JP2012234116A - Foil transfer method and toner for forming foil transfer face - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foil transfer method and a toner for forming a foil transfer face, by which both of foil transfer property and durability to additional printing can be achieved.SOLUTION: A foil transfer method includes: an electrostatic latent image formation step of forming an electrostatic latent image by exposing a photoreceptor; a foil transfer face formation step of forming a foil transfer face by supplying a toner T to the photoreceptor where the electrostatic latent image is formed; a first transfer step of transferring the foil transfer face H formed on the photoreceptor onto a substrate P; a fixing step of fixing the foil transfer face H transferred onto the substrate P; a supply step of supplying a transfer foil F to the substrate P where the foil transfer face H is fixed; and a second transfer step of transferring the transfer foil F onto the foil transfer face H by heating while the transfer foil F is in contact with the foil transfer face H. The toner T used in the foil transfer face formation step includes at least a polyester resin and a vinyl resin having an ionic crosslinking structure.

Description

  The present invention relates to a foil transfer method and a foil transfer surface forming toner.

In recent years, a processing technique called “foil stamping” has been performed in the fields of bookbinding, commercial printing, card business, or plastic molding of cosmetic containers and the like. This technology, also called “hot stamping”, uses a pressure member called a metal stamping die to transfer characters and patterns made of foil onto the surface of the substrate by the action of heat and pressure, and can be expressed in general printing. A high-quality image with a difficult metallic feeling and gloss can be imparted. Recently, foil transfer technology has also been developed for holograms provided for the prevention of counterfeiting and security of cash cards and credit cards.
The transfer foil used for foil pressing has, for example, a structure in which a release agent layer is provided on a resinous film-like substrate surface, and a protective layer, a transfer material layer, and an adhesive layer are disposed thereon, and the foil The transfer material layer containing is mainly formed using metal vapor deposition or ink. The transfer foil having such a structure has been improved with the expansion of materials and applications for transferring the foil. For example, a protective layer containing an organosilicon compound and a reactive organic compound is provided to improve the durability of the foil image, or a strong protective layer is formed by irradiating an electron beam after peeling from the substrate. The transfer foil etc. which were made were examined (for example, refer patent document 1, 2). Further, the transfer foil for the above-mentioned cash card and credit card is required to be transferred with a precise pattern accurately and without causing defects such as burrs or chips. For example, the transfer material layer contains a polymer liquid crystal material. This problem is solved (see, for example, Patent Document 3).

On the other hand, a method of performing foil transfer without taking time and labor has been studied, and a technique for forming a resin layer on a substrate using toner and transferring the foil thereon has been studied. In this technique, a synergistic action of an adhesive force generated by softening or melting of the toner by heating and an adhesive force generated by melting of the adhesive layer of the transfer foil is obtained. A strong adhesive force can be expressed. Specifically, there is a method in which a toner image is formed on a substrate to form a convex image or a costume pattern image, and a transfer foil is superimposed on the formed toner image surface and thermocompression bonded to transfer the foil ( For example, see Patent Document 4).
In addition, the toner is previously deposited on the base material, the vapor-deposited foil sheet is overlaid thereon, hot-pressed with an iron from the top, and then the vapor-deposited foil sheet is peeled off from the base material. There is also a technique for transferring the image (for example, see Patent Document 5).
In this way, the technology for transferring the foil using the toner can transfer the foil without using the stamping die, which has been required in the prior art. Enables simplification.

JP-A-9-1995 JP 2007-15159 A JP 2009-90464 A Japanese Patent Laid-Open No. 1-200985 JP 2000-127691 A

In some cases, after the foil is transferred onto the substrate, heat treatment is applied to the substrate onto which the foil has been transferred. Specifically, an image is formed using toner on a substrate onto which the foil has been transferred, and a case called reprinting for fixing the formed toner image, or another foil is transferred onto the created foil image. There are cases where a heat treatment for forming an overprint image is performed.
In this way, when heat treatment is performed on the substrate to which the foil has been transferred, in the case where the foil is transferred onto the toner layer, the toner layer is melted by reheating and streaks or the like enter the foil. The defective finish of the foil has a great influence on the quality of the product. In other words, when heat is applied to the toner adhering to the foil and fluidity is obtained, it can be dealt with by deforming against the applied pressure, but the foil itself cannot be deformed and cracks are generated due to the applied pressure. Will occur. The foil transferability is evaluated based on the degree of occurrence of burrs in which excess foil is attached around the foil image and omissions that cause defects in the foil image. Further, the above-mentioned resistance to overprinting is evaluated based on the presence or absence of streaks generated in the foil image after overprinting. In addition, in the case of further image formation (reprinting) on a substrate onto which a foil has been transferred using toner, it has been studied to cope with a method other than an electrophotographic method such as an inkjet method or offset printing. This is not preferable because it is limited and complicates the work process. Eventually, an electrophotographic method is desired.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a foil transfer method and a foil transfer surface forming toner capable of achieving both foil transfer properties and resistance to overprinting.

In order to solve the above problems, according to the invention of claim 1, an electrostatic latent image forming step of forming an electrostatic latent image by exposing a photosensitive member;
A foil transfer surface forming step of forming a foil transfer surface by supplying toner to the photoreceptor on which the electrostatic latent image is formed;
A first transfer step of transferring a foil transfer surface formed on the photoreceptor to a substrate;
A fixing step of fixing the foil transfer surface transferred to the substrate;
Supplying the transfer foil to the substrate on which the foil transfer surface is fixed;
A second transfer step in which the transfer foil is heated under the state of being in contact with the foil transfer surface to transfer the transfer foil to the foil transfer surface, and a foil transfer method comprising:
The toner used in the foil transfer surface forming step contains at least a polyester resin and a vinyl resin having an ionic cross-linking structure.

  According to the invention of claim 2, after the second transfer step, a toner image is formed on a substrate on which the transfer foil is transferred to the foil transfer surface, and the substrate on which the toner image is formed is heated, The foil transfer method according to claim 1, further comprising a toner image forming step of fixing the toner image.

According to the invention of claim 3, the binder resin contained in the toner used in the foil transfer surface forming step is
3. The foil transfer method according to claim 1, wherein a content of the vinyl resin having an ionic crosslinking structure is 5% or more and 50% or less.

  According to invention of Claim 4, the toner used at the said foil transfer surface formation process is a clear toner, The foil transfer method as described in any one of Claims 1-3 characterized by the above-mentioned. .

  According to invention of Claim 5, the said polyester resin is an amorphous polyester resin, The foil transfer method as described in any one of Claims 1-4 characterized by the above-mentioned is provided.

According to the invention of claim 6, a toner for forming a foil transfer surface containing at least a binder resin,
Provided is a toner for forming a foil transfer surface, wherein the binder resin contains at least a polyester resin and a vinyl resin having an ionic crosslinking structure.

  According to the present invention, the toner that forms the foil transfer surface has at least a polar group in the main chain, has good adhesion to the adhesive layer of the transfer foil, and is advantageous for foil transfer, and an ion cross-linked structure The vinyl-based resin having the above-described ionic cross-linking structure, the internal cohesive force in the toner layer can be increased by the ionic cross-linking structure, and the thermoplasticity is not greatly impaired even at high temperatures. It is possible to achieve both printability.

(a)-(e) is a schematic diagram for showing the procedure of the foil transcription | transfer method. It is the schematic of the foil transfer surface formation apparatus which forms a foil transfer surface by an electrostatic latent image system. It is a cross-sectional block diagram of the foil transfer surface formation apparatus which can form foil transfer surface and full color image formation simultaneously. It is the schematic of a foil transcription | transfer apparatus. (a), (b) is the schematic diagram of the foil image sample used by evaluation of the Example.

In order to suppress the occurrence of streaks during reprinting, the present inventors considered preventing the deformation of the toner layer forming the foil transfer surface against stress during reprinting. Therefore, in order to obtain the entanglement between the molecular chains and increase the cohesive force between the resin molecules to increase the internal cohesive force of the toner layer, the high molecular weight of the polyester resin formed by polycondensation reaction was examined. However, the polyester resin originally has a high softening point even at a low molecular weight because of its strong internal cohesion between resin molecules. The foil transferability itself has been lowered.
Therefore, as a means for increasing the internal cohesive force of the toner layer and suppressing the decrease in thermoplasticity even at a high temperature, a vinyl resin having an ionic crosslinking structure having a cohesive force stronger than the internal cohesive force between the polyester resins, By using it together with the polyester resin, it was possible to achieve both foil transferability and reprintability.

