Bonding method, and toner set and bonding device

Abstract

To provide a bonding method, and a toner set and a bonding device that can achieve both good bonding strength and high-temperature resistant offset properties even when an image pattern for bonding is formed of a plurality of toner layers.SOLUTION: A bonding method includes the steps of forming a pattern in which a first toner layer and a second toner layer are stacked in this order on a sheet, and laminating the sheets so that the second toner layers are brought into contact with each other and heating the patterns to bond the sheets to each other, thereby obtaining a bonding object. The calorific value of the first toner H1 [J / g] and the calorific value of the second toner H2 [J / g] are the calorific value within a range from 35°C to 75°C at an exothermic peak in a DSC curve obtained by increasing the temperature of the toner to 180°C and then cooling the toner in differential scanning calorimetry, and satisfy the following formulas (1) and (2). (1) 6.0≤H2≤24.0. (2) H1<H2.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a bonding method, a toner set, and a bonding device used in producing bonded printed matter using electrophotography or the like. [Background technology]

[0002] A technology has been disclosed in the past in which, using an image forming device such as a printer or copier, a powder adhesive (hereinafter, also simply referred to as "toner") is patterned on a sheet as an adherend, the sheets are stacked and glued together, and then processed into a paper bag. Also disclosed is a technology in which a stack of multiple sheets is glued together by a booklet making device, which is a post-processing device, to make a booklet. When such a booklet making device is installed in an image forming device that forms a color image using toners of multiple colors, the toner for forming the toner layer for adhesion is usually determined in advance to be one color.

[0003] However, forming an adhesive toner layer using only one color of toner results in a greater consumption of the adhesive toner compared to the consumption of other colors of toner. Therefore, for example, Patent Document 1 proposes a configuration in which an adhesive toner layer is formed using multiple toners in an image forming device that forms a color image in order to avoid increasing the consumption of a specific toner. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2004-209858 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the inventors have found that when forming an adhesive toner layer using multiple toners in the production of the booklet as described above, the adhesive strength of the produced booklet may be insufficient depending on the physical properties of the toner and the stacking order of the toner layers. In addition, in a stacking order of the toner layers that provides sufficient adhesive strength for the booklet, the image area may melt and a phenomenon (high-temperature offset property) may occur in which a part of the image area is transferred to the fixing device. Therefore, there is a problem that it is difficult to achieve both high adhesive strength and high-temperature offset resistance.

[0006] The present disclosure is directed to an adhesion method, a toner set, and an adhesion device that can provide both good adhesive strength and high-temperature offset resistance even when an image pattern for adhesion is formed using multiple toner layers. [Means for solving the problem]

[0007] The present disclosure provides a bonding method, comprising: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the amount of heat generated in the first toner is H1 [J / g] and the amount of heat generated in the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 (1) H1 <H2 ···(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; the amount of heat generated in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; The present invention relates to a bonding method comprising the steps of:

[0008] The present disclosure also relates to a toner set for use in the bonding method, the toner set having the first toner and the second toner separately. Effect of the Invention

[0009] According to the present disclosure, it is possible to provide an adhesion method, a toner set, and an adhesion device that can provide both good adhesive strength and high-temperature offset resistance even when an image pattern for adhesion is formed using multiple toner layers. [Brief description of the drawings]

[0010] [Figure 1] Schematic diagram of the bonding device (image forming device) [Diagram 2] Diagram explaining how to align sheets [Diagram 3] Diagram explaining the thermocompression unit [Figure 4] Schematic diagram showing an example of an adhesive image pattern [Diagram 5] Diagram explaining the evaluation method for booklet adhesive strength [Figure 6] FIG. 1 is a diagram illustrating an adhesive image pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure will be described in detail below, but the present disclosure is not limited to these descriptions. In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints, unless otherwise specified. When a numerical range is described in stages, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0012] The bonding method according to the present disclosure includes: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; has. The adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on the surface. Yes. The calorific value of the first toner is H1 [J / g], and the calorific value of the second toner is H2 [J / g], where H1 and H2 satisfy the following formulas (1) and (2). 6.0≦H2≦24.0 (1) H1 <H2 ···(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; The heat release amount is the amount of heat released in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the above steps.

