JPH08262789A - Fixing method and fixing solvent used for the same - Google Patents

Abstract

PURPOSE: To make it possible to securely fix a printing material contg. resin components to recording media, such as paper, cloth, fibers and non-woven fibers by bringing a fixing soln. contg. a crosslinking agent into the printing material contg. the resin components having crosslinkable functional groups. CONSTITUTION: This fixing method for fixing the printing material contg. at least coloring agent components and resin components onto the recording medium D includes a first stage of sticking the printing material contg. the resin components having the crosslinkable functional groups onto the recording medium D and a second stage for fixing the printing material to the recording medium D by bringing the fixing solvent contg. the crosslinking agent into contact with the stuck printing material. The fixing solvent contg. the crosslinking agent is brought into contact with the printing material after the sticking of the printing material onto the recording medium and the printing material is fixed onto the recording medium by utilizing the crosslinking reaction of the resin components and, therefore, the printing material is extremely securely fixed to the recording media having ruggedness on the surface and the recording media, such as paper, having a network structure entangled with fibers therein, by which the fixed images having excellent fastness to washing, fastness to friction and fastness to dry cleaning are formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fixing method, and more specifically, to a fixing method capable of firmly fixing a printing material containing a resin component to a recording medium such as paper, cloth, fiber and nonwoven fabric. The present invention relates to a fixing solvent used in.

[0002]

2. Description of the Related Art In recent years, the range of use of the electrophotographic process has become more and more widespread, and attention has been paid to not only conventional plain recording media such as plain paper but also recording methods such as fibers and fabrics. For example, in Japanese Patent Laid-Open No. 5-27474,
A technique for recording an image of polyamide resin particles on a natural fiber or synthetic fiber such as cotton, wool, hemp, silk and rayon by an electrostatic electrophotographic process has been shown. Generally, as a fixing method in the electrophotographic process, a method of fixing the toner adhering to the recording medium by using heat or pressure is generally used, and the heat and pressure are also used in JP-A-5-27474. The toner is fixed on the recording medium by a fixing method that also uses.

However, unlike the conventional plain paper, the above-mentioned cloth has a rough surface, and sufficient fixing is difficult only by applying heat or pressure from the surface. Also, considering fixing to paper, which is a general recording medium, when fixing with heat or pressure, the resin component of the toner is fixed only to the surface layer part of the pulp fiber of the paper, and inside the mesh structure of the pulp fiber. The resin component does not penetrate up to. Therefore, there is an inconvenience that the toner after fixing is peeled off. Such inconvenience is remarkable in the case of using a full-color toner containing a low molecular weight resin component for imparting translucency and forming a full-color image with a high frequency of forming a solid image.

Further, when a cloth or the like as described above is used as a recording medium, unlike plain paper used as a recording medium in a normal electrophotographic process, it is weak against heat and pressure depending on the kind of cloth or the like, and is described above. If the fixing technology by heat or pressure is applied as it is, not only problems such as discoloration and crimping of the fabric occur but also the selection fastness, rubbing fastness, and dry cleaning fastness required for the fabric on which the image is fixed are particularly high. Lacks in robustness.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new and useful fixing method which solves the above-mentioned problems in the prior art. A further object of the present invention is to provide a fixing method for firmly fixing a printing material onto a recording medium such as a cloth having an uneven surface or a paper having a mesh structure in which fibers are entangled inside. Another object of the present invention is to provide a fixing method which consumes less energy for fixing. Still another object of the present invention is to
It is an object of the present invention to provide a fixing method capable of forming a fixed image having excellent fastness to washing, fastness to rubbing, and fastness to dry cleaning.

[0006]

DISCLOSURE OF THE INVENTION The present invention which solves the above-mentioned object is a resin component containing a crosslinkable functional group in a fixing method for fixing a printing material containing at least a colorant component and a resin component on a recording medium. Including a first step of adhering a printing material containing the above onto a recording medium, and a second step of bringing the adhered printing material into contact with a fixing solvent containing a crosslinking agent to fix the printing material onto the recording medium. This is a characteristic fixing method.