Hereinafter, the present invention will be described in detail.
The foil transfer method according to the present invention includes the following steps (1) to (6).
(1) Electrostatic latent image forming step for forming an electrostatic latent image by exposing the photosensitive member (2) Foil transfer for forming a foil transfer surface by supplying toner to the photosensitive member on which the electrostatic latent image has been formed Surface forming step (3) First transfer step of transferring the foil transfer surface formed on the photosensitive member to the substrate (4) Fixing step of fixing the foil transfer surface transferred to the substrate (5) The foil transfer surface is Supplying step of supplying transfer foil to the fixed substrate (6) Second transfer step of transferring the transfer foil to the foil transfer surface by heating the transfer foil in contact with the foil transfer surface After the second transfer step (6), a full color toner image is formed on the substrate onto which the transfer foil has been transferred, and the substrate is heated to fix the toner image. (7) The toner image forming step may be included. .
In the foil transfer method of the present invention, the toner used in the foil transfer surface forming step (hereinafter also referred to as foil transfer surface forming toner) has at least a binder resin, and the binder resin has at least polycondensation. It contains a polyester resin formed by a reaction and a vinyl resin having an ionic crosslinking structure.

The “foil transfer surface forming toner” as used in the present invention is supplied onto a photoreceptor to form a toner layer called a foil transfer surface. Then, the foil transfer surface on the photoreceptor formed with the toner for forming the foil transfer surface is transferred and fixed onto a sheet-shaped substrate (product) typified by an image support. Further, the foil transfer surface fixed on the substrate is supplied with the transfer foil and, when heated, is firmly bonded to the transfer foil for transfer.
In addition, the “foil transfer surface” referred to in the present invention is a region where a foil on a substrate such as an image support or a plastic molded product is transferred, and is formed using the toner for forming a foil transfer surface according to the present invention. Is.
Further, the “base” in the present invention means a three-dimensional shape such as an image support such as paper or PET (polyethylene terephthalate) base or a plastic molded product, and is a material before decoration with a foil.
Furthermore, the “foil” referred to in the present invention is also referred to as “transfer foil”, and is intended to provide a character or pattern having a metallic feeling or glossiness that is difficult to express by general printing on an image support. It is what is used. As the foil, various kinds of foil such as a gold-silver foil for obtaining a golden or silver image, a color pigment foil for obtaining a color image having a metallic luster, a hologram foil for obtaining a hologram image, etc. Although there are some, the kind of foil used in the present invention is not particularly limited.

[Foil transfer surface forming toner]
The toner for forming a foil transfer surface used in the present invention contains a binder resin containing at least a polyester resin formed by a polycondensation reaction and a vinyl resin having an ionic crosslinking structure.
Thus, in the present invention, a vinyl resin having an ionic cross-linking structure having a cohesion stronger than the internal cohesion of the polyester resin is used together with the polyester resin as the binder resin for the foil transfer surface forming toner. In addition, the internal cohesive force of the toner layer is increased, making it possible to achieve both foil transferability and resistance to overprinting.

The polyester resin is obtained by polymerizing a raw material monomer of the polyester resin. In the present invention, a polyester resin is used from the viewpoint of toner fixability and durability.
The polyester resin is converted into a resin by polycondensation of dialcohol and dicarboxylic acid. Therefore, since there is an ester bond having polarity in the main chain, an electrostatic bond can be formed between the main chains. Therefore, the polarity is strong and sufficient adhesiveness can be given to the adhesive layer of the transfer foil. Also, the internal cohesive force is large, and when the transferred foil is peeled off after fixing the toner with a fixing device, the toner layer breaks, which is advantageous in suppressing the occurrence of transfer failure (missing) of the foil. .

The vinyl resin having an ionic crosslinking structure contained in the toner for forming a foil transfer surface is a vinyl resin in which a structural unit having an acid group is coordinated with a polyvalent metal ion.
The acid group used in the present invention is one or more of groups such as carboxylic acid, sulfonic acid, sulfinic acid, phosphonic acid or boric acid. Of these, carboxylic acids are particularly preferably used because of the strength of the acid and the ease of copolymerization. Specific examples of vinyl monomers having a carboxylic acid include (meth) acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and α- or β-alkyl derivatives; fumaric acid, maleic acid, citraconic acid Unsaturated dicarboxylic acids such as itaconic acid; unsaturated dicarboxylic acid monoester derivatives such as succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, phthalic acid monomethacryloyloxyethyl ester Etc.
An ionic cross-linked structure is a structure obtained by reacting a polyvalent metal with a resin having a structural unit having an acid group. For example, a cross-linked structure generated by a coordinate bond (ionic bond) between a carboxyl group and a magnesium ion is used. Can be mentioned.

  The content of the vinyl resin having an ionic crosslinking structure is preferably 5% by mass or more and 50% by mass or less with respect to the total binder resin of the vinyl resin. More preferably, it is 10 mass% or more and 30 mass% or less. If the vinyl resin having an ionic crosslinking structure is less than 5% and the polyester resin is 95% or more, the internal cohesive force of the toner at high temperature becomes insufficient and streaks may occur during reprinting. Further, if the vinyl resin having the ionic cross-linked structure exceeds 50% and the polyester resin is less than 50%, the toner cohesive force is too small, and there is a possibility that the foil transferability may not be sufficient (the lack occurs). There is a fear).

Examples of the polyvalent metal ions are divalent or trivalent metal ions such as magnesium ions, calcium ions, strontium ions, barium ions, zinc ions, and aluminum ions. Of these, magnesium ions and aluminum ions are preferred. A combination of these metal ions can also be used.
Examples of the compound having a polyvalent metal ion include chlorides, bromides, sulfides and hydrates of the above polyvalent metal ions.
In the present invention, as described later, at the time of preparation of toner particles, a part of the polyvalent metal ions used as an aggregating agent is taken into the toner and reacts with the carboxyl groups present on the surface of the core particles to form an ion cross-linked structure. It is preferable to do.
The addition amount of the compound having a polyvalent metal ion is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the core resin particles forming the core particles.
As described above, the vinyl resin having an ionic cross-linked structure is reduced in brittleness and exhibits toughness at room temperature, and as a result, when used in a toner for forming a foil transfer surface, stirring in the foil transfer surface forming apparatus. It prevents the external additives from being buried without being crushed by stress caused by.

The toner for forming the foil transfer surface used in the present invention is preferably a clear toner.
The “clear toner” referred to in the present invention is a toner whose color is not recognized by the action of light absorption or light scattering. The clear toner may be substantially colorless and transparent. For example, a toner that does not contain a colorant such as a pigment or a dye, a toner that contains a colorant such as a pigment or a dye that cannot recognize the color, a binder resin or a wax, Examples thereof include a toner whose transparency is slightly lowered depending on the type and amount of the external additive.

Next, a manufacturing method of the foil transfer surface forming toner will be described.
[Method for producing toner for forming foil transfer surface]
The toner for forming the foil transfer surface can be produced by a known production method such as a pulverization method, a suspension polymerization method, or an emulsion polymerization aggregation method.
Hereinafter, as an example of a method for producing a toner for forming a foil transfer surface, a production method by an emulsion polymerization aggregation method is shown.
The method for producing the toner for forming a foil transfer surface includes the following two methods because there are two methods for introducing an ion-crosslinked structure having a polyvalent metal.
First, as a method of introducing an ion cross-linked structure having a polyvalent metal,
(A) A polyester resin and a vinyl resin obtained by polymerizing at least a raw material monomer for a polyester resin, a raw material monomer for a vinyl resin formed from a radical polymerizable monomer, and a bireactive monomer. Producing a composite resin in which an ion-crosslinked structure is introduced by reacting a carboxyl group of a vinyl resin in the composite resin with a polyvalent metal ion under the polyvalent metal ion,
(B) The polyester resin dispersion and the vinyl resin dispersion are reacted under a polyvalent metal ion to react the carboxyl group of the vinyl resin with the polyvalent metal ion to introduce an ionic crosslinking structure. how to,
Is mentioned.