[0013] The present inventors have found that the above-mentioned structure makes it possible to achieve both sufficient adhesive strength and high-temperature offset resistance. The present inventors speculate that the reason for this is as follows.

[0014] The calorific value of the toner in the range of 35°C to 75°C in differential scanning calorimetry (DSC) corresponds to the amount of crystalline components such as wax and crystalline polyester resin precipitated on the surface of the toner in the fixing process. Therefore, the calorific value H2 [J / g] is considered to correspond to the amount of crystalline components precipitated on the surface of the second toner in the fixing process. Below, the case where wax is contained as a crystalline component in the toner will be described. The higher H2 is, the more the release action of the wax precipitated on the surface of the second toner layer works, and the higher the high-temperature offset resistance is improved. By making H2 6.0 J / g or more, the high-temperature offset resistance can be improved. If H2 is less than 6.0 J / g, the wax does not precipitate sufficiently, and the high-temperature offset resistance is insufficient.

[0015] On the other hand, the smaller H2 is, the better the adhesive strength is in the adhesion process step in which the adhesive image pattern having the fixed toner image of the second toner on its surface is superimposed and adhered after the fixing step. This is because the adhesion inhibition caused by the wax precipitated on the surface of the adhesive image pattern can be suppressed. By setting H2 to 24.0 J / g or less, sufficient adhesive strength can be obtained. If H2 is more than 24.0 J / g, the adhesion inhibition caused by the wax becomes large, making it difficult to obtain sufficient adhesive strength.

[0016] However, according to the study by the present inventors, it is difficult to achieve both high-temperature offset resistance and adhesive strength by only controlling H2 as described above. The present inventors have found that by making the calorific value H1 [J / g] of the first toner in differential scanning calorimetry (DSC) smaller than H2, that is, by satisfying the above formula (2), it is possible to achieve both high-temperature offset resistance and adhesive strength.

[0017] Usually, in unmelted toner, the wax is unevenly distributed inside the toner particles due to the difference in crystallinity between the binder resin and wax contained in the toner particles. In the fixing process (a process for forming an image pattern for adhesion) and the adhesion treatment process (a process for obtaining an adhesion product), the toner is sufficiently melted. Therefore, the molten wax can move freely in the molten binder resin. During fixing, the wax, which can now move freely in the binder resin, seeps out onto the surface of the fixed image (image pattern for adhesion), thereby achieving separation between the fixed image and the fixing device. On the other hand, in the adhesion treatment step performed after the fixing step, the surfaces of the adhesive image patterns are heated in a state of being overlapped. In this case, since the wax concentration of each of the overlapped adhesive image patterns is high, the wax concentration locally increases in the overlapped portion. At that time, the melted wax is thought to diffuse away from the overlapping portion (adhesive portion) and toward the sheet side so that the concentration gradient becomes smaller.

[0018] Therefore, when H1 is smaller than H2, it is considered that the wax unevenly distributed on the surface of the adhesive image pattern moves to the sheet side during the adhesion process. This action reduces the uneven distribution of the wax on the adhesion surface (the portion where the adhesive image patterns are superimposed on each other), improving the adhesive strength. As a result, it is possible to achieve both high-temperature offset resistance and adhesive strength. The present inventors speculate as follows about the reason why the wax behaves differently in the fixing process and the adhesion process. In the fixing process, the wax is heated from the surface of the second unfixed toner layer, and is heated for only a short time of about several msec while passing through the fixing device, so that the wax that has become mobile due to melting tends to move toward the heat source, that is, toward the surface of the adhesive image pattern. On the other hand, in the adhesion process, the adhesive image pattern is heated through the sheet, so the heat source is the sheet side. In addition, the heating time in the adhesion process is about 2 seconds, as described later, which is longer than that in the fixing process, and the wax is in a molten state for a longer time. Therefore, it is considered that the wax unevenly distributed on the adhesion surface moves toward the sheet side so that the unevenness is alleviated.