The present invention is also a fixing solvent used for fixing a printing material containing a resin component having a crosslinkable functional group, wherein the crosslinking agent capable of reacting with the functional group and the resin component are not dissolved. It shows a fixing solvent containing at least a swelling organic solvent.

[0008]

As described above, according to the present invention, in fixing the printing material containing at least the colorant component and the resin component on the recording medium, after adhering the printing material on the recording medium,
A fixing solvent containing a cross-linking agent is brought into contact, and the printing material is fixed on the recording medium by utilizing the crosslinking reaction of the resin component. Even on recording media such as paper, which has a mesh structure in which fibers are entangled, the printing material is extremely firmly fixed in the irregularities and mesh structure, and has excellent wash fastness, friction fastness, and dry cleaning fastness. An image can be formed. Further, as described above, in the present invention, conventionally known fixing methods such as heat and pressure are not essential, which is energy saving, and even when these conventional fixing methods are combined, a small amount of heat and a pressure value are sufficient for recording. The medium is not overloaded and the recording medium is not damaged. Also,
According to the present invention, a conventionally known fixing method such as heat and pressure can be omitted altogether, and thus a fixing method that consumes less energy can be achieved.

Hereinafter, the present invention will be described in more detail based on the embodiments. In the fixing method of the present invention, the first step is
It is a step of forming an image of a printing material containing a resin component having a crosslinkable functional group on a recording medium. For example, an image of a printing material formed on an image bearing member such as a photoconductor, an electrostatic recording member or a magnetic latent image bearing member is transferred onto a recording medium electrostatically or by pressure to form an image of the printing material. how to,
A method of electrostatically transferring an image of a printing material formed on an image carrier to plain paper or the like, and further electrostatically transferring the image of the printing material from the plain paper or the like onto a recording medium, This is carried out by a method of directly forming a latent image on a recording medium and developing it with a printing material to form an image, or a method of directly forming an image of the printing material on the recording medium by an inkjet or the like.
Further, heat or pressure may be applied to the recording medium on which the image of the printing material is formed by the above method to enhance the adhesive force of the printing material to the recording medium. The method is not limited to the above method, and any method may be used as long as it forms an image of a printing material containing a resin component containing a crosslinkable functional group on a recording medium.

Preferably, the printing material is electrostatically deposited on the recording medium. Specifically, a printing material such as toner formed on an image bearing member such as a photoconductor is electrostatically electrostatically transferred onto a recording medium such as paper or cloth by a corona charger or an electrostatic transfer roller and is attached. By doing so, transfer can be achieved without disturbing the image. However, the present invention is not limited to this, and transfer by pressure or the like can be applied.

In the second step of the present invention, the image of the printing material formed on the recording medium in the first step is brought into contact with a fixing solvent containing a crosslinking agent to crosslink the printing material and fix it on the recording medium. It is a process to do.

The fixing solvent mentioned here is a solvent which dissolves or swells the resin component contained in the printing material, and by itself, it fixes even the surface of a recording medium having irregularities on the surface such as a nonwoven fabric. Even in a recording medium having a mesh structure such as paper or knit, the printing material penetrates into the inside of the recording medium and is fixed deep inside the recording medium. However, the wash fastness required in the field of clothing (JIS L 084
9), fastness to rubbing (JIS L 0849), fastness to dry cleaning (JIS L 0860) and the like cannot obtain 4 to 5 grades. However, the fastness can be improved by adding a component that crosslinks the resin having a crosslinkable functional group contained in the printing material to the fixing solvent as in the present invention and crosslinking during fixing.

Further, in the fixing method of the present invention, pressure or the like is not essential for fixing the printing material on the recording medium. Even when pressure and the like are used together, less energy is required than when fixing is performed by the conventional fixing method. Therefore, the printing material can be fixed without imposing a burden on the recording medium, so that the recording material can be fixed to a recording medium weak in pressure, such as silk, rayon, cupra and the like.
Although heat is not essential, it is preferably used at the time of fixing (at the time of contact between the fixing solvent and the printing material) in order to dry the fixing solvent and promote the crosslinking reaction.