Therefore, the method for producing the toner for forming a foil transfer surface by the introduction method (a) includes the following steps (a-1) to (a-6).
(A-1) A polyester resin and a vinyl resin obtained by polymerizing at least a raw material monomer of a polyester resin, a raw material monomer of a vinyl resin formed from a radical polymerizable monomer, and both reactive monomers, The step of producing a combined composite resin (a-2) The step of producing composite resin particle dispersion by dispersing composite resin particles (a-3) The composite resin fine particle dispersion and metal polyvalent ions are mixed, Salting out, agglomerating, and fusing these in an aqueous medium to form toner particles salting out, agglomerating, fusing step (a-4) (aqueous medium) separating toner particles from the dispersion of toner particles; Filtration and washing step (a-5) for removing the surfactant from the toner particles (a-5) Drying step for drying the washed toner particles (a-6) Step for adding an external additive to the dried toner particles

Further, the toner production method by the introduction method (b) has the following steps (b-1) to (b-6).
(B-1) Step of producing polyester resin particle dispersion by dispersing polyester resin particles (b-2) Step of producing vinyl resin particle dispersion by dispersing vinyl resin (b-3) Polyester resin A salting-out, agglomeration, and fusion process in which a particle dispersion, a vinyl resin particle dispersion, and a metal multivalent ion are mixed and salted out, agglomerated, and fused in an aqueous medium to form toner particles. (B-4) Filtering to remove toner particles from the toner particle dispersion (aqueous medium), removing the surfactant from the toner particles, and washing step (b-5) Drying the treated toner particles (B-6) a step of adding an external additive to the dried toner particles

Next, each process will be described.
Step (a-1) As the step of producing the composite resin, the following three methods may be mentioned.
i) A method of performing a polycondensation reaction after performing an addition polymerization reaction, adding a raw material monomer of a trivalent or higher polyester resin as a crosslinking agent to the reaction system as necessary, and further proceeding the polycondensation reaction;
ii) After performing the polycondensation reaction, an addition polymerization reaction is performed, and after the addition polymerization reaction, a raw material monomer of a trivalent or higher polyester resin that serves as a cross-linking agent is added to the reaction system as necessary, and the polycondensation reaction is performed. A method of further proceeding the polycondensation reaction under suitable temperature conditions,
iii) Performing addition polymerization reaction and polycondensation reaction in parallel under temperature conditions suitable for the addition polymerization reaction, and after completion of the addition polymerization reaction, a trivalent or higher monovalent polyester resin serving as a crosslinking agent, if necessary A body is added to the reaction system, and the polycondensation reaction further proceeds under temperature conditions suitable for the polycondensation reaction

  In the composite resin, since the polyester resin and the addition polymerization resin are bonded via the both reactive monomers, as a specific production method, for example, the two reactive monomers may be used as a raw material monomer for the polyester resin and / or Used together with the raw material monomer of the addition polymerization resin, preferably used together with the raw material monomer of the addition polymerization resin, at least at any time before, during and after the step of addition polymerization of the raw material monomer of the addition polymerization resin The raw material monomer of the resin is present in the addition polymerization reaction system to cause polycondensation reaction.

Steps (a-2), (b-1), (b-2) In the aqueous medium, (a-2) is a composite resin, (b-1) is a polyester resin, and (b-2) is a polyester resin. A vinyl resin is added and dispersed by a disperser to prepare a dispersion in which each resin is dispersed in fine particles. Each resin is preferably dispersed in a volume-based median diameter of 60 to 500 nm.

Steps (a-3) and (b-3) An aqueous solution (aggregating agent) of polyvalent metal ions is added to the obtained resin particle dispersion of each resin, and the release agent particles are dispersed as necessary. Add liquid. In the present invention, the polyvalent metal ion contained in the flocculant reacts with the carboxyl group present on the surface of the core particle in the toner to form an ion cross-linked structure.
In this way, toner particles are formed by aggregation and fusion.
As the aggregation / fusion method, a salting-out fusion method is preferable. The salting-out fusion method is a method in which aggregation and fusion are advanced in parallel, and when the aggregated particles have grown to a desired particle size, an aggregation stop agent is added to stop the particle growth. In this method, heating for controlling the particle shape is continued as necessary.

The size of the toner particles is preferably 3 to 10 μm in terms of volume-based median diameter, and particularly preferably 3 to 7 μm. The volume-based median diameter of the core particles is a device in which a computer system (Beckman Coulter) equipped with data processing software "Software V3.51" is connected to Coulter Multisizer 3 (Beckman Coulter). Use to measure and calculate.
As a measurement procedure, 0.02 g of a sample is conditioned with 20 ml of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10-fold with pure water for the purpose of dispersing the sample). Then, ultrasonic dispersion is performed for 1 minute to prepare a sample dispersion. The prepared dispersion is pipetted into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand until the display concentration of the measuring instrument becomes 5 to 10%. By setting this concentration range, a reproducible measurement value can be obtained. In the measuring instrument, the frequency value is calculated by dividing the range of 2 to 60 μm, which is the measurement range, into 256 divisions with a measurement particle count of 25000, an aperture diameter of 100 μm. The particle diameter of 50% from the larger volume integrated fraction is defined as the volume-based median diameter.

  The said aqueous medium means that a main component (50% mass or more) consists of water. Examples of components other than water include organic solvents that dissolve in water. For example, methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like can be mentioned.

In addition, it is good also as passing through a maturing process after an aggregation / fusion process.
Specifically, the heating temperature is lowered in the agglomeration / fusion process to suppress the progress of fusion between the particles and to make the agglomerated particles uniform. Thereafter, in the ripening step, the surface of the toner particles is controlled to have a uniform shape by lowering the heating temperature and lengthening the time.

(A-4) Cooling / Washing Step In the cooling / washing step, the obtained dispersion of toner particles is cooled at a cooling rate of, for example, 1 to 20 ° C./min. When cooled to a predetermined temperature, the toner particles are solid-liquid separated from the cooled dispersion of toner particles. Solid-liquid separation may be any method other than centrifugation, such as vacuum filtration using a Nutsche or the like, filtration using a filter press or the like. Next, the toner cake obtained by solid-liquid separation (wet toner particles prepared in a cylindrical shape such as a cake) is washed to remove deposits such as surfactants and salting-out agents.

(A-5) Drying step In the drying step, the washed toner cake is dried. For the drying treatment, a spray dryer, a vacuum freeze dryer, a vacuum dryer or the like can be used. The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

(A-6) External Addition Processing Step In the external addition processing step, an external additive is mixed with the toner particles obtained by drying to obtain an electrostatic charge developing toner.

(式中、ＲＯ及びＯＲはオキシアルキレン基であり、Ｒはエチレン及び／又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの付加モル数を示し、それぞれ正の数であり、ｘとｙの和の平均値は1〜16が好ましく、1〜8がより好ましく、1.5〜4がさらに好ましい)で表されるビスフェノールＡのアルキレンオキサイド付加物が好ましい。かかるビスフェノールＡのアルキレンオキサイド付加物の含有量は、耐久性の観点から、アルコール成分中、50モル％以上が好ましく、60モル％以上がより好ましく、80モル％以上がさらに好ましく、90モル％以上がよりさらに好ましい。 Next, the material used for manufacturing the foil transfer surface forming toner will be described.
In addition, the polyester resin and vinyl resin in the method (a) can be the same as the polyester resin and vinyl resin in the method (b).
<Polyester resin>
The polyester resin is obtained by polymerizing a raw material monomer of the polyester resin. In the present invention, a polyester resin is used from the viewpoint of fixability and durability of the toner for forming a foil transfer surface.
The raw material monomer for polyester is not particularly limited, and examples thereof include a raw material monomer containing an alcohol component composed of a divalent or higher alcohol and a carboxylic acid component composed of a divalent or higher carboxylic acid compound.
As the alcohol having a valence of 2 or more, from the viewpoint of storage stability of the toner, the formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y represent the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable, and an alkylene oxide adduct of bisphenol A is preferable. The content of the alkylene oxide adduct of bisphenol A is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 80 mol% or more, and 90 mol% or more in the alcohol component from the viewpoint of durability. Is even more preferable.

  Examples of the alkylene oxide adduct of bisphenol A represented by the above formula (I) include ethylene oxide adducts having 2 carbon atoms such as polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene Examples thereof include propylene oxide adducts having 3 carbon atoms such as propylene-2,2-bis (4-hydroxyphenyl) propane.

  As alcohol components other than the alkylene oxide adduct of bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol , Pentaerythritol, glycerol, trimethylolpropane and the like.

  Examples of the divalent or higher carboxylic acid compound include adipic acid, fumaric acid, maleic acid, succinic acid (for example, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isooctenyl succinic acid, Aliphatic carboxylic acids such as succinic acid substituted with alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms such as isooctyl succinic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2, 4-Benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, aromatic carboxylic acids such as pyromellitic acid, anhydrides of these acids and lower alkyl (C1-3) esters, etc. Is mentioned. In addition, the acids as described above, anhydrides of these acids, and alkyl esters of the acids are collectively referred to as carboxylic acid compounds in this specification.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoint of adjusting the molecular weight and improving the offset resistance of the toner.

  The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, in an inert gas atmosphere at a temperature of 180 to 250 ° C., but can be performed in the presence of an esterification catalyst, a polymerization inhibitor, or the like. preferable. Examples of the esterification catalyst include tin (II) compounds having no Sn—C bond, such as dibutyltin oxide, titanium compounds, tin octylate, etc., and these can be used alone or in combination.

Further, as the polyester resin, a crystalline polyester resin or an amorphous polyester resin may be used. However, since the crystalline polyester resin has superior meltability compared to the amorphous polyester resin, The viscosity is remarkably reduced, and the toner image after fixing tends to be thicker than the image before fixing. If the toner image is thick, there is a risk of promoting the occurrence of burrs. Therefore, in the present invention, it is preferable to use an amorphous polyester resin.
Here, the presence or absence of crystallinity in the polyester resin refers to a resin having a clear endothermic peak instead of a stepwise endothermic change in differential scanning calorimetry (DSC). The clear endothermic peak specifically means a peak in which the half-value width of the endothermic peak is within 15 ° C. when measured at a rate of temperature increase of 10 ° C./min in differential scanning calorimetry (DSC). To do.