[0019] The difference between H2 and H1 (H2-H1) is preferably 1.5 J / g or more. H2-H1 is preferably 1.5 to 23.5 J / g, and more preferably 5.0 to 20.0 J / g. When H2-H1 is 1.5 J / g or more, the wax is more likely to migrate to the sheet side, so that the adhesive strength is further improved and it becomes easier to achieve a high degree of compatibility between high temperature offset resistance and adhesive strength.

[0020] H1 is preferably 2.0 to 18.0 J / g, and more preferably 4.0 to 15.0 J / g. By making H1 2.0 J / g or more, the releasing action of the wax works well, and the high temperature offset resistance can be further improved when the first toner is used alone for printing. Also, by making H1 18.0 J / g or less, the deposition of the wax is further suppressed, the fixing property of the first toner and the sheet is further improved, and the adhesive strength can be further improved.

[0021] From the viewpoint of achieving a high compatibility between high-temperature offset resistance and adhesive strength, H2 is preferably from 10.0 to 24.0 J / g, and more preferably from 10.0 to 21.0 J / g. H1 and H2 can be controlled by changing the amount or type of crystalline components such as wax. For example, increasing the amount of wax can increase the amount of heat generated, and decreasing it can decrease the amount of heat generated.

[0022] The first toner is preferably a black toner containing carbon black. For example, the first toner preferably contains toner particles, and the second toner preferably contains toner particles. The toner particles in the first toner preferably contain carbon black. Carbon black has a high oil absorption, so when the first toner is a black toner containing carbon black, the wax of the second toner is easily absorbed by the carbon black of the first toner when the second toner and the first toner are melted in the adhesion treatment step. Therefore, the wax on the surface of the second toner layer, which is the adhesion surface, is further reduced, and the adhesion strength is further improved.

[0023] In addition, the first toner and the second toner each contain a hydrocarbon wax, and the content of the hydrocarbon wax per 100 parts by mass of the binder resin or polymerizable monomer in the first toner is W1 [parts by mass], and the content of the hydrocarbon wax per 100 parts by mass of the binder resin or polymerizable monomer in the second toner is When the content of the hydrocarbon wax is W2 [parts by mass], it is preferable that W1 and W2 satisfy the following formulas (3) and (4). By satisfying the above, it is possible to more satisfactorily achieve both high-temperature offset resistance and adhesive strength. 5.8≦W2≦13.1 (3) W1 <W2 ···(4)

[0024] The larger W2 is, the more the release effect of the hydrocarbon wax works, and thus the high-temperature offset resistance is improved. By making W2 5.8 parts by mass or more, the high-temperature offset resistance can be improved. The difference between W2 and W1 (W2-W1) is preferably 0.5 parts by mass or more. W2-W1 is more preferably 0.5 to 9.7 parts by mass, and even more preferably 2.1 to 8.1 parts by mass. When W2-W1 is 0.5 parts by mass or more, the hydrocarbon wax is more likely to migrate to the sheet side, which further improves the adhesive strength and makes it easier to achieve a high degree of compatibility between high-temperature offset resistance and adhesive strength.

[0025] W1 is preferably 4.0 parts by mass to 10.7 parts by mass, and more preferably 5.0 parts by mass to 9.4 parts by mass. By making W1 4.0 parts by mass or more, the releasing action of the hydrocarbon wax works well, and the high temperature offset resistance can be further improved when the first toner is used alone for printing. In addition, by making W1 10.7 parts by mass or less, the deposition of the wax is further suppressed, the fixation of the first toner and the sheet is further improved, and the adhesive strength can be further improved. From the viewpoint of achieving a high compatibility between high-temperature offset resistance and adhesive strength, W2 is preferably from 7.1 to 13.1 parts by mass, and more preferably from 7.1 to 11.2 parts by mass.