In the present invention, the crosslinkable functional group contained in the resin component is appropriately selected according to the crosslinking reaction used in the present invention. The cross-linking reaction used in the present invention is preferably one that sequentially reacts. This is because the sequential reaction is a fast reaction and a low energy reaction. The sequential reaction includes a polycondensation reaction in which relatively simple molecules such as water are desorbed and the molecules are bound, or a polyaddition reaction in which functional groups are added and bound.
The bond generated thereby is, for example, a urea bond (polyaddition), a urethane bond (polyaddition), an ester bond (polycondensation), an amide bond (polycondensation) and the like.

When a urea bond is used, examples of the resin component containing a functional group include amino-modified styrene-acrylic resin and amino-modified polyester resin. As the cross-linking agent to be brought into contact with such a resin component, for example, a polyfunctional cyanate ester containing two or more cyanate groups is used. Specifically, 1,3- or 1,4-dicyanatobenzene, 1,3-, 1,4-,
1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene,
4,4-dicyanatobiphenyl, bis (4-dicyanatophenyl) methane, bis (3,5-dimethyl-4-dicyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2, 2-bis (3,5-dibromo-4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis ( Four
-Cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphate, tris (4-cyanatophenyl) phosphite, polycarbonate cyanate, styryl-
Pyridine-cyanate etc. can be illustrated. Other examples include polyfunctional isocyanate compounds containing two or more isocyanate groups. Specifically, 2,4- or 2,6-
Tolylene diisocyanate (dimer), p- or m-
Xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3-dimethyl-diphenyl-4,4-diisocyanate, 3,3-dimethyl-diphenyl-4,4-
Diisocyanate, 3,3-dimethyl-diphenylmethane-4,4-diisocyanate, metaphenylene diisocyanate, triphenylmethane-triisocyanate, polymethylenephenyl isocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isophorone diisocyanate , 4, 4
-Methylenebis (cyclohexyl isocyanate), methylcyclohexanone-2,4-diisocyanate,
Examples thereof include 1,3-bis (isocyanatomethyl) cyclohexanone.

When a urethane bond is used, examples of the resin component containing a functional group include a polyester resin and a hydroxyl group (eg, 2-hydroxypropyl methacrylate) -containing styrene-acrylic resin. And
Examples of the cross-linking agent to be brought into contact with such a resin component include the above-mentioned compounds containing a cyanate group or an isocyanate group.

When a polyester bond is used, the resin component containing a functional group includes a polyester resin, a styrene-acrylic resin containing a hydroxyl group (for example, 2-hydroxypropyl methacrylate), a styrene containing a carboxylic acid (for example, methacrylic acid). An acrylic resin etc. can be illustrated. And as a crosslinking agent to be brought into contact with such a resin component, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4- Methylresorcin,
4-ethylresorcin, 4-t-butylresorcin, 4
-Hexylresorcin, 4-chlororesorcin, 4-benzylresorcin, 4-acetylresorcin, 4-carbomethoxyresorcin, 2-methylresorcin, 5-methylresorcin, t-butylhydroquinone, 2,5-
Di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcarboaminoahydroquinone, methylureido hydroquinone, henzonorbornene-3,6-diol, bisphenol A, bisphenol S , 3,3-dichlorobisphenol S,
2,2-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 4,4-dihydroxydiphenyl, 2,2-dihydroxydiphenylmethane, 3,4-
Bis (p-hydroxyphenyl) hexane, 1,4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hydroxyphenyl) methylamine,
1,3-, 1,4-, 1,5- or 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2- or 4-hydroxybenzyl alcohol, 2
-Hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenylacetate, resorcinol-2-hydroxyethyl ether , Hydroxyhydroquinone, gallic acid, ethyl 3,4,5-trihydroxybenzoate, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylol Ethane, 1, 2, 6-
Hexanetriol, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododece Nylsuccinic acid, n-dodecylsuccinic acid,
Isododecyl succinic acid, n-octenyl succinic acid, n-
Octyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,
4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid,
1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane,
Examples include 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, and empol trimer.

When the amide bond is utilized, examples of the resin component containing a functional group include amino-modified styrene-acrylic resin and amino-modified polyester resin. And, as the crosslinking agent to be contacted with such a resin component, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid , Malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, 1,2,4-benzenetricarboxylic acid, 2, 5,7
-Naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butane tricarboxylic acid,
1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7, 8-
Examples thereof include octane tetracarboxylic acid, pyromellitic acid, and empol trimer. However, the material is not limited to these, and any material may be used as long as the crosslinking reaction is possible.

