JP2020140049A - Recorded matter formation method, recorded matter and toner - Google Patents

Abstract

To provide a recorded matter formation method which is excellent in coating property and adhesion of varnish while satisfactorily maintaining separability.SOLUTION: A varnish contains a polymerizable monomer for varnish, the polymerizable monomer for varnish is a monomer having a polymerizable functional group, a toner has toner particles containing a binder resin and a release agent, the release agent contains a polymerizable wax copolymerizable with the polymerizable monomer for varnish, the polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group, a content of the polymerizable wax in the toner particles is 1 mass% or more and 30 mass% or less with respect to the total mass of the toner particles, and a weight average molecular weight of the polymerizable wax is 300 or more and 10,000 or less.SELECTED DRAWING: None

Description

The present invention relates to a recording material forming method, a recording material and a toner.

In recent years, with the development of image forming apparatus using an electrophotographic process, an image forming apparatus corresponding to the production printing market has been put on the market. In the production printing market, there is a demand for an image forming apparatus capable of high-quality images and various usages. One example of its use is to apply varnish to at least a portion of an image for the purpose of improving the quality and durability of the image.

However, in an image formed by toner using an electrophotographic process, that is, a so-called toner image, the toner image may repel varnish and an appropriate coating film (varnish layer) may not be obtained. Further, although the varnish does not repel, the adhesion between the toner image and the varnish layer is insufficient, and the varnish layer may be easily peeled off.

In an image forming apparatus using an electrophotographic process, a toner having toner particles containing wax is often used in order to improve the separability between the toner image and the fixing member at the time of fixing.

However, the above-mentioned problems with the varnish layer are often mainly due to the wax deposited on the surface of the toner image during fixing.

Patent Document 1 describes a technique for improving the affinity between varnish and wax by using polar wax, and improving the coatability of varnish and the adhesion between the toner image and the varnish layer. Patent Document 2 describes a technique for improving the affinity between varnish and wax by using a crystalline compound having an acryloyl group.

Japanese Unexamined Patent Publication No. 2012-78565 Japanese Unexamined Patent Publication No. 2014-215542

However, as a result of studies by the present inventors, it was found that there is still room for improvement in the varnish coating property and the adhesion between the toner image and the varnish layer even when the technique described in Patent Document 1 is used. .. Further, it was found that when the technique described in Patent Document 2 was used, the compatibility between the release agent and the binder resin was increased, and the separability was deteriorated.

An object of the present invention is to provide a recording material forming method having excellent varnish coatability and adhesion while maintaining good separability.

The present invention
A process of forming a toner image on at least a part of a recording medium with toner using an electrophotographic process.
The step of applying varnish to at least a part of the toner image and
A recording material forming method including a step of curing the varnish in this order.
The varnish contains a polymerizable monomer for varnish and contains
The polymerizable monomer for varnish is a monomer having a polymerizable functional group.
The toner has toner particles containing a binder resin and a mold release agent, and has
The release agent contains a polymerizable wax copolymerizable with the polymerizable monomer for varnish.
The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.
The content of the polymerizable wax in the toner particles is 1% by mass or more and 30% by mass or less with respect to the total mass of the toner particles.
A method for forming a recorded material, characterized in that the weight average molecular weight of the polymerizable wax is 300 or more and 10000 or less.

According to the present invention, it is possible to provide a method for forming a recorded material having excellent varnish coatability and adhesion while maintaining good separability.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.

The recording method of the present invention
A process of forming a toner image on at least a part of a recording medium with toner using an electrophotographic process.
The step of applying varnish to at least a part of the toner image and
A recording material forming method including a step of curing the varnish in this order.
The varnish contains a polymerizable monomer for varnish and contains
The polymerizable monomer for varnish is a monomer having a polymerizable functional group.
The toner has toner particles containing a binder resin and a mold release agent, and has
The release agent contains a polymerizable wax copolymerizable with the polymerizable monomer for varnish.
The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.
The content of the polymerizable wax in the toner particles is 1% by mass or more and 30% by mass or less with respect to the total mass of the toner particles.
The polymerizable wax has a weight average molecular weight of 300 or more and 10000 or less.