《Vinyl resin》
The vinyl resin is obtained by polymerizing a raw material monomer of a vinyl resin.
As a raw material monomer for the vinyl resin, at least styrene is preferably used, and a styrene acrylic resin is particularly preferable. The content of styrene is preferably from 30 to 95% by weight, more preferably from 60 to 92% by weight, and even more preferably from 80 to 92% by weight, based on the raw material monomer of the addition polymerization resin, from the viewpoint of toner storage stability.

  As raw material monomers for addition polymerization resins other than styrene, styrene derivatives such as α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; acetic acid Vinyl esters such as vinyl and vinyl propionate; alkyl (carbon number 12 to 22) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl methyl ether, etc. Vinyl ethers; vinylidene halides such as vinylidene chloride; and vinyl resin monomers such as N-vinyl compounds such as N-vinylpyrrolidone. Among these, ease of control of polymerization reaction and toner From the viewpoint of high-temperature offset resistance, (meth) actyl having a long-chain alkyl group on the side chain Alkyl Le acid (carbon number 12 to 22) esters. In the present specification, “(meth) acryl” means methacrylic acid and / or acrylic acid.

  12-22 are preferable and, as for carbon number of the alkyl group in the alkyl ester of (meth) acrylic acid, 14-22 are more preferable.

  The content of alkyl (carbon number 12 to 22) ester of (meth) acrylic acid is preferably 5 to 70 wt%, more preferably 8 to 40 wt%, and more preferably 8 to 20 wt% in the raw material monomer of the vinyl resin. Further preferred.

  In addition, the weight ratio of styrene and alkyl (carbon number 12 to 22) ester of (meth) acrylic acid [styrene / alkyl (carbon number 12 to 22) ester of (meth) acrylic acid] is the high temperature offset resistance of the toner. From the viewpoint, 100/50 to 100/5 is preferable, and 100/30 to 100/5 is more preferable.

  Furthermore, the total content of styrene and alkyl (carbon number 12-22) ester of (meth) acrylic acid is preferably 70% by weight or more, more preferably 80% by weight or more, in the raw material monomer of the vinyl resin, 90% by weight. % Or more is more preferable.

The addition polymerization reaction can be carried out by a conventional method, for example, in the presence of a radical polymerization initiator, a crosslinking agent or the like, in an organic solvent or in the absence of a solvent, but the temperature condition is preferably 110 to 200 ° C., 140 to 180 ° C is more preferred.
Examples of the radical polymerization initiator include dialkyl peroxide, dibutyl peroxide, butyl peroxy-2-ethylhexyl monocarboxylic acid and the like, and these are used alone or in combination.
The abundance of the radical polymerization initiator in the reaction system controls the molecular weight peak top value of the vinyl resin, and from the viewpoint of improving the low temperature fixing property, high temperature offset resistance and durability of the toner, 10-25 mass parts is preferable with respect to 100 mass parts in total, and 12-22 mass parts is more preferable.

<Amotropic monomer>
Both reactive monomers are used for the production of the composite resin (a-1).
Both reactive monomers have at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably a hydroxyl group and / or carboxyl. It is preferably a compound having a group, more preferably a carboxyl group and an ethylenically unsaturated bond, that is, a vinyl carboxylic acid. Specific examples of the both reactive monomers include, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like, and these hydroxyalkyl (1 to 3 carbon atoms) esters may be used. In view of the above, acrylic acid, methacrylic acid and fumaric acid are preferable.

  In addition, it is preferable from the viewpoint of durability that a monovalent vinyl carboxylic acid is used as the bireactive monomer rather than a polyvalent vinyl carboxylic acid. This is presumably because the monovalent vinyl carboxylic acid is highly reactive with the raw material monomer of the addition polymerization resin and is therefore easily hybridized. On the other hand, when a dicarboxylic acid such as fumaric acid is used as the bireactive monomer, the durability is slightly inferior. This is presumably because the dicarboxylic acid has a low reactivity with the raw material monomer of the addition polymerization resin and is difficult to uniformly hybridize, and thus takes a domain structure.

  From the viewpoint of improving the low-temperature fixability, high-temperature offset resistance and durability of the toner, the amount of both reactive monomers used is 1-10 parts by mass with respect to 100 parts by mass of the total amount of raw material monomers of the addition polymerization resin. Preferably, 4-8 mass parts is more preferable, 0.3-8 mass parts is preferable with respect to 100 mass parts of total amounts of the raw material monomer of a polyester resin, and 0.5-5 mass parts is more preferable.

<Release agent>
Examples of the wax (release agent) that can be used in the toner for forming a foil transfer surface of the present invention include conventionally known waxes. Specific examples include the following.
(I) Hydrocarbon wax (ii) Ester wax (iii) Amide wax Ethylenediamine dibehenylamide, trimellitic acid tristearylamide, etc.
(IV) Dialkyl ketone waxes, distearyl ketone, etc. (v) Others Carnauba wax, Montan wax, etc.

<Others>
The toner for forming a foil transfer surface in the present invention may use a charge control agent, an external additive or the like as necessary.
Examples of the charge control agent include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium chlorides, azo metal complexes, salicylic acid metal salts or metal complexes thereof. Examples of the metal contained include Al, B, Ti, Fe, Co, and Ni. Particularly preferred as the charge control agent is a metal complex compound of a benzylic acid derivative.

  As the external additive, in addition to the known hydrophobic silica and hydrophobic metal oxide, it is particularly preferable to add cerium oxide particles or higher alcohol particles having 20 to 50 carbon atoms from the viewpoint of filming resistance. In the case of adding cerium oxide particles, those having a number average particle diameter of 150 to 800 nm are preferably used and more preferably 250 to 700 nm are used from the viewpoint of enhancing filming resistance. Further, the addition amount of the cerium oxide particles is preferably 0.5 to 3.5% by mass with respect to the toner, and by setting the amount to 0.5 to 3.5% by mass, good cleaning properties can be obtained. It is maintained and the effect of filming resistance can be stably obtained. In addition, in the case where the addition amount is excessive, the adhesive strength of the toner particles melted during heat fixing is suppressed and the fixing strength is lowered. However, by setting the above range, such a problem of lowering the fixing strength does not occur.

Next, the foil transfer method according to the present invention will be described.
[Foil transfer method]
FIG. 1 is a diagram for explaining the foil transfer method of the present invention, and in particular, the foil transfer method reflecting the steps (4) to (6) among the steps (1) to (6) described above. It is the schematic diagram which showed the procedure of.
That is, a foil transfer surface is formed on the substrate through the electrostatic latent image forming step (1), the foil transfer surface forming step (2) and the first transfer step (3) which are not shown in FIG. The foil is supplied to the foil transfer surface, the supplied foil is brought into contact with the foil transfer surface, and heating is performed in this state to transfer the foil to the foil transfer surface.
Hereinafter, FIG. 1 will be described in detail.

FIG. 1A is a cross-sectional view showing a state where the foil transfer surface H is fixed on the substrate P using the foil transfer surface forming toner T on the sheet-like substrate P (fixing step (4)). FIG.
A method for forming the foil transfer surface H on the substrate P through the steps (1) to (3) will be described later. FIG. 1A is a cross-sectional view of a sheet-like substrate P on which a foil transfer surface produced using the toner according to the present invention is formed. A method for forming the foil transfer surface H on the substrate P through the steps (1) to (3) will be described later.

FIG. 1B shows a state in which the transfer foil F having at least the adhesive layer f1 is supplied onto the substrate P (supplying step (5)). The transfer foil F has the adhesive layer f1 that is the foil transfer surface H. Supplied to form a contact state. At this time, the supplied adhesive layer f1 of the transfer foil F is assumed to be in contact with the entire surface of the base P, and at least in contact with the foil transfer surface H formed in a convex shape on the surface of the base P. It can be said that it forms. On the surface of the foil transfer surface H formed using the above-mentioned toner for forming the foil transfer surface, the toner and the adhesive layer f1 are melted by heating, and a state in which the toner easily adheres to the adhesive layer f1 of the transfer foil F is formed. Presumed to be.
The transfer foil F used in the present invention has at least an adhesive layer f1 and a foil layer f2 on a base film f0. Here, the layer configuration other than the adhesive layer f1 and the foil layer f2 is omitted. . The transfer foil F that can be used in the present invention will be described later.