A fixing solvent (hereinafter also referred to as "base solvent") which is a base of a fixing solvent containing the crosslinking agent according to the present invention (hereinafter referred to as "crosslinking agent-containing fixing solvent").
The solvent that can be used as the solvent must be a solvent that dissolves or finely disperses the cross-linking agent and dissolves or swells the resin used in the printing material. The reason why the crosslinking agent is dissolved or finely dispersed is that the crosslinking agent uniformly contacts the resin. Further, a solvent that dissolves or swells the resin used in the printing material in order to swell the printing material in the recording medium and to accelerate the crosslinking reaction is preferable.

In the fixing solvent containing a crosslinking agent, the above-mentioned crosslinking agent is
It is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the total amount of the base solvent. Depending on the coating amount of the fixing solvent, it is difficult to obtain the effect of the crosslinking agent when the amount of the crosslinking agent is less than 0.1% by weight, while unreacted crosslinking agent remains on the recording medium when it exceeds 50% by weight. However, the image may be distorted.

The reason why the cross-linking agent is added to the base solvent and used is that if the cross-linking agent is uniformly dispersed or dissolved in the base solvent, the cross-linking reaction occurs uniformly and the fixing property is enhanced.

As the base solvent, diethyl succinate,
Dimethyl succinate, ethyl laurate, fatty acid esters such as ethyl linoleate, benzene, toluene, aromatic hydrocarbons or derivatives thereof such as xylene, cyclohexane, cycloaliphatic alicyclic hydrocarbons such as cyclohexanone or derivatives thereof, methylene chloride, trichloroethane, Halogenated hydrocarbons such as carbon tetrachloride or its derivatives, ethers such as tetrahydrofuran (THF), ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol and isopropyl alcohol, ethylene glycol, ethylene glycol dimethyl ether,
Glycols such as acetic acid diethylene glycol monoethyl ether and triethylene glycol or derivatives thereof can be used alone or in combination.

These organic solvents dissolve or swell the resin used in the printing material and dissolve or evenly disperse the crosslinking agent to penetrate the printing material into the recording medium and accelerate the crosslinking reaction. There is an action. The amount of addition is preferably 10 to 100% of the total amount of the base solvent. This is because if it is less than 10%, the effect of the above action cannot be obtained.

Further, in order to improve the fixing property when the recording medium is paper or cloth, and when an organic solvent which is incompatible with water is used, the organic solvent and water are stably mixed. In addition, a surfactant may be added to the crosslinking agent-containing fixing solvent. It is considered that the surfactant has a function of improving the fixing property by allowing the fixing solvent to enter the mesh structure of the recording medium such as paper.

As the surface active agent, any of anionic surface active agents, cationic surface active agents, amphoteric surface active agents and nonionic surface active agents can be used. .

Illustrating specifically, examples of the anionic surfactant include fatty acid salts, alkyl sulfate ester salts,
Alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfate ester salts, naphthalene sulfonic acid formalin condensates, polycarboxylic acid polymer surfactants Etc.

Examples of the cationic surfactants and amphoteric surfactants include alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides and the like.

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, oxyethylene-oxypropylene copolymer, sorbitan acid fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, etc. Is mentioned.

These surfactants may be used alone or in the form of 2
More than one species can be used in combination. A particularly preferred surfactant is an ethylene oxide addition-type nonionic compound represented by the chemical formula RO (CH ₂ CH ₂ ) _n H (wherein R represents an alkyl group or an alkylphenyl group, and n represents an integer of 1 to 10). It is a surfactant.

When the surfactant is added, the surfactant is added in the range of 0.1 to 10% by weight, preferably about 1 to 3% by weight based on the total amount of the base solvent. 0.1
If it is less than 10% by weight, the effect of the addition is insufficient. On the other hand, if it is more than 10% by weight, bubbles and the like tend to be generated and handling becomes difficult.

When paper is used as the recording medium in the present invention, it is preferable to add water to the crosslinking agent-containing fixing solvent of the present invention. That is, in the paper, pulp fibers are made up of hydrogen bonds, but the addition of water has the effect of spreading the bonds, thus fixing the toner deep inside the fibers.