The present inventors infer the reason why the above-mentioned problems have been solved by the present invention as follows.

As described above, the wax on the surface of the toner image is considered to be the main factor in the coatability and peelability of the varnish. In the present invention, an aliphatic hydrocarbon wax is used as the wax. Aliphatic hydrocarbon waxes have low polarity and can be quickly deposited on the surface of the toner image in the fixing process of the electrophotographic process, suppressing the adhesion of the toner image to the fixing member and improving the separability of the toner image. Is.

Then, after applying the varnish on the toner image, when the varnish is cured by irradiation with ultraviolet rays, the varnish and the wax have a polymerizable functional group that can be copolymerized with each other. Are tightly coupled. As a result, in the obtained recorded matter, the varnish layer and the toner image are strongly adhered to each other and are not easily peeled off.

<varnish>
The varnish used in the present invention contains a polymerizable monomer for varnish. This polymerizable monomer for varnish is a monomer having a polymerizable functional group. The layer of the cured product of the varnish containing the polymerizable monomer for the varnish is the varnish layer.

The varnish used in the present invention is not particularly limited as long as it polymerizes (cures) in the coexistence with a compound or a polymerization initiator which is alone or copolymerized. The polymerization (curing) of the varnish is preferably carried out by irradiating the varnish with ultraviolet rays.

Examples of the polymerizable functional group include an ethylenic double bond and a functional group containing a carbon-carbon double bond such as maleimide.

Among the polymerizable functional groups, a polymerizable functional group containing an ethylenic double bond is preferable from the viewpoint of reactivity.

As the polymerizable functional group containing an ethylenic double bond, a (meth) acryloyl group is preferable.

Examples of the monomer having a polymerizable functional group containing an ethylenic double bond include, for example.
Polymer compounds such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and
Tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, N, N-dimethylacrylamide, 4-hydroxybutyl acrylate, tricyclodecane methacrylate, 2-hydroxyethyl methacrylate, N-vinylpyrrolidone, 1,6-hexane Monofunctional or bitubular capabilities such as diol diacrylate, 1,9-nonane diol di (meth) acrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, EO-modified bisphenol A diacrylate Acrylate compounds and
Polyfunctional monomers such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane triacrylate,
Silicone compounds with (meth) acryloyl groups such as methacryl-modified silicone and acrylic-modified silicone, and
Examples thereof include acrylic acid esters of polyhydric alcohols, epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates, acrylate alkides, and melamine acrylates.

The varnish used in the present invention may be a varnish containing only one kind of polymerizable monomer for varnish, or a varnish containing two or more kinds of polymerizable monomers for varnish.

Further, the varnish used in the present invention may contain a polymerization initiator, a sensitizer, a surfactant, a polymerization inhibitor, an additive and the like. Among these, it is preferable to include a polymerization initiator, and it is also preferable to include a sensitizer. Among the polymerization initiators, a photopolymerization initiator used for curing with light such as ultraviolet rays is preferable. Further, a radical polymerization initiator is preferable.

Examples of the photopolymerization initiator include
Benzophenone, benzoin isobutyl ether, benzoin ethyl ether, methyl benzoyl benzoate, 4-chlorobenzophenone, 4-phenylbenzophenone, 4p-trithiobenzophenone, 2-hydroxy-2,2-dimethylacetophenone, 2,2-diethoxyacetophenone, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide,
BASF's Lucillin TPO, Lucillin TPO-L,
Irgacure184, Irgacure907, Irgacure1850, Irgacure1700, Irgacure819, Irgacure369
And so on.

As a sensitizer, for example
Aromatic polycondensate compounds such as anthracene, 9,10-dialkoxyanthracene, pyrene and perylene,
Aromatic ketone compounds such as acetophenone, benzophenone, thioxanthone, and Michler ketone,
Heterocyclic compounds such as phenothiazine and N-aryloxazolidinone can be mentioned.