[0026] A preferred embodiment of the toner will be described below, but the present disclosure is not limited to the following preferred embodiment. The first toner and the second toner preferably contain toner particles and an external additive.

[0027] The toner particles may contain a binder resin. The binder resin is not particularly limited, and known binder resins can be used. For example, aromatic vinyl compounds such as polystyrene and polyvinyltoluene and homopolymers of their substitutes; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ... Examples of the copolymers include copolymers of aromatic vinyl compounds such as styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; homopolymers of aliphatic vinyl compounds and their substituted derivatives such as polyethylene and polypropylene; vinyl resins such as polyvinyl acetate, polyvinyl propionate, polyvinyl benzoate, polyvinyl butyrate, polyvinyl benzoate, polyvinyl formate, and polyvinyl butyral; vinyl ether resins; vinyl ketone resins; acrylic polymers; methacrylic polymers; silicone resins; polyester resins; polyamide resins; epoxy resins; phenolic resins; rosin, modified rosin, and terpene resins. These may be used alone or in combination of two or more.

[0028] The binder resin preferably contains a copolymer of an aromatic vinyl compound. Among them, the binder resin is preferably a styrene-methyl acrylate copolymer, a styrene-ethyl ... More preferably, the copolymer contains a styrene-acrylic resin such as a styrene-butyl acrylate copolymer, a styrene-octyl acrylate copolymer, a styrene-dimethylaminoethyl acrylate copolymer, a styrene-methyl methacrylate copolymer, a styrene-ethyl methacrylate copolymer, a styrene-butyl methacrylate copolymer, or a styrene-dimethylaminoethyl methacrylate copolymer, and further preferably contains a styrene-butyl acrylate copolymer.

[0029] Examples of the polymerizable monomer that forms the copolymer of the aromatic vinyl compound include the following. Examples of the styrene or styrene derivatives include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene.

[0030] Examples of the polymerizable monomer that forms an acrylic polymer include acrylic polymerizable monomers such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate.

[0031] Examples of polymerizable monomers that form methacrylic polymers include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

[0032] The polyester resin may be a condensation polymer of a carboxylic acid component and an alcohol component as listed below. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

[0033] The polyester resin may be a polyester resin containing a urea group. The polyester resin is preferably one in which the carboxyl group at the terminal or the like is not capped (substituted by another substituent). For example, the binder resin may contain a polyester resin in addition to the copolymer of an aromatic vinyl compound. The content of the copolymer of an aromatic vinyl compound in the binder resin is preferably 50 to 100% by mass, more preferably 80 to 99% by mass, and further preferably 90 to 98% by mass. The method for producing the polymer is not particularly limited, and any known method can be used.

[0034] Next, the wax will be described. It is preferable that the first toner and the second toner each contain a wax. The wax is not particularly limited, and examples thereof include the following.

[0035] Low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax and other hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax; waxes in which fatty acid esters have been partially or completely deoxidized, such as deoxidized carnauba wax; saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, melissyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis-stearyl Examples of such waxes include saturated fatty acid bisamides such as ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'dioleyl adipic acid amide, and N,N'dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'distearyl isophthalic acid amide; fatty acid metal salts (generally known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid; partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and fats. The waxes mentioned above can be used alone or in combination of two or more.

[0036] The wax preferably contains a hydrocarbon wax. H1 and H2 are, for example, the heat values ​​of the exothermic peaks corresponding to the wax (preferably the hydrocarbon wax). The hydrocarbon wax is, for example, a release agent. In addition to the hydrocarbon wax, the wax may further contain an ester wax as a plasticizer.

[0037] Examples of fatty alcohols which form ester waxes include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, myristyl alcohol, 1-hexadecanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ethylene glycol, and the like. Examples of aliphatic carboxylic acids that form ester waxes include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid.