FIG. 1 (c) shows a state (second transfer step (6)) in which the transfer foil F is passed between the heating and pressurizing rollers R1 and R2 as heating means while being in contact with the base P. In the state where the adhesive layer f1 of the transfer foil F is in contact with the foil transfer surface H on the substrate P, it passes between the heating and pressing rollers R1 and R2 which are heating means.
By passing between the heat and pressure rollers R1 and R2, the foil transfer surface H and the adhesive layer f1 of the transfer foil F are melted, and after passing, the foil transfer surface H and the adhesive layer f1 are cooled and cured. At this time, the adhesive layer f1 of the transfer foil F in contact with the foil transfer surface H of the transfer foil F intersects to form a strong adhesive state. Thus, in the present invention, the transfer foil F forms an adhesive state with the foil transfer surface H via the adhesive layer f1 in contact with the foil transfer surface H formed in a convex shape on the base P. It is possible to transfer the foil layer f <b> 2 from the transfer foil F into a shape that faithfully corresponds to the shape of the foil transfer surface H.

  FIG. 1 (d) shows a state in which the transfer foil F is peeled off from the substrate P. When the transfer foil F is peeled off, as shown in FIG. 1 (e), only on the foil transfer surface H on the substrate P. The foil layer f2 is transferred together with the adhesive layer f1. Here, the foil layer f2 can be transferred to a shape corresponding to the shape of the foil transfer surface H by using the foil transfer surface forming toner according to the present invention, and without using a metal stamping die. It is possible to accurately transfer the foil layer f2 having a predetermined shape without causing chipping or burrs.

Next, an example of a foil transfer surface forming apparatus used in the foil transfer method according to the present invention will be described.
FIG. 2 is a diagram showing an internal configuration of the foil transfer surface forming apparatus.
The foil transfer surface forming apparatus is capable of carrying out the steps (1) to (3) among the steps (1) to (6) described above, and is a photoconductor that forms an electrostatic latent image by exposure. The foil transfer surface forming toner is supplied to the photoconductor to form a foil transfer surface corresponding to the electrostatic latent image. The formed foil transfer surface is transferred from the photoreceptor to the substrate.

In the foil transfer surface forming apparatus 1 in FIG. 2, an electrostatic latent image is formed by irradiating the exposure light L onto the photoconductor 11 charged by the charging roller 12 in the drawing (the electrostatic latent image in (1)). Forming step).
The electrostatic latent image formed on the photoconductor 11 receives the supply of the foil transfer surface forming toner from the foil transfer surface forming toner supply device 21 disposed in the vicinity of the photoconductor 11, thereby changing the foil transfer surface. Form (foil transfer surface forming step (2)). At this time, the built-in toner supply roller 14 rotates in the toner transfer device 21 for forming the foil transfer surface, and the toner attached to the toner supply roller 14 is supplied to the photoconductor 11, and the foil is transferred onto the photoconductor 11. Form a surface.

  Next, when the charge on the photoconductor 11 is neutralized by the static elimination lamp 22, the foil transfer surface on the photoconductor 11 is transferred onto the substrate P at the transfer portion where the photoconductor 11 and the transfer roller 13 are close to each other (see FIG. (3) First transfer step). The substrate P shown in FIG. 2 has a sheet shape typified by transfer paper, and is transported to a transfer portion by a transport roller 23 from a paper feed cassette (not shown). The transfer roller 13 has a charge opposite in polarity to the foil transfer surface forming toner. Is granted. The substrate P can transfer the foil transfer surface from the photoconductor 11 by the electrostatic action of the charge having the reverse polarity applied by the transfer roller 13.

  The substrate P to which the foil transfer surface has been transferred is separated from the photoconductor 11 and then conveyed to a fixing device (not shown) by the conveyance belt 24. The fixing device has a fixing means composed of, for example, a heating roller and a pressure roller, and melts and fixes the foil transfer surface formed on the substrate P (fixing step (4)).

  2, an electrostatic latent image corresponding to the shape of the foil is formed on the photoconductor 11, and the foil on the photoconductor 11 is supplied by supplying the foil transfer surface forming toner. A transfer surface is formed. The foil transfer surface formed on the photoconductor 11 is transferred to the base P by the transfer roller 13 and then fixed by a fixing device.

Note that the charging roller 12H in the drawing can charge the photoreceptor 11 by the following procedure, for example. That is, the charging roller 12 receives a bias voltage composed of a direct current (DC) component and an alternating current (AC) component from the power source 27 to charge the photosensitive member 11.
Charging using the charging roller 12 shown in FIG. 2 is a so-called contact method. In the present invention, in addition to the charging method shown in FIG. 2, non-contact charging used in the apparatus shown in FIG. It is also possible to do this. The bias voltage applied to the charging roller 12 includes, for example, a DC bias of ± 500 to 1000 V that is a direct current component and an AC bias of 100 Hz to 10 kHz and 200 to 3500 V that are alternating current components. .

  The transfer roller 13 shown in FIG. 2 is formed on the photoconductor 11 at the transfer site by receiving a bias voltage composed of a direct current (DC) component and an alternating current (AC) component from the power source 28, similarly to the charging roller 12. The foil transfer surface is transferred onto the substrate P. As a specific example of the bias voltage applied to the transfer roller 13, as in the specific example of the bias voltage applied to the charging roller 12, a DC bias of DC component ± 500 to 1000 V and an AC component of 100 Hz to 10 kHz, 200 to There is a superposition of 3500V AC bias.

  The charging roller 12 and the transfer roller 13 are driven or forcibly rotated while being pressed against the photoconductor 11. The pressing force of these rollers to the photoconductor 11 is, for example, 9.8 × 10−2 to 9.8 × 10−1 N / cm, and the rotational speed of the roller is, for example, 1 of the peripheral speed of the photoconductor 11. ~ 8 times. The pressing force of the roller to the photoconductor 11 can be realized by applying a pressing force of about 1N to 10N to both ends of the charging roller 12, for example.

  Note that the photoconductor 11 having the foil transfer surface transferred to the substrate P is removed by a cleaning blade 25b provided in the cleaning device 25 so that the next foil transfer surface is formed.

  In the present invention, it is also possible to form a foil image and a visible image on the substrate P on which the foil transfer surface is formed. The method for forming a visible image on the substrate P is not particularly limited, and for example, it may be prepared using a known image forming method such as an electrophotographic method, a printing method, an ink jet method, or a silver salt photographic method. Is possible. For example, after forming a foil transfer surface on the substrate P and transferring the transfer foil onto the foil transfer surface, a toner image can be created around the transfer foil by an electrophotographic image forming method. In addition, it is possible to create an image with different colors by placing color toner on the transfer foil, and by these methods, it is possible to give further bright expression to the substrate to which the transfer foil is transferred. .

  FIG. 3 is a cross-sectional configuration diagram of a foil transfer surface forming apparatus capable of forming the foil transfer surface and the electrophotographic full-color image formation of FIG. 2 described above. The foil transfer surface forming apparatus shown in FIG. 3 has substantially the same configuration as the foil transfer surface forming apparatus 1 shown in FIG. 2, and includes a fixing device 50 that cures the formed foil transfer surface H by heating and pressing. It is what is installed.

  This foil transfer surface forming apparatus has the same configuration as an electrophotographic image forming apparatus called a so-called “tandem color image forming apparatus”, and has a foil transfer surface toner image forming unit 20H and yellow, magenta, cyan, or The color toner image forming portions 20Y, 20M, 20C, and 20Bk that form a black toner image, and the foil transfer surface forming toner image forming portion 20H or the color toner image forming portions 20Y, 20M, 20C, and 20Bk are formed. An intermediate transfer unit 10 that transfers a toner image onto a substrate P (image support), a fixing device 50 that fixes the toner image by applying pressure while heating the substrate P (image support), and a substrate P (image). And a foil transfer device 70 for supplying a transfer foil 80 (see FIG. 4) to the support.

  The colored toner image forming unit 20Y forms a yellow toner image, the colored toner image forming unit 20M forms a magenta toner image, and the colored toner image forming unit 20C forms a cyan toner image. Then, a black toner image is formed in the colored toner image forming unit 20Bk.

  The foil transfer surface toner image forming unit 20H includes a photoreceptor 11H that is an electrostatic latent image carrier, a charging unit 23H that applies a uniform potential to the surface of the photoreceptor 11H, and a uniformly charged photoreceptor 11H. An exposure unit 22H that forms an electrostatic latent image of a desired shape thereon, a developing unit 21H that transports the foil transfer surface forming toner onto the photoconductor 11H to visualize the electrostatic latent image, and after the primary transfer And a cleaning unit 25H that collects residual toner remaining on the photoconductor 11H.