Examples of the polymerization inhibitor include
Compounds containing phenolic hydroxy groups,
Quinones such as methquinone (hydroquinone monomethyl ether), hydroquinone, 4-methoxy-1-naphthol,
Hindered amine antioxidants,
1,1-diphenyl-2-picrylhydrazyl free radicals, N-oxyl free radical compounds,
Nitrogen-containing heterocyclic mercapto compounds,
Thioether sulfide,
Hindered phenolic antioxidant,
Ascorbic acids,
Zinc sulphate,
Thiocyanates,
Thiourea derivative,
Various sugars,
Phosphate antioxidant,
Nitrite,
Sulfites,
Thiosulfate,
Hydroxylamine derivative,
Aromatic amine,
Phenylenediamines,
Imines,
Sulfonamides,
Urea derivative,
Oxime,
Polycondensate of dicyandiamide and polyalkylene polyamine,
Sulfur-containing compounds such as phenothiazine,
Tetraaza annulen (TAA) -based complexing agent,
Examples include hindered amines.

<Bundling resin>
The toner particles of the toner used in the present invention include a binder resin.

As a binder resin for toner particles, for example,
Homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions, and
Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacryl Methyl acid acid copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-inden copolymer, etc. Styrene-based copolymers and
Polyvinyl chloride, phenol resin, natural resin modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin , Polyvinyl butyral, terpene resin, kumaron-inden resin, petroleum resin and the like. One of these resins may be used alone, or two or more of these resins may be used in combination.

Among these resins, polyester resin is preferable from the viewpoint of compatibility with the release agent. When the polyester resin is used, it is incompatible with the release agent, so that the release agent easily exudes at the time of fixing, and the separability is improved.

The polyester resin is preferably a polycondensation polymer of an alcohol component and an acid component. Examples of the monomer for producing the polyester resin include the following compounds.

Examples of the alcohol component include the following divalent dialcohol components.
Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol , 2-Ethyl-1,3-hexanediol, hydrogenated bisfer A, bisphenol represented by the following formula (I) and its derivatives, and diols represented by the following formula (II).

As the alcohol component, as the trihydric or higher polyhydric alcohol, for example, 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol and the like may be used.

(In the formula, R represents an ethylene group or a propylene group, X and Y are integers of 0 or more, respectively, and the average value of X + Y is 0 or more and 10 or less.)

As the alcohol component, bisphenol represented by the above formula (I) is preferable.

Examples of the bisphenol represented by the above formula (I) include
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene Examples thereof include alkylene oxide adducts of bisphenol A such as (2.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane. Be done. Among the alkylene oxide adducts of bisphenol A, the propylene oxide adduct of bisphenol A is preferable.

Examples of the acid component include the following divalent carboxylic acids.
Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides,
Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides,
Succinic acid or its anhydride substituted with an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms, or
Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydrides thereof.

As the acid component, as a trivalent or higher valent carboxylic acid, for example,
1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and their acid anhydrides or lower alkyl esters, etc. You may use it.

Among the monomer units derived from the dialcohol component contained in the polyester resin, the content of the monomer units derived from the propylene oxide adduct of bisphenol A is preferably 50 mol% or more and 100 mol% or less with respect to all the monomer units. .. More preferably, it is 70 mol% or more and 100 mol% or less.

The content of the binder resin in the toner particles is preferably 30% by volume or more and 90% by volume or less, and more preferably 40% by volume or more and 80% by volume or less.

<Release agent>
The release agent used in the present invention contains a polymerizable wax copolymerizable with the polymerizable monomer for varnish contained in the varnish. The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.

Examples of the polymerizable functional group include an ethylenic double bond and a functional group containing a carbon-carbon double bond such as maleimide.

Among the polymerizable functional groups, a polymerizable functional group containing an ethylenic double bond is preferable from the viewpoint of reactivity.

The polymerizable wax preferably has two or more polymerizable functional groups containing an ethylenic double bond.

Aliphatic hydrocarbon wax refers to a wax whose main skeleton is composed only of carbon atoms and hydrogen atoms. A functional group such as a hydroxy group may be contained at the terminal or the like. Among the aliphatic hydrocarbon-based waxes, an aliphatic hydrocarbon wax in which the entire molecule including the terminal is composed of only carbon atoms and hydrogen atoms is preferable.