[0038] The content of the wax is preferably 0.5 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin or the polymerizable monomer. For example, the content of the ester wax in the first toner and the second toner is preferably 5.0 to 25.0 parts by mass, and more preferably 10.0 to 20.0 parts by mass, based on 100 parts by mass of the binder resin or polymerizable monomer.

[0039] Next, colorants will be described. The toner particles may contain a colorant. In particular, the powder adhesive can be used as a normal printing toner by using a colorant. The colorant is not particularly limited, and for example, the following known colorants can be used. Yellow pigments include yellow iron oxide, Nabels Yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Condensed azo compounds such as quinoline yellow lake, permanent yellow NCG, and tartrazine lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180. Orange pigments include the following: Permanent Orange GTR, Pyrazolone Orange, Balkan Orange, Benzidine Orange G, Induthrene Brilliant Orange RK, Induthrene Brilliant Orange GK, etc.

[0040] Examples of red pigments include condensed azo compounds such as red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

[0041] Examples of blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, copper phthalocyanine compounds such as indanthrene blue BG and their derivatives, anthraquinone compounds, basic dye lake compounds, etc. Specific examples include the following. CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.

[0042] Purple pigments include Fast Violet B and Methyl Violet Lake. Green pigments include Pigment Green B, Malachite Green Lake, Final Yellow Green G, and the like. Examples of white pigments include zinc oxide, titanium oxide, antimony white, and zinc sulfide. Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and pigments toned to black using the above-mentioned yellow, red and blue colorants. These colorants may be used alone or in mixture, or further in the form of a solid solution. If necessary, the colorant may be surface-treated with a substance that does not inhibit polymerization. The content of the colorant is preferably 1.0 to 15.0 parts by mass relative to 100.0 parts by mass of the binder resin or polymerizable monomer. In the case of a black toner containing carbon black, the content of the carbon black is preferably 1.0 to 15.0 parts by mass, more preferably 7.0 to 15.0 parts by mass, relative to 100.0 parts by mass of the binder resin or polymerizable monomer.

[0043] Next, the charge control agent will be described. The toner particles may contain a charge control agent as necessary. Any known charge control agent can be used, but a charge control agent that has a high triboelectric charging rate and can stably maintain a constant triboelectric charge amount is preferred. Furthermore, when the toner particles are produced by a polymerization method, a polymerization inhibitor is preferably used. Preferably, the charge control agent has low solubility and is substantially free of solubilizing agents in aqueous media. The charge control agent may be one that controls the toner to be negatively charged or one that controls the toner to be positively charged.

[0044] Examples of the toner that can be controlled to have a negative charge include the following. Examples of the metal compounds include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds; aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides and esters; phenol derivatives such as bisphenol; urea derivatives; metal-containing salicylic acid-based compounds; metal-containing naphthoic acid-based compounds; boron compounds; quaternary ammonium salts; calixarenes; and resin-based charge control agents.

[0045] On the other hand, examples of toner that can be controlled to have a positive charge include the following. Examples of suitable pigments include nigrosine and modified nigrosine such as fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; and onium salts such as phosphonium salts which are analogues of these, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lacing agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; and resin-based charge control agents (charge control resins).

[0046] The above charge control agents can be used alone or in combination of two or more. Among these charge control agents, metal-containing salicylic acid compounds are preferred, and those in which the metal is aluminum or zirconium are particularly preferred. As the charge control resin, it is preferable to use a polymer having a sulfonic acid group, a sulfonate salt group or a sulfonate ester group, or a copolymer having these. The amount of the charge control agent added is preferably 0.1 to 20.0 parts by mass, and more preferably 0.5 to 10.0 parts by mass, relative to 100.0 parts by mass of the binder resin.

[0047] Next, the external additives will be described. The toner may contain an external additive if necessary. For example, the toner has toner particles and an external additive. The external additive can control, for example, the fluidity, chargeability, cleaning property, and the like. Examples of the external additives used include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, and inorganic titanic acid compound fine particles such as strontium titanate fine particles and zinc titanate fine particles. The external additives can be used alone or in combination of two or more kinds.