  The colored toner image forming portions 20Y, 20M, 20C, and 20Bk are uniform on the surfaces of the photoreceptors 11Y, 11M, 11C, and 11Bk that are electrostatic latent image carriers and the photoreceptors 11Y, 11M, 11C, and 11Bk. Charging means 23Y, 23M, 23C, and 23Bk for providing an appropriate potential, and exposure means 22Y, 22M, and 22C for forming electrostatic latent images of a desired shape on the uniformly charged photoreceptors 11Y, 11M, 11C, and 11Bk. , 22Bk, developing means 21Y, 21M, 21C, 21Bk for conveying the color toner onto the photoreceptors 11Y, 11M, 11C, 11Bk to visualize the electrostatic latent images, and the photoreceptors 11Y, 11M, Cleaning means 25Y, 25M, 25C, and 25Bk for collecting the residual toner remaining on 11C and 11Bk are provided.

  The intermediate transfer unit 10 includes an intermediate transfer member 16, a primary transfer roller 13H for transferring the foil transfer surface forming toner image formed by the foil transfer surface toner image forming unit 20H to the intermediate transfer member 16, and a colored toner image. Transferred onto the intermediate transfer body 16 by the primary transfer rollers 13Y, 13M, 13C, and 13Bk for transferring the colored toner images formed by the forming portions 20Y, 20M, 20C, and 20Bk to the intermediate transfer body 16, and the primary transfer roller 13H The transferred toner image for forming the foil transfer surface or the visible toner image transferred onto the intermediate transfer body 16 by the primary transfer rollers 13Y, 13M, 13C, and 13Bk is transferred onto the image support P on which the foil image is formed. A secondary transfer roller 13 </ b> A and a cleaning unit 12 </ b> H that collects residual toner remaining on the intermediate transfer body 16 are included.

  The intermediate transfer body 16 has an endless belt shape that is stretched by a plurality of support rollers 16a to 16d and is rotatably supported.

  The fixing device 50 is provided in a state in which a pair of heat and pressure rollers 51 and 52 are in pressure contact with each other and a nip portion N is formed in the pressure contact portion.

  As shown in FIG. 4, the foil transfer device 70 includes a foil transfer roller 73a that is driven by appropriate driving means and rotated clockwise, and a foil transfer roller 73b that is rotated by being driven by the foil transfer roller 73a. The sheet P is provided in a state of being pressed against each other via a long sheet-shaped transfer foil 80 having a transfer foil 80 to be supplied to the substrate P (image support), and runs through the transfer foil 80. Conveying means 79 is provided.

  The foil transfer device 70 includes a separation mechanism (not shown) in which the foil transfer rollers 73a and 73b are separated from each other. The separation mechanism further forms a toner image after forming the foil image. When the substrate P (image support) on which the foil image discharged from the fixing device 50 and the visible image are formed passes through the foil transfer device 70, the foil transfer rollers 73a and 73b are separated from each other. Change to state.

  The conveying means 79 for running the transfer foil 80 includes an original winding portion 71 having an original winding roller 71A around which the transfer foil 80 is wound and reverse tension is applied to prevent the transfer foil 80 from being loosened, and a drive source. And the winding portion 72 having the winding roller 72A rotated counterclockwise (arrow direction in FIG. 4), and the traveling direction of the transfer foil 80 is the same as the moving direction of the surface of the foil transfer roller 73a. It is arranged as follows.

  The rotational speed of the take-up roller 72A of the transport means 79 is such that the transport speed of the transfer foil 80 at the pressure contact portion of the foil transfer rollers 73a and 73b is the same as the transport speed of the substrate P (image support) at the pressure contact portion. It is said.

  The foil transfer rollers 73a and 73b have the same function as the heating and pressing rollers R1 and R2 in FIG. 1, and one or more rollers are provided with a heating source (not shown).

Next, the transfer foil that can be used in the present invention will be described.
As shown in FIG. 1, the transfer foil F usable in the present invention exhibits at least a film-like support f0 made of a resin or the like, a foil layer f2 containing a colorant, a metal, or the like, and adhesiveness. An adhesive layer f1 containing an organic material is provided, and the foil layer f2 and the adhesive layer f1 are transferred onto the substrate P.

  First, the support f0 is a film or sheet made of a resin or the like. Examples of the material of the support f0 include known resin materials such as polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polypropylene (PP) resin, polyether sulfone resin, and polyimide resin. In addition to these resin materials, materials such as paper can be used.

  Further, as the support f0, one having a single layer structure or a multilayer structure can be used. In the case of adopting a multilayer structure for the support f0, the support f0 preferably includes a release layer that can be used for adjusting the peeling resistance as the outermost surface layer on the foil layer f2 side. Examples of the material for the release layer include a thermosetting resin using melamine or isocyanate as a curing agent, a UV or electron beam curable resin containing an acrylate or epoxy resin, and a known release agent added thereto. It is done. Examples of known release agents that can be added to the release layer include fluorine-based or silicon-based monomers or polymers.

  The foil layer f2 contains a colorant, a metal material, and the like, and expresses an aesthetic appearance after being transferred onto the substrate P. When transferring onto the substrate P, the foil layer f2 is required to have a performance of peeling more smoothly than the support f0. Since the outermost surface of the substrate P is formed after the transfer, durability is also required. The foil layer f2 can be formed by applying a known resin that satisfies the above performance on the support f0 using a coater such as a gravure coater, a micro gravure coater, and a roll coater. Examples of such a known resin include an acrylic resin, a styrene resin, a melamine resin, and the like, and the resin can be colored by adding a known dye or pigment.

  Moreover, when forming the finished foil which has metallic luster, it is possible to form by providing a reflection layer in the above-mentioned resin by a well-known method using a metal etc. As a metal material for forming the reflective layer, for example, a nickel-chromium-iron alloy, an alloy such as bronze, aluminum bronze, or the like can be used in addition to a carrier such as aluminum, tin, silver, chromium, nickel, and gold. It is. Examples of a method for forming the reflective layer using the metal material include known methods such as vapor deposition, sputtering, and ion plating, and a reflective layer having a thickness of about 10 nm to about 100 nm is formed. Is possible. In addition, the reflective layer can be subjected to a patterning process for imparting a regular pattern by using a known processing method such as a washing sea light process, an etching process, or a laser process.

  The adhesive layer f1 contains a heat-sensitive adhesive called a so-called hot melt type that develops tackiness by heating. Examples of the heat-sensitive adhesive include known thermoplastic resins that can be used for hot-melt type adhesives such as acrylic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, and ethylene-vinyl alcohol copolymer. Can be mentioned. The adhesive layer f1 can be formed by applying the above-described resin on the foil layer f2 using a coater such as a gravure coater, a micro gravure coater, and a roll coater.

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.
<Manufacture of composite resin SE-1>
St-Ac (styrene acrylic) constituents shown in Table 1 below, a chain transfer agent (NOM), both reactive monomers (acrylic acid) and a radical polymerization initiator (potassium peroxide) were placed in a dropping funnel. Put the polyester constituents shown in Table 1 into a 10 L reaction vessel equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introducing device, raise the temperature to 170 ° C., and stir the St-Ac constituents from the previous dropping funnel under stirring. After dropping, aging was performed for 1 hour. Thereafter, 40 parts by mass of tin octylate as a polycondensation catalyst was added, the temperature was raised to 235 ° C., the reaction was allowed to proceed for 8 hours under normal pressure (101.3 kPa), and then the desired softening point was reached under reduced pressure (20 kPa). The reaction was continued until the value reached "Composite Resin SE-1".

<Manufacture of composite resins SE-2 to SE-6>
In the production of the composite resin SE-1, composite resins SE-2 to 6 were obtained based on the components shown in Table 1, respectively.

<Preparation of composite resin particle dispersion A1>
500 parts by mass of the obtained “Composite Resin SE-1” was dissolved in 2000 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.) and mixed with 3200 parts of a 0.26% by mass sodium lauryl sulfate solution prepared in advance. While stirring, ultrasonically disperse with an ultrasonic homogenizer “US-150T” (manufactured by Nippon Seiki Seisakusho) at V-LEVEL 300 μA for 2 hours, and then heated to 40 ° C., a diaphragm vacuum pump V-700 (manufactured by BUCHI) is used. The ethyl acetate was completely removed while being stirred under reduced pressure for 3 hours to obtain a “composite resin particle dispersion A1” having an average particle diameter (median (D ₅₀ ) in volume average) of 210 nm.

<Preparation of composite resin particle dispersions A2 to A6>
In the preparation of the composite resin particle dispersion A1, the composite resin particle dispersions A2 to A6 were changed in the same manner except that “composite resin SE-1” was changed to “double resin SE-2 to SE-6”, respectively. Obtained.

表１中、ＮＯＭとはｎ−オクチルメルカプタン、ＫＰＳとは過酸化カリウム、ＢＰＡ−ＰＯとはビスフェノールＡプロピレンオキサイド付加物、ＢＰＡ−ＥＯとはビスフェノールＡエチレンオキサイド付加物を示す。また、表１中の単位は、質量部を示す。

In Table 1, NOM is n-octyl mercaptan, KPS is potassium peroxide, BPA-PO is bisphenol A propylene oxide adduct, and BPA-EO is bisphenol A ethylene oxide adduct. Moreover, the unit in Table 1 shows a mass part.