In the fixing solvent, water is 1 to 9 of the total amount of the base solvent.
The content is 0% by weight, preferably 20 to 85% by weight. If the amount of water used is too large, the binding force between the paper fibers will be weakened too much or the fibers of the paper will be destroyed. Water usage is 1
When the amount is less than the weight%, the effect of spreading the fibers of the paper cannot be obtained, and there is a great possibility that the toner does not properly permeate into the paper.

Further, the fixing agent containing the crosslinking agent of the present invention includes
You may add an organic acid as needed. By incorporating an organic acid in the fixing solvent, the permeability of the fixing solvent into the resin component of the toner is improved. Such organic acids include saturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. Acid, unsaturated aliphatic carboxylic acid,
For example, acrylic acid, propiolic acid, methacrylic acid,
Crotonic acid, oleic acid, linoleic acid, erucic acid, ricinoleic acid, abietic acid, rosin acid, etc., or aromatic carboxylic acids such as benzoic acid, toluic acid, naphthoic acid, cinnamic acid, 2-fulic acid, nicotinic acid and Isonicotinic acid or the like can be used. These organic acids can be used alone or in admixture of two or more. When adding these organic acids, the addition amount is not particularly limited,
1 to 50% by weight of the total amount of the base solvent, more preferably 5 to
It is about 30% by weight.

Further, a fixing solvent which hardly dissolves a dye added to the toner, a colorant component such as a pigment, or a dye added as a charge control agent is preferable from the viewpoint of not contaminating a recording medium such as cloth.

On the other hand, the printing material according to the present invention may contain some functional components, if necessary, in addition to the resin component and the colorant component containing a functional group capable of undergoing a crosslinking reaction. For example, a charge control agent, a fluidizing agent, an offset preventing wax, etc. may be included.

[0036] The resin containing crosslinkable functional groups, as illustrated above, a sequential reactions functional groups -COOH, -OH, resins having one or more -NH ₂ or the like in a molecule There is no particular limitation so long as it is, for example, styrene-acrylic resin, styrene resin, (meth) acrylic resin, olefin resin, polyester resin, amide resin, polycarbonate resin, polyether resin, poly Examples thereof include thermoplastic resins such as sulfone-based resins, epoxy-based resins, urea-based resins, urethane-based resins, copolymers thereof, and blends thereof. The physical properties depend on the type of resin,
Generally, the molecular weight is Mn 3000-20000, Mw
/ Mn 2-60, Tg 55-70 degreeC is preferable.

Known colorants are acidic or basic dyes, metal complex dyes, acidic or basic mordant dyes,
It is a pigment of each color such as white pigments such as titanium white and zinc white, and black pigments such as aniline black and carbon black.

As the charge control agent, in the case of positive chargeability,
Examples of the quaternary ammonium salt, nigrosine dye, imidazole compound, nitrogen-containing resin, and the like, and negative chargeability include metal complex dyes and calixarene compounds.

As the fluidizing agent, various inorganic oxide particles such as silicon oxide (silica), nitric oxide (titania), aluminum oxide (alumina), fluorine-containing resin (Teflon), styrene resin, acrylic resin , Styrene-
Examples include various organic synthetic resin particles such as acrylic resin.

Further, as the anti-offset agent, carnauba wax, candelilla wax, low molecular weight polyethylene wax, low molecular weight oxidized polyethylene wax, low molecular weight polypropylene wax, low molecular weight oxidized polypropylene wax, higher fatty acid wax, higher fatty acid ester wax, etc. It is possible to exemplify that they are used alone or as a mixture of two or more kinds. The amount of the offset preventive agent used is 1 with respect to 100 parts by weight of the binder resin component in the toner.
It is preferable that the amount is -15 parts by weight, preferably 2-8 parts by weight.

When these printing materials are fixed as a toner on a recording medium by an electrophotographic technique, these toners have a volume average particle diameter of 2 to 15 μm, preferably 3-1.
About 0 μm is preferable in terms of balance between image quality and handling.