Examples of the aliphatic hydrocarbon wax include, for example.
Dialen 208 (C20-28), Dialen 30 (C30 or higher) (Mitsubishi Kasei Co., Ltd.),
VYBAR # 260 (C30 or higher), VYBAR # 6041 (C30 or higher) (Petrolite Co., Ltd.)
Examples thereof include α-olefins such as, polydiene and hydrogenated products thereof.

From the viewpoint of reactivity with varnish, it is preferable to use polydiene having a plurality of ethylenic double bonds in the molecule and a hydrogenated product thereof, and a hydrogenated product of polydiene is more preferable.

As the release agent, only an aliphatic hydrocarbon-based wax having a polymerizable functional group copolymerizable with the polymerizable monomer for varnish may be used, or may be used in combination with other waxes.

Examples of the release agent that can be used in combination include, for example.
Low molecular weight polyolefins such as polyethylene,
Silicones that have a melting point (softening point) by heating,
Fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide,
Ester waxes such as stearyl stearate and
Vegetable waxes such as carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc.
Animal wax like beeswax,
Mineral and petroleum waxes such as Montan wax, Ozokerite, Celesin, Paraffin wax, Microcrystalline wax, Fishertroph wax, Ester wax,
Examples thereof include modified products thereof.

The toner particles of the toner used in the present invention contain polymerizable wax (aliphatic hydrocarbon wax having a polymerizable functional group) in an amount of 1% by mass or more and 30% by mass or less based on the total mass of the toner particles. Within this range, it is possible to achieve both excellent separability of the toner image with respect to the fixing member and excellent adhesion between the toner image and the varnish layer.

The weight average molecular weight of the polymerizable wax used in the present invention is 300 or more and 10,000 or less. Within this range, it is possible to achieve both excellent separability of the toner image with respect to the fixing member and excellent adhesion between the toner image and the varnish layer.

The iodine value of the polymerizable wax used in the present invention is preferably 2 or more and 300 or less, preferably 100 or more and 300 or more, from the viewpoint of adhesion between the toner image and the varnish layer and varnish coating property on the toner image. Is more preferable.

<Toner manufacturing method>
Examples of the toner production method include an emulsion aggregation method, a pulverization method, and a suspension polymerization method.

Hereinafter, a method for producing toner by the pulverization method will be described as an example.

In the raw material mixing step, for example, a binder resin and a mold release agent, and if necessary, other components such as a colorant (pigment) and a charge control agent are weighed and blended as materials constituting the toner particles. , Mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd.).

Next, the mixed materials are melt-kneaded.

In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Bambary mixer or a continuous-type kneader can be used, and a single-screw or two-screw extruder is preferable because of the advantage of continuous production. The temperature of melt-kneading is preferably about 100 to 200 ° C.

As a device that can be used for melt kneading, for example,
KTK type 2-axis extruder (manufactured by Kobe Steel), TEM type 2-axis extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikegai Co., Ltd.), 2-axis extruder (KTK) Co., Ltd.), Co-Kneader (manufactured by Bus), Kneedex (manufactured by Nippon Coke Industries Co., Ltd.)
And so on.

The resin composition obtained by melt-kneading is rolled with two rolls or the like, and is rapidly cooled with water or the like in the cooling step.

Then, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step.

In the crushing step, coarse crushing is performed with a crusher such as a crusher, a hammer mill, or a feather mill. After that, for example, a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Freund Turbo Co., Ltd.), or an air jet pulverizer is used. Smash.

Then, if necessary,
Inertia classification elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification turboplex (manufactured by Hosokawa Micron Co., Ltd.), TSP separator (manufactured by Hosokawa Micron Co., Ltd.), faculty (manufactured by Hosokawa Micron Co., Ltd.)
Classify products (toner particles) by classifying them using a classifier such as a classifier or a sieve classifier.

The obtained toner particles may be used as they are as toner. If necessary, the surface of the toner particles may be externally treated with an external additive to obtain toner. As a method of externally treating the external additive, a predetermined amount of toner particles and the external additive are mixed.
Double control mixer,
V-type mixer,
Drum type mixer,
Super mixer,
Henschel mixer,
Nauta mixer,
Mechano Hybrid (manufactured by Nippon Coke Industries Co., Ltd.),
Nobilta (manufactured by Hosokawa Micron Co., Ltd.)
A method of stirring and mixing using a mixing device such as the above as an external addition machine can be mentioned.