[0048] The total amount of external additives added is preferably 0.05 to 10.00 parts by mass, and more preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of toner particles. The external additive can be fixed to the surface of the toner particles by a known method, such as a dry method using a Henschel mixer or a wet method in which the toner particles and the external additive are dispersed in a solvent and then aggregated to fix the particles.

[0049] Next, a method for producing the toner particles will be described. Known methods can be used for producing toner particles. For example, dry production methods such as a kneading and grinding method; and wet production methods such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and an emulsion polymerization aggregation method. In particular, it is desirable to sharpen the particle size distribution of toner particles and to obtain the average circularity of toner particles. From the viewpoints of improving the properties and forming a core-shell structure, it is preferable to use a wet production method.

[0050] For example, when toner particles are manufactured by a kneading and pulverization method, which is a dry manufacturing method, a binder resin and, if necessary, a wax, a colorant, a charge control agent, and other additives are thoroughly mixed in a mixer such as a Henschel mixer, a ball mill, etc. Then, various materials are dispersed or dissolved by melt-kneading using a thermal kneader such as a heating roll, a kneader, or an extruder, and the mixture is subjected to a cooling and solidifying step, a pulverizing step, a classification step, and, if necessary, a surface treatment step to obtain toner particles.

[0051] In the pulverization step, a known pulverization device such as a mechanical impact type or a jet type may be used. The order of the classification step and the surface treatment step does not matter. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

[0052] Next, a case where toner particles are produced by a suspension polymerization method, which is an example of a wet production method, will be described. Below, a detailed example of a method for producing toner particles using a suspension polymerization method will be described, but the present disclosure is not limited thereto. In the suspension polymerization method, first, a polymerizable monomer for producing a binder resin, and, if necessary, a wax, a colorant, a charge control agent, a crosslinking agent, a polymerization initiator, and other additives are uniformly dissolved or dispersed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine to obtain a polymerizable monomer composition (polymerizable monomer composition preparation process).

[0053] Next, the polymerizable monomer composition is poured into a previously prepared aqueous medium, and droplets of the polymerizable monomer composition are formed into the desired toner particle size using a stirrer or disperser having high shear force (granulation process).

[0054] It is preferable that the aqueous medium in the granulation process contains a dispersion stabilizer in order to control the particle size of the toner particles, to sharpen the particle size distribution, and to suppress the coalescence of the toner particles during the manufacturing process. Dispersion stabilizers are generally broadly classified into polymers that exhibit repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive force. Fine particles of poorly water-soluble inorganic compounds are dissolved by acid or alkali. Therefore, they are preferably used because they can be dissolved and easily removed by washing with acid or alkali after polymerization.

[0055] As the dispersion stabilizer of the poorly water-soluble inorganic compound, one containing any one of magnesium, calcium, barium, zinc, aluminum, and phosphorus is preferably used. More preferably, one containing any one of magnesium, calcium, aluminum, and phosphorus. Specific examples thereof include the following. Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide.

[0056] When using a poorly water-soluble inorganic dispersant, it may be used as it is, but in order to obtain finer particles, inorganic dispersant particles may be generated in an aqueous medium and used. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution are mixed under high speed stirring to generate water-insoluble tricalcium phosphate, which enables more uniform and fine dispersion.

[0057] The above dispersion stabilizers may be used in combination with organic compounds such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch. The dispersion stabilizer is preferably used in an amount of 0.1 to 20.0 parts by mass based on 100 parts by mass of the polymerizable monomer.

[0058] Furthermore, in order to make the dispersion stabilizer finer, 0.1 to 10.0 parts by mass of a surfactant may be used in combination with 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic, or cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

[0059] After the granulation step or while the granulation step is being carried out, the temperature is preferably set to 50 to 90° C. to polymerize the polymerizable monomers contained in the polymerizable monomer composition, thereby obtaining a toner particle dispersion (polymerization step).

