern of a foaming inhibitor on a foamed raw material quickly and easily without going through a plate making process. can do. Therefore, by heating this foam, a highly-designed foam useful as a building interior material or the like 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 printing system of the present invention,
Since the intermediate transfer member is interposed so that the dielectric and the foamed material as the printing medium do not come into direct contact with each other, there is less damage due to the contact pressure as compared with the case where the dielectric and the foamed fabric are in direct contact. Further, even if thermal transfer is performed, the dielectric is not heated, so that it is not thermally damaged. Therefore, the life of the dielectric is long.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a printing system according to the present invention.

FIG. 2 is a schematic diagram illustrating an example of a developer supply unit.

FIG. 3 is a schematic diagram illustrating another example of a developer supply unit.

FIG. 4 is a schematic view showing another example of the printing system according to the present invention.

FIG. 5 is a schematic diagram showing an operation state of a recording head of the ion printer.

FIG. 6 is a schematic diagram showing another example of the printing system according to the present invention.

FIG. 7 is a partial plan view showing an example of an original foam.

8 is a diagram schematically showing a cross section AA of the raw foam of FIG. 7;

FIG. 9 is a partial plan view showing an intermediate product in which a glitter image is printed on the surface of a raw foam by electrophotography.

FIG. 10 is a view schematically showing a BB cross section of the intermediate product of FIG. 9;

FIG. 11 is a partial plan view showing an intermediate product provided with a brilliant image and a portion to which a foam inhibitor is attached.

12 is a view schematically showing a cross section taken along the line CC of the intermediate product of FIG. 11;

13 is a diagram schematically showing a DD section of the intermediate product of FIG. 11;

FIG. 14 is a partial plan view showing an example of a foam body provided with a glitter image and a three-dimensional pattern.

FIG. 15 is a diagram schematically showing an EE cross section of the foam of FIG.

FIG. 16 is a diagram schematically showing a cross section FF of the foam of FIG. 14;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 (1A, 1B, 1C) ... Printing system 2 ... Latent image holding means 3 ... Static elimination / cleaning means 4 ... Latent image forming means 5 ... Developing means 6 ... Output means 7 ... Conductive part forming means 11 ... Photosensitive drum (dielectric 11a: Side surface portion of photosensitive drum (bearing surface of electrostatic latent image) 12: Blade 13: Mass exposure device 14: Corona discharge device (charging mechanism) 15: Laser light irradiation device (exposure mechanism) 16: Developing roller ( (Developer supply portion) 16a: side surface portion of development roller 16b: central axis of development roller 17: reversing roller 18: storage tank 19: foam-suppressing wet developer 20: development electrode 20a: supply path 21: minute gap 22: middle Transfer member 22a: Side surface of intermediate transfer member (temporary holding surface of electrostatic latent image) 24: Impression cylinder 25: Printed object 26: Dielectric drum 26a: Side surface of dielectric drum 26b Central axis of dielectric drum 27 ... Ion head 28 ... Solid discharge type recording head 29 ... Line electrode 30 ... Finger electrode 31 ... Positive and negative ions 32 ... Ion flow 33 ... Screen electrode 34 ... Plate cylinder 34b ... Plate cylinder central axis 35 ... Electrostatic printing plate 35a ... Electrostatic printing plate surface 36 ... Laser beam irradiation device 40 ... Foam foam 41 ... Foamable part 42 ... Support 43 ... Intermediate product 44 ... Glitter image 45 ... Intermediate product 46 ... Foam suppression Attachment part of agent 47 ... Foam 48 ... Convex part 49 ... Recess

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H069 BA01 CA03 CA07 CA30 DA02 DA07 2H074 AA03 AA06 AA09 AA11 AA41 AA46 BB02 BB42 EE09 4D011 CB03 CB11

Claims (14)