The toner used in the present invention preferably has a volume-based median diameter of 3.0 μm or more and 30.0 μm or less, and more preferably 4.0 or more and 20.0 μm or less.

<Image formation method>
The toner used in the present invention is used in an image forming method using an electrophotographic process, and can be suitably used in an image forming method including a fixing step by a contact heating method. For example, an electrostatic latent image electrostatically formed on an electrostatic latent image carrier is manifested with toner to obtain a toner image, and the toner image is transferred to a recording medium. After that, the toner image transferred on the recording medium is fixed on the recording medium by fixing treatment with a contact heating type fixing member, whereby a toner image is obtained.

<recoding media>
The recording medium used for the toner of the present invention includes, for example, plain paper from thin paper to thick paper, coated printing paper such as high-quality paper, art paper, and coated paper, commercially available Japanese paper and postcard paper, and OHP. Plastic film, cloth, etc.

<Method of forming varnish layer>
The image forming method of the present invention includes a step of applying varnish to at least a part of a toner image on a recording medium immediately after forming a toner image on at least a part of a recording medium or after leaving the image. Further, the step of forming a varnish layer by irradiating the coating film formed by applying the varnish with, for example, ultraviolet rays and curing the varnish is included.

Examples of the varnish application method include a method using a flexographic coater, a roll coater, a gravure coater, a gravure offset coater, a bar coater, an offset printing machine, a sheet-fed printing machine, an in-line varnish coating machine, and a screen printing machine.

Examples of the light source of ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, LED-UV lamps, carbon arc lamps, and the like.

Hereinafter, the image forming method will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

Hereinafter, a method for measuring physical properties related to the present invention will be described.

<Measurement of molecular weight of THF-soluble component of resin>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the THF-soluble components of the binder resin used for the toner particles are measured by gel permeation chromatography (GPC) as follows.

First, the sample is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.

Device: HLC8120GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin is used. Examples of the standard polystyrene resin include the trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" manufactured by Toso Co., Ltd. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "
And so on.

<Measurement of average volume particle size and particle size distribution of toner particles>
A precision particle size distribution measuring device "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electrical resistance method.
Dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data,
Is used to measure with 25,000 effective measurement channels, and the measurement data is analyzed and calculated.

<Synthesis of mold release agent (W-1)>
To 100 parts of B-1000 (polybutadiene, weight average molecular weight 1200, manufactured by Nippon Soda Corporation) in a reaction vessel, 5 parts of palladium carbon was added as a hydrogenation catalyst, and the reaction was carried out at a hydrogen pressure of 2 MPa and 50 ° C. for 5 hours. Was done. After allowing to cool and release pressure, palladium carbon was removed by filtration, the filtrate was concentrated, and further vacuum dried to obtain a release agent (W-1).

<Synthesis of mold release agent (W-5)>
In the synthesis of the release agent (W-1), the release agent (W-5) was obtained in the same manner except that the reaction time and the reaction temperature were adjusted.

<Synthesis of mold release agent (W-7)>
In the synthesis of the release agent (W-1), release is performed in the same manner except that G-1000 (terminal hydrogenated polybutadiene, weight average molecular weight 1400, manufactured by Nippon Soda Corporation) is used instead of B-1000. A mold (W-7) was obtained.

<Synthesis of mold release agent (W-2)>
338 g of n-hexane was placed in a 1 L flask and cooled to −40 ° C. To this was added a cyclohexane solution of 56 g of sec-butyllithium (concentration: 10.6% by mass), and then 84 g of butadiene liquefied at −78 ° C. was added dropwise. The mixture was stirred at −20 ° C. for 2 hours. This polymer solution was sampled and measured by GPC, but no polymer was produced. Subsequently, 18 g of THF was added to this polymer solution, the mixture was stirred at −20 ° C. for 30 minutes, and 30 g of methanol was added.

The solution was washed twice with 300 g of 0.3% hydrochloric acid and then twice with 300 g of pure water. 11 g of anhydrous magnesium sulfate was added to the organic layer, and the mixture was allowed to stand for 30 minutes. A filtration operation was performed, the filtrate was concentrated, and the solvent was distilled off to obtain 89 g of a liquid resin.