Further, the method for producing the toner is not particularly limited, but a pulverized toner produced by pulverizing and classifying a resin kneaded product, a polymerizable toner obtained by various polymerization methods such as emulsion polymerization and suspension polymerization, and polymerization. An example is a granulated toner in which the following polymer is dissolved in an organic solvent or the like, and this solution is dried in a droplet form to obtain a toner.

[0043]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to the examples shown below.

<Toner used in the experiment> (1) Toner 1 (trade name CF-80 (Minolta Co., Ltd.)
Toner) (yellow toner) 100 parts by weight of amino-modified polyester (Tg: 61.8 ° C.) 3 parts by weight of charge control agent (zinc complex) 4 parts by weight of benzidine compound (cyan toner) • amino-modified polyester (Tg: 61.8 ° C.) 100 parts by weight Charge control agent (zinc complex) 4 parts by weight Copper phthalocyanine compound 4 parts by weight (magenta toner) Amino modified polyester (Tg: 61.8 ° C.) 100 parts by weight Control agent (zinc complex) 3 parts by weight-Azo compound 4 parts by weight (black toner) -Amino-modified polyester (Tg: 61.8 ° C) 100 parts by weight-Charge control agent (zinc complex) 4 parts by weight-Benzidine compound , Mixture of copper phthalocyanine compound and azo compound 8 parts by weight (fluidizing agent) -silica and titania mixture 1 part by weight (2 Toner 2 styrene (cyan toner) 1000 parts by weight of xylene 6
00 parts by mol, butyl acrylate 200 parts by mol, methacrylic acid 16 parts by mol, and 3 parts by weight of azobisisobutyronitrile were added to all the monomers, reacted at 125 ° C. for 8 hours, and then dried at 160 ° C. in a vacuum dryer. Then, xylene and residual monomers were distilled off to obtain a resin. The resin (Mn 8000, Mw / Mn 6.3) 100 parts by weight Coloring material Cyan (copper phthalocyanine) 4 parts by weight Charge control agent E-81 (manufactured by Orient Chemical Co., Ltd.) 4 parts by weight The above materials are mixed in a twin-screw extruder. After kneading, pulverization and classification were performed to obtain 9 μmno particle size particles. Toner was obtained by mixing 0.5 part by weight of silica (R-974 manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of the particles. (Magenta Toner) A magenta toner was obtained in the same manner except that the above color material was changed to magenta (quinacridone compound). (Yellow Toner) A yellow toner was obtained in the same manner except that the above colorant was changed to yellow (azo compound). (Black Toner) A black toner was obtained in the same manner except that the above color material and the number of parts added were changed to 5 parts by weight of black (carbon black).

(3) Toner 3 Toner 3 was obtained in the same manner as in Toner 2, except that the number of moles of methacrylic acid added was changed to 8 moles.

(4) Toner 4 Toner 4 was obtained in the same manner as in Toner 2, except that the number of moles of methacrylic acid added was changed to 4 moles.

Evaluation Method of Each Fabric Selection Fastness (JIS L 0844) A test piece was treated with a test solution based on the method according to the standard, treated, washed with water and dried, and then discolored and attached to the test piece. The degree of stain of the white cloth was compared with the gray scale for fading or the gray scale for stain, respectively, to determine its fastness.

Rubbing fastness (JIS L 0849) Based on the standard method using a friction tester, the test piece and the white cotton cloth for rubbing are rubbed against each other, and the degree of coloring of the white cotton cloth for rubbing is determined by the gray scale for contamination. The robustness was judged by comparing with.

Fastness to dry cleaning (JIS L
0860) The test piece was treated with the test solution together with the stainless steel balls according to the prescribed method, and after drying, the discoloration of the test piece and the degree of contamination of the attached white cloth were respectively evaluated as the discoloration grayscale or the contamination grayscale. By comparison, the fastness was judged.