<Preparation of St-Ac resin particle dispersion B1>
(First stage polymerization)
A solution prepared by dissolving 4.3 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate in 1270 ml of ion-exchanged water was charged into a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device. After heating to ℃, 124 parts by mass of styrene, 45 parts by mass of n-butyl acrylate, 12 parts by mass of methacrylic acid, 0.5 parts by mass of n-octyl mercaptan, 77 parts by mass of microcrystalline wax (HNP-0190, manufactured by Nippon Seiki Co., Ltd.) A polymerizable monomer solution in which a part is dissolved at 80 ° C. is added and mixed and dispersed for 15 minutes by a mechanical disperser “CREARMIX (manufactured by M Technique Co., Ltd.) having a circulation path, and emulsified particles (oil droplets) are dispersed. A dispersion containing was prepared.
Next, an initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 118 ml of ion-exchanged water is added to the dispersion, and the system is polymerized by heating and stirring at 80 ° C. for 1 hour to disperse the resin particles. A liquid was prepared.
(Second stage polymerization)
A solution prepared by dissolving 11 parts by mass of potassium persulfate in 201 ml of ion-exchanged water was added to the above resin particle dispersion. Under a temperature condition of 82 ° C., 386 parts by mass of styrene, 141 parts by mass of n-butyl acrylate, methacrylic acid A polymerizable monomer solution consisting of 37 parts by mass and 13 parts by mass of n-octyl mercaptan was added dropwise over 1 hour.
After completion of the dropwise addition, polymerization was performed by heating and stirring for 1 hour, and then cooling to 28 ° C. to obtain St-Ac resin particle dispersion B1.

<Preparation of amorphous polyester resin particle dispersion C1>
In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, 316 parts by mass of bisphenol A propylene oxide 2 mol adduct, 138 parts by mass of terephthalic acid, and 2 parts by mass of titanium tetraisopropoxide as a polycondensation catalyst. The reaction was divided into 10 times and reacted at 200 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under reduced pressure of 13.3 kPa (100 mmHg), and when the weight average molecular weight reached 15000, the reaction was stopped to produce an amorphous polyester resin.
200 parts by mass of the obtained amorphous polyester resin was dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.), mixed with 638 parts by mass of a 0.26 wt% sodium lauryl sulfate solution prepared in advance, and stirred. While using ultrasonic homogenizer “UT-150T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) for 30 minutes with V-LEVEL 300 μA for 30 minutes, the diaphragm vacuum pump V-700 (manufactured by BUCHI) was heated to 40 ° C. The ethyl acetate was completely removed while stirring under reduced pressure for 3 hours to obtain “amorphous polyester resin particle dispersion C1” having an average particle diameter (volume median diameter (D50)) of 180 nm. .

<Preparation of crystalline polyester resin particle dispersion C2>
In a reaction vessel equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device, 200 parts by mass of 1,10-dodecanedioic acid, 140 parts by mass of 1,9-nonanediol and titanium tetraisopropoxide 2 as a polycondensation catalyst The mass part was divided into 10 portions and reacted at 200 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Next, the reaction was carried out under reduced pressure of 13.3 kPa (100 mmHg), and when the weight average molecular weight reached 17000, the reaction was stopped to produce a crystalline polyester resin.
200 parts by mass of the obtained crystalline polyester resin was dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.), mixed with 638 parts by mass of a 0.26 wt% sodium lauryl sulfate solution prepared in advance, and stirred. While ultrasonically dispersing with an ultrasonic homogenizer “UT-150T” (manufactured by Nippon Seiki Seisakusho) at V-LEVEL 300 μA for 30 minutes, the diaphragm vacuum pump V-700 (manufactured by BUCHI) was heated to 40 ° C. The ethyl acetate was completely removed while being stirred under reduced pressure for 3 hours to obtain “crystalline polyester resin particle dispersion C2” having an average particle diameter (median diameter (D50) based on volume) of 190 nm.

<Preparation of release agent dispersion F1>
100 parts by mass of microcrystalline wax (HNP-0190: manufactured by Nippon Seiki Co., Ltd.), 21 parts by mass of an anionic surfactant (Neogen RK: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 860 parts by mass of ion-exchanged water were mixed to 110 ° C. After heating and dispersing using a homogenizer (Ultra Turrax T50: manufactured by IKA), dispersion treatment was performed using a Menton Gorin high-pressure homogenizer (Gorin) to obtain a release agent fine particle dispersion F-1. The average particle size of the release agent fine particles in the obtained dispersion was 250 nm.
<Preparation of Toner Particle 1>
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, 450 parts by mass (in terms of solid content) of composite resin particle dispersion A1 and 41 parts by mass of “release agent dispersion F1” (in terms of solid content) (In terms of solid content), 2 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate and 900 parts by mass of ion-exchanged water were added, the liquid temperature was adjusted to 25 ° C., and 25 wt% sodium hydroxide aqueous solution was added. The pH was adjusted to 10.
Next, as a polyvalent metal ion compound, an aqueous solution in which 70 parts by mass of magnesium chloride is dissolved in 105 ml of ion-exchanged water is added with stirring at 30 ° C. over 30 minutes, and after 3 minutes, the temperature rise is started. The system was heated to 80 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining the temperature at 80 ° C.
In this state, the particle size of the aggregated particles is measured with “Coulter Multisizer 3”, and when the desired particle size is reached, an aqueous solution in which 75 parts by mass of sodium chloride is dissolved in 290 ml of ion-exchanged water is added to the particles. Stop growth.
Further, by heating and stirring at a liquid temperature of 88 ° C. as a ripening step, toner particles are formed while fusing the particles until the average circularity becomes 0.960 as measured by “FPIA-2100”. Thereafter, the solution was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped.
The toner particles generated in the above process are solid-liquid separated with a basket-type centrifuge “MARK III model number 60 × 40” (manufactured by Matsumoto Kikai Co., Ltd.) to form a toner particle wet cake. In the basket type centrifuge, the filtrate is washed with ion exchange water at 45 ° C. until the electric conductivity of the filtrate reaches 5 μS / cm, and then transferred to “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.). The toner particles were obtained by drying to 0% by mass.

<Preparation of toner particles 2 to 6>
Toner particles 2 to 6 were obtained in the same manner as in the production of toner particles 1 except that the composite resin particle dispersion A1 was changed to the composite resin particle dispersions A2 to A6.

<Preparation of toner particles 7>
Composite resin particle dispersion A1, 126 parts by mass (in terms of solid content) of St—Ac resin particle dispersion B1, 324 parts by mass (in terms of solid content) of amorphous polyester resin particle dispersion C1, and “release agent dispersion Toner particles 7 were obtained in the same manner as in the production of toner particles 1 except that “F1” was changed to 30 parts by mass (in terms of solid content).

<Preparation of Toner Particles 8>
The composite resin particle dispersion A1, the St-Ac resin particle dispersion B1 is 126 parts by mass (in terms of solid content), the crystalline polyester resin particle dispersion C2 is 324 parts by mass (in terms of solid content), and “release agent dispersion F1 The toner particles 8 were obtained in the same manner as in the production of the toner particles 1 except that 30 parts by mass (in terms of solid content) was changed.

<Preparation of toner particles 9>
Toner particles 9 were obtained in the same manner as in the production of toner particles 1 except that the composite resin particle dispersion A1 was changed to the amorphous polyester resin particle dispersion C1.

<Preparation of Toner Particle 10>
Into a 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device, 450 parts by mass (converted to solid content) of composite resin particle dispersion A3 and 900 parts by mass of ion-exchanged water were charged, and the liquid temperature was adjusted. After adjusting to 25 ° C., the pH was adjusted to 10 by adding 25 wt% sodium hydroxide aqueous solution.
Next, an aqueous solution in which 200 parts by mass of sodium chloride was dissolved in 800 ml of ion-exchanged water was added over 30 minutes at 30 ° C. with stirring, and the temperature was increased after holding for 3 minutes. The temperature was raised to 90 ° C., and the particle growth reaction was continued while maintaining 90 ° C.
In this state, the particle size of the agglomerated particles is measured by “Coulter Multisizer III”, and when the desired particle size is reached, 1000 ml of ion-exchanged water is added to stop particle growth.
Further, by heating and stirring at a liquid temperature of 90 ° C. as a ripening step, toner particles are formed while fusing the particles until the average circularity becomes 0.960 as measured by “FPIA-2100”. Thereafter, the solution was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped.
The toner particles generated in the above process are solid-liquid separated with a basket-type centrifuge “MARK III model number 60 × 40” (manufactured by Matsumoto Kikai Co., Ltd.) to form a toner particle wet cake. In the basket type centrifuge, the filtrate is washed with ion exchange water at 45 ° C. until the electric conductivity of the filtrate reaches 5 μS / cm, and then transferred to “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.). The toner particles 10 were obtained by drying to 0% by mass.
Table 2 below shows the constituent components of the produced toner particles 1 to 10, the component ratio of styrene acrylic and polyester, the monomers for forming ionic crosslinks, and the types of polyvalent metals. In Table 2, MAA represents methacrylic acid.