The obtained resin was placed in a reaction vessel, and 5 parts of palladium carbon was added as a hydrogenation catalyst to 100 parts of the obtained resin, and the reaction was carried out under the conditions of a hydrogen pressure of 2 MPa and 50 ° C. for 5 hours. After allowing to cool and release pressure, palladium carbon was removed by filtration, the filtrate was concentrated, and further vacuum dried to obtain a release agent (W-2).

<Synthesis of mold release agents (W-3), (W-4), (W-6), (W-9) to (W-10), (W-12), (W-13)>
In the synthesis of the release agent (W-2), the release agents (W-3), (W-4), (W-6), (W) are similarly adjusted except that the reaction time and the reaction temperature are adjusted. -9) to (W-10), (W-12), and (W-13) were synthesized.

<Synthesis of mold release agent (W-11)>
In a four-necked flask equipped with a thermometer, nitrogen introduction tube, stirrer and cooling tube,
638 g of triacontanol (CH ₃ (CH ₂ ) ₂₉ OH) (“Unilin 425” (manufactured by Baker Petrolite: melting point 91 ° C.)) as an alcohol component and 100 g of acrylic acid as an acid component.
Was added, and the reaction water was distilled off at 220 ° C. under a nitrogen stream, and the reaction was carried out at normal pressure for 15 hours or more to obtain a release agent (W-11).

Table 1 shows the physical property values of the release agents (W-1) to (W-13).

The iodine value in Table 1 was measured by a method based on the wax analysis method described in the standard fat analysis method. The molecular weight in Table 1 is the weight average molecular weight of the release agent (polymerizable wax).

<Production example of binder resin 1>
A 5 L four-necked flask equipped with a nitrogen inlet tube, a cooling tube, a stirrer and a thermocouple was replaced with nitrogen. Then, 60 mol% of BPA-PO (average number of mols of propylene oxide adduct of bisphenol A added 2.7 mol), 40 mol% of terephthalic acid and tin (II) octylate were added, and the temperature was raised at 180 ° C. and then reacted for 10 hours. It was. Further, the reaction was carried out at 15 mmHg for 5 hours. Then, as a second reaction step, 0.04 mol% of trimellitic anhydride and 10 mol% of benzoic acid were added according to Table 2 and reacted at 180 ° C. for 3 hours to obtain an amorphous polyester resin A1. The physical properties of the amorphous polyester resin A1 were a number average molecular weight of 2300, a glass transition temperature (Tg) of 50 ° C., and a melting point (Tm) of 82 ° C.

<Production example of developer D-1>
・ Bundling resin 1 100 parts ・ Release agent W-1 6 parts ・ HNP-51 (manufactured by Nippon Seiwa Co., Ltd.) 3 parts ・ Pigment blue 15: 39 parts ・ 3,5-di-t-butylsalicylic acid Aluminum compound 0.3 part (Bontron E88, manufactured by Orient Chemical Industry Co., Ltd.)
The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20 s- ¹ and a rotation time of 5 minutes, and then a biaxial kneader (PCM-) set at a temperature of 140 ° C. 30 type, manufactured by Ikekai Co., Ltd.) was kneaded. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Freund Turbo Co., Ltd.). Further, using Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 130s ^-1 and a distributed rotor rotation speed of 120s ^-1 . Further, the fine particle side powder separated from the toner particles 1 in the classification step was separately collected and used for analysis.

With 100 parts of toner particles
1 part of hydrophobic silica (BET: 200m ² / g) and
1 part of titanium oxide fine particles (BET: 80 m ² / g) surface-treated with isobutyltrimethoxysilane and
Was placed in a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Kakoki Co., Ltd.) and mixed at a rotation speed of 30 s- ¹ and a rotation time of 10 minutes to obtain toner 1. The weight average particle size (D4) of the toner 1 was 6.4 μm.

A ferrite carrier (average particle size 42 μm) surface-coated with a silicone resin was mixed so that the toner concentration was 8% by mass to prepare a developer D-1.