[Claims] (A) a latent image holding means provided with a dielectric; (B) a latent image forming means for forming an electrostatic latent image on a surface of the dielectric; and (C) a latent image forming means for forming a latent image on the surface of the dielectric. Developing means for supplying the following foam-suppressing wet developer to develop the electrostatic latent image and forming a pattern of the foam-suppressing agent; and (foaming-suppressing wet developer) at least in the electrically insulating dispersion medium. A copolymer comprising a copolymer resin composed of two or more types of monomer units including a first monomer unit and a second monomer unit and including a foaming inhibitor capable of suppressing foaming of the foamable resin composition. A wet developer in which resin particles are dispersed, wherein (1) the electric insulating dispersion medium and the copolymer resin are: (i) a solubility parameter of a homopolymer composed of only the first monomer unit of the copolymer resin; Value δ
the difference Δ (δp ¹ −δd) between p ¹ and the solubility parameter value δd of the electrically insulating dispersion medium is 1.0 or more, and (ii)
Difference Δ (δp ² −δ) between the solubility parameter value δp ^{2 of} the homopolymer composed of only the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
d) is 1.0 or less, and (iii) the difference Δ (δ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
p ¹ −δp ² ) is equal to or greater than 0.5, and (2) the copolymer resin particles enclose the core portion insoluble in the electrically insulating dispersion medium and the core portion And an outer edge portion which dissolves or swells in the electrically insulating dispersion medium. (D) transferring the pattern of the foaming inhibitor from the surface of the dielectric and temporarily supporting it, and then forming the foaming inhibitor pattern at least a part of the raw foam, and forming the foamable resin composition. An intermediate transfer member having a surface that can be thermally transferred to the surface of a foamable portion formed of a material, and heating the temporary transfer surface of the intermediate transfer member to a temperature at which thermal transfer can be performed. A printing system for forming a foam inhibitor pattern, comprising: an output unit having a mechanism. 2. The dielectric of the latent image holding means has a cylindrical shape having a side surface serving as a surface for holding an electrostatic latent image, and rotates around a central axis thereof. A developer supply unit that supplies a wet developer to the electrostatic latent image holding surface by electrostatic action while maintaining a non-contact positional relationship with the electrostatic latent image holding surface of the dielectric; The intermediate transfer member of the means has a cylindrical shape whose side surface is a temporary holding surface for a foam inhibitor, and the holding surface of the electrostatic latent image of the dielectric and the intermediate transfer member are The pattern of the foaming inhibitor is transferred to the intermediate transfer body by being arranged in parallel with the dielectric so that the temporary support surface has contact therewith and rotating around its own central axis in synchronization with the dielectric. The printing system according to claim 1, wherein the printing is performed. 3. The copolymer resin has a melting point of 75 to 140 ° C.
The printing system according to claim 1, wherein: 4. The developing device according to claim 1, wherein the latent image forming unit and the latent image holding unit are a combination capable of forming a negatively charged electrostatic latent image on an electrostatic latent image holding surface of the dielectric. The agent supply unit is capable of supplying a negatively-charged antifoaming wet developer to reversely develop the electrostatic latent image of the negative charge, and the negatively-charged antifoaming wet developer used therein, As the copolymer resin, the first monomer unit is a monomer unit having an acidic group, and the second monomer unit is ethylene, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate. A copolymer resin which is a monomer unit derived from at least one monomer selected from the group consisting of The method according to any one of claims 1 to 3, wherein the charge control agent is a phospholipid, a neutral or basic metal petronate, or a metal salt compound of an organic acid. Printing system as described. 5. A latent image forming means, comprising: a charging mechanism capable of charging a surface of the dielectric material carrying an electrostatic latent image to a negative charge; An exposure mechanism capable of performing exposure, wherein the dielectric of the latent image holding means is formed of a photosensitive conductor that temporarily exhibits conductivity only in an exposed portion. 5. The printing system according to 4. 6. The monomer unit having an acidic group is a monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and vinyl acetate. A printing system according to claim 4 or claim 5. 7. The copolymer resin is at least one selected from the group consisting of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, and derivatives thereof. The printing system according to claim 6, comprising a copolymer of 8. A method for producing a foam having surface irregularities, comprising at least the following steps. (A) a step of forming and carrying an electrostatic latent image on the surface of a dielectric, and (B) developing the electrostatic latent image using a foam-suppressing wet developer described below to form a foam-suppressing agent pattern (Foaming suppressing wet developer) a foaming resin comprising a copolymer resin composed of at least two types of 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 capable of suppressing foaming of the composition are dispersed, wherein (1) the electric insulating dispersion medium and the copolymer resin are as follows: i) Solubility parameter value δ of homopolymer composed only of first monomer unit of copolymer resin
the difference Δ (δp ¹ −δd) between p ¹ and the solubility parameter value δd of the electrically insulating dispersion medium is 1.0 or more, and (ii)
Difference Δ (δp ² −δ) between the solubility parameter value δp ^{2 of} the homopolymer composed of only the second monomer unit of the copolymer resin and the solubility parameter value δd of the electrically insulating dispersion medium.
d) is 1.0 or less, and (iii) the difference Δ (δ) between the solubility parameter values δp ¹ and δp ² of the ^two homopolymers.
p ¹ −δp ² ) is equal to or greater than 0.5, and (2) the copolymer resin particles enclose the core portion insoluble in the electrically insulating dispersion medium and the core portion And an outer edge portion which dissolves or swells in the electrically insulating dispersion medium. (C) a step of transferring the formed pattern of the foaming inhibitor to the surface of the intermediate transfer body and temporarily supporting the same; (D) heating the surface of the intermediate transfer body to form the foaming inhibitor carried thereon. A step of thermally transferring the pattern to at least a part of the raw foam and thermally transferring the foamable portion to the surface of the foamable portion formed of the foamable resin composition; and Forming irregularities on the surface of the site. 9. The foam-suppressing wet-type developer is electrostatically applied to the surface of the dielectric carrying an electrostatic latent image from a developer supply unit while maintaining a non-contact positional relationship therebetween. The method for producing a foam according to claim 8, wherein the foam is supplied to develop the electrostatic latent image. 10. The melting point of the copolymer resin is from 75 to 140.
The method for producing a foam according to claim 8 or 9, wherein the temperature is ℃. 11. A negatively charged electrostatic latent image is formed and carried on the surface of the dielectric, and the negatively foamed foam-suppressing wet developer is supplied to the surface carrying the electrostatic latent image to reverse the image. The negatively charged foam-suppressing wet developer used for the development and used therein is a copolymer resin in which the first monomer unit is a monomer unit having an acidic group, and the second monomer unit is ethylene, 2-ethylhexyl. Acrylate, lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and a copolymer resin that is a monomer unit derived from at least one monomer selected from the group consisting of stearyl methacrylate, and charge control. Phospholipids, neutral or basic metal petronates, or organic acid gold The method for producing a foam according to claim 8, further comprising a genus salt compound. 12. The method according to claim 1, wherein a photosensitive conductive material that temporarily exhibits conductivity only in an exposed portion is used as the dielectric material, and the surface thereof is imagewise exposed to form an electrostatic latent image.
A method for producing a foam according to claim 11. 13. The monomer unit having an acidic group,
Acrylic acid, methacrylic acid, and a monomer unit derived from at least one monomer selected from the group consisting of vinyl acetate, characterized by the fact that the highly decorative article according to claim 11 or 12, Production method. 14. The copolymer resin is at least one selected from the group consisting of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, and derivatives thereof. The method for producing a foam according to claim 13, comprising a copolymer of