(Example 1) As a recording medium, cotton is easily adhered to a mount (plain paper). The attachment method is 3 of the mount
The fabric was fixed to the mount by sticking the cloth to the sides with double-sided tape. A commercially available full-color copying machine (CF80, manufactured by Minolta Co., Ltd.) was used to form a toner image on the cloth attached to the mount, and the toner image was temporarily attached. That is, an electrostatic latent image is formed by laser writing on a negatively charged photoreceptor in a dark place. This is first developed with yellow toner,
Electrostatic transfer is performed by applying an electrostatic charge from the back surface of the intermediate transfer member onto the recording medium on the above-mentioned mount that is chucked on the intermediate transfer member. The same operation was sequentially repeated for each of the cyan toner, the magenta toner, and the black toner, and the full-color toner image was electrostatically transferred onto the recording medium on the mount. The recording medium was heated together with the mount by a heater, and the adhesion was further strengthened by a fixing unit including a pair of rollers that are in pressure contact with each other. Heat roller temperature: 160 ° C. Heat roller pressure: 2.5 kgf / cm ² Subsequently, the fixing solvent shown in Table 1 was contacted with each fabric after the image was attached. The method of contacting the fixing solvent is to place the cloth horizontally on a flat plate with the toner image side facing up, and spray the fixing solvent evenly with a mist spray from above, or to fill the tray with fixing solvent. In the present experiment, the former method was used. The fabric after contact was then dried. Since each fabric tends to shrink when it is dried by applying high heat rapidly, the fabric in which the fixing solvent has penetrated is left on the filter paper for about 20 minutes to prevent the fabric from shrinking, and the solvent is absorbed into the filter paper. After that, put it on a warmer with a cloth on a metal plate,
By applying heat (about 100 ° C.), the fixing solvent was completely evaporated and the crosslinking reaction was accelerated to fix the toner image. The obtained results are shown in Table 2.

(Experimental Example 2) Commercial full-color copying machine (C
F80, Minolta Co., Ltd. was modified to prepare a copier in which the fixing roller unit by heat and pressure was excluded from the copier. That is, the toner image formed on the photoconductor is electrostatically adhered to the plain paper by the non-contact type corona charger discharge, and then it is modified so that it is discharged to the outside of the copying machine without any processing. . A contact type roller charger may be used in the electrostatic transfer. Using the same modified copying machine, a color toner image was adhered to the A3 size plain paper with the same toner as in Example 1. The toner image is only electrostatically attached on the plain paper. Next, the toner image adhering to the plain paper was electrostatically transferred onto a cloth (raised polyester type, about 2 mm of hair) as a recording medium by the apparatus shown in FIG. That is, the plain paper 3 on which the toner image is attached and the cloth are placed in close contact between the electrodes 1 and 2, and the power source 4 is placed between the electrodes.
The toner image was electrostatically transferred from the plain paper to the cloth D by applying a voltage of +1.5 kV. Next, the cloth D having the toner image transferred thereon is placed on a metal plate set to a temperature of about 100 ° C. with the toner image surface facing upward, and heated for about 1 minute to thermally heat the toner image. Attached. Subsequently, the cloth was immersed in the same fixing solvent as in Experimental Example 1 and exposed to an atmosphere of 80 ° C. to completely evaporate the fixing solvent and accelerate the crosslinking reaction to fix the toner image. The obtained results are shown in Table 2.

The device for electrostatically transferring the toner image on the cloth, which is the recording medium, may be a device having the structure shown in FIG. The apparatus rotates a conductive roller 6 connected to a power source 4 on a plain paper 3 with a toner image placed on an electrode 5 in the direction of the arrow in the figure to electrostatically transfer the toner image to the cloth. It is to be transcribed.

In the above method, the physical pressure applied to the toner image becomes 0, and the fixing to the cloth such as pile fabric having unevenness on the surface such as raised hair and loops gives a three-dimensional effect without impairing the unevenness. It can be done as it is. The temperature applied to the metal plate is not particularly limited, and may be any temperature at which the toner image is attached to the recording medium to the extent that the toner image is disturbed when finally fixed with the fixing solvent. 50 to 150 for a toner containing a general resin component
C, preferably 60 to 120 C, more preferably 70.
-100 degreeC can be illustrated.