<Production Examples of Developers D-2 to D-21>
In the production example of the developer D-1, the developers D-2 to D-21 were produced in the same manner except that the type of the binder resin, the type and the amount of the release agent were adjusted according to Table 2.

Nucrel N1525 in Table 2 is an ethylene-methacrylic acid resin manufactured by Mitsui DuPont Polychemical Co., Ltd. VYBAR # 260 is an α-olefin manufactured by Petrolite Co., Ltd. The unit of the amount of the release agent in Table 2 is "parts (mass part)".

<Evaluation of Example 1>
Evaluation was performed using the obtained developer 1.

As an image forming apparatus, a modified machine of imageRUNNER ADVANCE C9280PRO (trade name), which is a printer for digital commercial printing manufactured by Canon Inc., was used. A two-component developer 1 is placed in a developer at the cyan position to form a toner image in which the amount of toner loaded on the electrostatic latent image carrier (photosensitive drum) or recording medium (paper) is a predetermined amount, which will be described later. Evaluation was performed.

As the modification points, the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, the laser power, the fixing temperature, and the process speed were changed so that they could be freely set.

For the image output evaluation, an FFh image (solid image) having a desired image ratio was output. FFh is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..

Evaluation is based on the following evaluation methods, and the results are shown in Table 2.

<Separability>
Evaluation image: A toner image with a width of 60 mm is placed at a position 4 mm from the tip of A4 paper. Toner loading amount: 1.20 mg / cm ² (FFh image)
Process speed: 350 mm / sec Test environment: High temperature and high humidity environment (temperature 30 ° C / humidity 80% RH (hereinafter H / H))
An unfixed toner image was formed under the above conditions using the above image forming apparatus.

After the formed unfixed toner image was left in an H / H environment for 2 nights, the fixing temperature was raised by 5 ° C. in order from 100 ° C., and the temperature at which the fixed image was wrapped around the fuser was measured and evaluated according to the following criteria. ..

<Evaluation criteria>
A: Winding temperature is 180 ° C or higher B: Winding temperature is 165 ° C or higher and lower than 180 ° C C: Winding temperature is 150 ° C or higher and lower than 165 ° C D: Winding temperature is lower than 150 ° C The higher the winding temperature, the better.

<Adhesion>
Evaluation image: Full solid image of A4 paper (toner image)
Toner loading amount: 1.20 mg / cm ² (FFh image)
Process speed: 350 mm / sec A fixed image was created under the above conditions using the above image forming apparatus.

UV VECTA coat varnish PC-3kW2 (manufactured by T & K Co., Ltd.) was applied on the prepared fixed image with a bar coater so as to have a thickness of 5 μm. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated so that the integrated light amount on the image surface was 120 to 130 mJ / cm ^2, and the varnish was cured to form a varnish layer. UV VECTA coat varnish PC-3kW2 contains a polymerizable monomer for varnish and a photopolymerization initiator (radical polymerization initiator). The polymerizable monomer for varnish has a polymerizable functional group containing an ethylenic double bond.

Kapton tape (3M) was attached to the surface of the varnish layer of the obtained image, and the adhesion was evaluated based on the following evaluation criteria by peeling the varnish layer when the tape was peeled off.

<Adhesion>
A: No peeling of the varnish layer is observed.
B: The peeled portion of the varnish is 5% or less.
C: The peeled portion of the varnish is 50% or less.
D: The peeled portion of the varnish exceeds 50%.

It is best that no peeling is observed, and the smaller the percentage of the peeled portion, the better.

<Applicability>
Evaluation image: Solid image of A4 paper (toner image)
Toner loading amount: 1.20 mg / cm ² (FFh image)
Process speed: 350 mm / sec A fixed image was created under the above conditions using the above image forming apparatus.

UV VECTA coat varnish PC-3kW2 (manufactured by T & K Co., Ltd.) was applied on the prepared fixed image with a bar coater so as to have a thickness of 5 μm. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated so that the integrated light amount on the image surface was 120 to 130 mJ / cm ^2, and the varnish was cured to form a varnish layer.

The surface of the varnish layer of the obtained image was visually observed, and the applicability was evaluated by the presence or absence of repelling based on the following evaluation criteria.