<Preparation of toner developer for forming foil transfer surface>
The toner particles 1 to 10 are mixed with a ferrite carrier having a volume average particle diameter of 40 μm formed by coating a methyl methacrylate resin so that the toner concentration becomes 6% by mass, and takes the form of a two-component developer. Toner developers 1 to 10 for forming a foil transfer surface were prepared.

<Evaluation experiment>
(Evaluation conditions)
The adjusted “foil transfer surface forming toner developers 1 to 10” were respectively mounted on the foil transfer surface toner image forming portion 20H of the foil transfer surface forming apparatus having the configuration shown in FIG. 3 to form a foil transfer surface. The foil transfer surface was formed on a commercially available image support (substrate) “OK top coat + (basis weight 157 g / m ² , paper thickness 131 μm) (manufactured by Oji Paper Co., Ltd.)”. In the foil transfer surface forming apparatus, the foil transfer surface was formed by setting the supply amount of the foil transfer surface forming toner to 4 g / m ² .
The fixing speed of the image support in the fixing device 50 was set to 230 mm / sec, the surface material of the heating roller was set to polytetrafluoroethylene (PTFE), and the surface temperature of the heating roller was set to 135 ° C.
After forming the foil transfer surface with each toner on the image support using the foil transfer surface forming apparatus, the image support has the layer structure shown in FIG. 1 according to the procedure of the schematic diagram shown in FIG. The transfer foil was transferred onto a foil transfer surface formed on the image support using a commercially available transfer foil. In addition, “BL No. 2 Gold 2.8” manufactured by Murata Gold Leaf Co., Ltd. was used as the transfer foil.
The foil transfer was performed under the conditions shown below by the procedure shown in FIG. That is,
-Heating roll: a 3 mm thick silicone rubber layer placed on an aluminum base with an outer diameter of 100 mm and a thickness of 10 mm, and the surface temperature set to 150 ° C-Pressurizing roll: an outer diameter of 80 mm, thickness of 10 mm A silicone rubber layer with a thickness of 3mm is placed on an aluminum substrate, and the surface temperature is set to 100 ° C. Heat source: Halogen lamps are placed inside the heating roll and pressure roll, respectively (temperature controlled by a thermistor)
・ Nip width between heating roll and pressure roll: 7mm
-Image support conveyance speed: 200 mm / sec-Transfer material conveyance direction: A3 size transfer material is conveyed in the vertical direction-Evaluation environment: normal temperature and normal humidity environment (temperature 20 ° C., relative humidity 50% RH)
Under the above conditions, two types of foil image samples Sa and Sb shown in FIGS. 5A and 5B were prepared on the image support.
After evaluating the absence of the transfer foil in the foil image obtained above, the sheet is further passed through the fixing device at an image support conveying speed of 90 mm / sec.

About the transfer foil formed on the sample produced in the above procedure, the occurrence of burrs of the transfer foil on the foil transfer surface was evaluated. “Burr generation on the foil transfer surface” means that the internal cohesive force of the toner layer that bonds the paper and the foil image is too large when the transfer foil is peeled immediately after passing through the fixing device, and the foil is transferred more than necessary. It is to evaluate whether it is not done.
The generation of streaks on the foil transfer surface was evaluated by re-passing the foil image through the fixing device. “Generation of streaks on the foil transfer surface” evaluates whether or not the remeltability of the toner layer adhering to the foil by heat is insufficient.

(Generation of burrs on the foil transfer surface)
The foil image sample Sa formed on each sample was visually observed with the naked eye and a magnifying glass having a magnification of 10 times, and the presence or absence of foil burrs on the foil transfer surface was evaluated as follows. ◎, ○ and △ were accepted, and x was rejected. That is,
◎; No burr of the foil was observed even by loupe observation.
◯: Although there was no problem in the naked eye observation, the occurrence of minute burrs was observed by loupe observation in one or two places.
Δ: Level of no problem in visual observation, but burrs were observed in 3 or more places by loupe observation.
X: Generation | occurrence | production of the burr | flash of foil is recognized by visual observation.

(Presence of streaks)
The foil image sample Sb formed on each sample was visually observed with the naked eye and a magnifier with a magnification of 10 times, and the presence or absence of streaks on the foil transfer surface was evaluated as follows. ◎, ○ and △ were accepted, and △ and x were rejected. That is,
A: No loss of foil was observed in the magnifying glass for all the foil images. O: Although there was no problem in the naked eye observation, there was one fine streak by the magnifying glass.
Δ: Level of no problem in visual observation, but there were two or more fine streaks by loupe observation.
X: Streaks of the foil are observed by visual observation.

The results of the above evaluation experiment are shown in Table 2.

From the results of Table 2, when forming a foil image using toner particles 1 to 4 to 8 having the configuration of the present invention, in the presence or absence of occurrence of burrs and streaks of the transfer foil on the foil transfer surface, It was within the above-mentioned acceptable range. On the other hand, when the foil image was formed using the toner particles 9 and 10 as the comparative example, the above-described failure range was observed in the presence or absence of streaks on the foil transfer surface.
Therefore, by using the toner for forming a foil transfer surface having the configuration of the present invention, a good adhesive force is imparted between the foil transfer surface and the transfer foil, and foil transfer is performed without generating burrs. It can also be seen that streaking can be suppressed by re-feeding the foil image to the fixing device.

DESCRIPTION OF SYMBOLS 1 Foil transfer surface formation apparatus 11 Photoconductor 12 Charging roller 13 Transfer roller 14 Toner supply roller 21 Foil transfer surface formation toner supply apparatus 22 Static elimination lamp 23 Conveyance roller 24 Conveyor belt 25 Cleaning device 25b Cleaning blade 27, 28 Power supply 10 Intermediate transfer Sections 11H, 11Y, 11M, 11C, 11Bk Photoconductor 12H Cleaning means 13H, 13Y, 13M, 13C, 13Bk Primary transfer roller 16 Intermediate transfer bodies 16a to 16d Support roller 20H Foil transfer surface toner image forming sections 20Y, 20M, 20C, 20Bk Colored toner image forming portions 21H, 21Y, 21M, 21C, 21Bk Developing means 22H, 22Y, 22M, 22C, 22Bk Exposure means 23H, 23Y, 23M, 23C, 23Bk Charging means 25H, 25Y, 25M, 25C, 25Bk Cleaner Fusing means 50 Fixing devices 51, 52 Heating and pressing roller 70 Foil transfer device 71 Original winding portion 71A Original winding roller 72 Winding portion 72A Take-up rollers 73a, 73b Foil transfer roller 79 Conveying means 80 Transfer foil F Transfer foil f0 Support f1 adhesive layer f2 foil layer
H foil transfer surface P substrate (image support)
R1, R2 Heating and pressing roller T Foil transfer surface forming toner (toner)
Sa, Sb foil image sample

Claims (6)

An electrostatic latent image forming step of forming an electrostatic latent image by exposing the photoreceptor;
A foil transfer surface forming step of forming a foil transfer surface by supplying toner to the photoreceptor on which the electrostatic latent image is formed;
A first transfer step of transferring a foil transfer surface formed on the photoreceptor to a substrate;
A fixing step of fixing the foil transfer surface transferred to the substrate;
Supplying the transfer foil to the substrate on which the foil transfer surface is fixed;
A second transfer step in which the transfer foil is heated under the state of being in contact with the foil transfer surface to transfer the transfer foil to the foil transfer surface, and a foil transfer method comprising:
The toner used in the foil transfer surface forming step contains at least a polyester resin and a vinyl resin having an ionic crosslinking structure.   After the second transfer step, a toner image is formed by fixing a toner image by forming a toner image on a substrate having a transfer foil transferred to the foil transfer surface and heating the substrate on which the toner image is formed. It has a process, The foil transfer method of Claim 1 characterized by the above-mentioned. The binder resin contained in the toner used in the foil transfer surface forming step is
The foil transfer method according to claim 1 or 2, wherein the content of the vinyl resin having an ionic cross-linked structure is 5% or more and 50% or less.   The foil transfer method according to any one of claims 1 to 3, wherein the toner used in the foil transfer surface forming step is a clear toner.   The foil transfer method according to any one of claims 1 to 4, wherein the polyester resin is an amorphous polyester resin. A foil transfer surface forming toner containing at least a binder resin,
The foil transfer surface forming toner, wherein the binder resin contains at least a polyester resin and a vinyl resin having an ionic crosslinking structure.

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