(Experimental Example 3) Commercial full-color copying machine (C
F80, Minolta Co., Ltd. was modified to prepare a copying machine in which the heater portion was removed from the fixing roller unit by heat and pressure. Also, the pressure setting of the fixing roller was changed: ・ Heat roller temperature: 0 ° C. ・ Heat roller pressure: 1.0 kgf / cm 2, modified so that the toner image was transferred onto the plain paper only by pressure, not by heat. . The recording medium used in the experiment was a fabric (nylon) that is weak against heat, and the fabric was attached to a mount (plain paper) in the same manner as in Experimental Example 1, and the entire mount was passed through the modified copying machine. The obtained fabric to which the toner image is attached is dipped in the same fixing solvent as in Experimental Example 1 and exposed to an atmosphere of 80 ° C. to completely evaporate the fixing solvent and accelerate the crosslinking reaction to fix the toner image. It was The obtained results are shown in Table 2. When the fixing to the cloth by the above method is performed, the fixing to the cloth weak against heat is possible, and further, the fixing to the cloth is very strong. Further, the pressure to be applied is not particularly limited, and in short, when the toner is finally fixed with the fixing solvent, the pressure may be such that the toner image is attached to the recording medium without being disturbed. For a toner containing a general resin component, 0.2 to 3.0 Kgf / cm ² , preferably 0.4 to 2.5 Kgf / cm ² , and more preferably 0.8 to 2.0 Kgf / cm ^2. It is a degree.

Experimental Example 4 The same C as used in Experimental Example 2
A full-color toner image was electrostatically transferred to a cloth (nell) fixed to the mount paper in the same manner as in Experimental Example 1, using a modified F80 machine (a copying machine in which the fixing unit by heat and pressure was removed).
Next, the same fabric on which the toner image was transferred was directly immersed in the same fixing solvent as in Experimental Example 1 and exposed to an atmosphere of 80 ° C. to completely evaporate the fixing solvent and accelerate the crosslinking reaction to form a toner image. It was fixed. When fixing with this method, neither pressure nor heat is required to attach the toner image to the recording medium, and the subsequent contact with the fixing solvent is only a dipping treatment, so that fixing with very energy saving is possible. Become. The obtained results are shown in Table 2.

(Experimental Examples 5 to 13) The same procedure as in Experimental Example 1 except that a fixing solvent having the composition shown in Table 1 was used.
By the method, the full-color toner image was fixed on the cloth fixed to the mount. The obtained results are shown in Table 2.

(Comparative Examples 1 to 5) A full-color toner image was fixed on a cloth fixed to a mount by the same procedure and method as in Experimental Example 1 except that the fixing solvent having the composition shown in Table 1 was used. . The obtained results are shown in Table 2.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

As described above, according to the fixing method of the present invention, the printing material is crosslinked in the fixed state, so that the recording medium having the uneven surface, which has been difficult to fix in the past, or the inside of which the fiber is formed. Even on a recording medium such as paper having a entangled mesh structure, the printing material is extremely firmly fixed in the irregularities and the mesh structure.

Further, according to the fixing method of the present invention, conventionally known fixing methods such as heat and pressure are not indispensable, so that energy saving is achieved, and even when these conventional fixing methods are combined, a small amount of heat and pressure value are sufficient. Therefore, the recording medium is not overloaded and the recording medium is not damaged. Also,
According to the fixing method of the present invention, conventionally known fixing methods such as heat and pressure can be omitted altogether, so that a fixing method consuming less energy can be provided. Further, according to the fixing solvent of the present invention, the fixing method described above can be embodied.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus for transferring a toner image onto a recording medium,

FIG. 2 is a schematic view of a modified apparatus that transfers a toner image onto a recording medium.

[Explanation of symbols]

 1 electrode 2 electrode 3 plain paper 4 power supply D recording medium (cloth D) 5 electrode 6 conductive rotating roller

Claims (2)

[Claims] 1. A fixing method for fixing a printing material containing at least a colorant component and a resin component on a recording medium, wherein a printing material containing a resin component containing a crosslinkable functional group is attached onto the recording medium. A fixing method comprising: a step; and a second step of bringing the attached printing material into contact with a fixing solvent containing a crosslinking agent to fix the printing material on the recording medium. 2. A fixing solvent used for fixing a printing material containing a resin component containing a crosslinkable functional group, wherein the crosslinking agent is capable of reacting with the functional group and an organic compound capable of dissolving or swelling the resin component. A fixing solvent containing at least a solvent.