(Applicability)
A: No peeling of the varnish is observed.
B: Only a slight varnish is observed.
C: Varnish repelling is observed in some parts.
D: Varnish repelling is observed on the entire surface.

<Evaluation of Examples 2 to 16 and Comparative Examples 1 to 6>
In the evaluation of Example 1, the same evaluation was performed by changing the types of toner (developer) and varnish used. The results are shown in Table 3.

In Example 9, a mixture of 50 mol% of N-butylmaleimide and 50 mol% of dodecyl vinyl ether was used as the varnish.

Claims (17)

A process of forming a toner image on at least a part of a recording medium with toner using an electrophotographic process.
The step of applying varnish to at least a part of the toner image and
A recording material forming method including a step of curing the varnish in this order.
The varnish contains a polymerizable monomer for varnish and contains
The polymerizable monomer for varnish is a monomer having a polymerizable functional group.
The toner has toner particles containing a binder resin and a release agent, and has
The release agent contains a polymerizable wax that is copolymerizable with the polymerizable monomer for varnish.
The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.
The content of the polymerizable wax in the toner particles is 1% by mass or more and 30% by mass or less with respect to the total mass of the toner particles.
A method for forming a recorded material, characterized in that the weight average molecular weight of the polymerizable wax is 300 or more and 10000 or less. The method for forming a recorded material according to claim 1, wherein the iodine value of the polymerizable wax is 2 or more and 300 or less. The method for forming a record according to claim 1 or 2, wherein the polymerizable wax has two or more polymerizable functional groups containing an ethylenic double bond. The method for forming a record according to any one of claims 1 to 3, wherein the polymerizable wax is a hydrogenated additive of polydiene. The method for forming a record according to any one of claims 1 to 4, wherein the varnish contains the polymerizable monomer for varnish and the radical polymerization initiator. The method for forming a record according to any one of claims 1 to 5, wherein the polymerizable monomer for varnish has a polymerizable functional group containing an ethylenic double bond. The method for forming a recorded material according to any one of claims 1 to 6, wherein the release agent is incompatible with the binder resin. The method for forming a recorded material according to any one of claims 1 to 7, wherein the binding resin contains a polyester resin. The recording material forming method according to any one of claims 1 to 8, wherein the step of curing the varnish is a step of irradiating the varnish with ultraviolet rays to cure the varnish. A recording medium having a recording medium, a toner image formed of toner on at least a part of the recording medium, and a varnish layer formed of varnish on at least a part of the toner image.
The varnish layer is a layer of a cured product of a varnish containing a polymerizable monomer for varnish.
The polymerizable monomer for varnish is a monomer having a polymerizable functional group.
The toner has toner particles containing a binder resin and a mold release agent, and has
The release agent contains a polymerizable wax copolymerizable with the polymerizable monomer for varnish.
The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.
The content of the polymerizable wax in the toner particles is 1% by mass or more and 30% by mass or less with respect to the total mass of the toner particles.
A recorded product characterized in that the weight average molecular weight of the polymerizable wax is 300 or more and 10000 or less. The record according to claim 10, wherein the iodine value of the polymerizable wax is 2 or more and 300 or less. The record according to claim 10 or 11, wherein the polymerizable wax has two or more polymerizable functional groups containing an ethylenic double bond. The record according to any one of claims 10 to 12, wherein the polymerizable wax is a hydrogenated product of polydiene. A toner having toner particles containing a binder resin and a mold release agent.
The release agent contains a polymerizable wax and contains
The polymerizable wax is an aliphatic hydrocarbon-based wax having a polymerizable functional group.
The content of the polymerizable wax in the toner particles is 1% by mass or more and 30% by mass or less with respect to the total mass of the toner particles.
A toner characterized in that the weight average molecular weight of the polymerizable wax is 300 or more and 10000 or less. The toner according to claim 14, wherein the polymerizable wax has an iodine value of 2 or more and 300 or less. The toner according to claim 14 or 15, wherein the polymerizable wax has two or more polymerizable functional groups containing an ethylenic double bond. The toner according to any one of claims 14 to 16, wherein the polymerizable wax is a hydrogenated product of polydiene.