[0060] In the polymerization step, it is preferable to carry out a stirring operation so that the temperature distribution in the vessel is uniform. When a polymerization initiator is added, it can be added at any timing and for any required time. In addition, the temperature may be raised in the latter half of the polymerization reaction in order to obtain a desired molecular weight distribution, and further, in order to remove unreacted polymerizable monomers, by-products, etc. from the system, a part of the aqueous medium may be distilled off by a distillation operation in the latter half of the reaction or after the reaction is completed. The distillation operation can be carried out under normal pressure or reduced pressure.

[0061] The polymerization initiator used in the suspension polymerization method preferably has a half-life of 0.5 to 30 hours during the polymerization reaction. When the polymerization reaction is carried out using an amount of 0.5 to 20.0 parts by mass per 100 parts by mass of the polymerizable monomer, a polymer having a maximum weight average molecular weight between 5,000 and 50,000 can be obtained.

[0062] As the polymerization initiator, an oil-soluble initiator is generally used, for example, the following: Examples of the initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide initiators such as acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide.

[0063] The polymerization initiator may be used in combination with a water-soluble initiator as necessary, and examples thereof include the following. Ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyromidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, 2,2'-azobisisobutyronitrile sodium sulfonate, ferrous sulfate, or hydrogen peroxide. These polymerization initiators can be used alone or in combination of two or more. In order to control the degree of polymerization of the polymerizable monomer, it is also possible to further add a chain transfer agent, a polymerization inhibitor, etc.

[0064] The particle size of the toner particles is preferably a weight average particle size of 3.0 to 10.0 μm from the viewpoint of obtaining a high-definition and high-resolution image. The weight average particle size of the toner particles and the toner can be measured by a capillary electrical resistance method. For example, it can be measured using a "Coulter Counter Multisizer 3" (manufactured by Beckman Coulter, Inc.). After the polymerization process, the toner particle dispersion is subjected to a filtration process for solid-liquid separation of the toner particles and the aqueous medium. and is sent.

[0065] The solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be carried out by a general filtration method, and then, in order to remove foreign matter that has not been completely removed from the surface of the toner particles, it is preferable to further wash the toner particles by reslurrying or washing with washing water. After sufficient washing, solid-liquid separation is carried out again to obtain a toner cake. Then, the toner is dried by a known drying means, and if necessary, particles having a particle size other than the specified particle size are separated by classification to obtain toner particles. The particles having a particle size other than the specified particle size separated at this time may be reused to improve the final yield.

[0066] Next, the developer will be described. The toner can be used as a magnetic or non-magnetic one-component developer, but may also be mixed with a carrier and used as a two-component developer. As the carrier, magnetic particles made of known materials such as metals such as iron, ferrite, magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Of these, it is preferable to use ferrite particles. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as resin, or a resin dispersion type carrier in which magnetic fine powder is dispersed in a binder resin can also be used. The carrier preferably has a volume average particle size of 15 to 100 μm, and more preferably 25 to 80 μm.

[0067] Next, the bonding method will be described. To form a pattern using toner as a powder adhesive, for example, electrophotography can be used. The toner is charged, and a latent image drawn by the potential is developed with the toner, and then electrostatically transferred to a sheet as an adherend, forming a toner image on the sheet. The toner images are then superimposed and heated to bond the sheets together. Images can also be printed within the sheet using the toner.

[0068] The bonding method includes the following steps. (1) forming a first unfixed toner layer on a first surface of a sheet using a first toner; (2) forming a second unfixed toner layer on the first unfixed toner layer using a second toner; (3) A step of applying heat from the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet. (4) A step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed, thereby obtaining an adhesion product. The adhesive image pattern formed during the adhesion process has a fixed toner image on the surface thereof, the fixed toner image being derived from the second unfixed toner layer.

[0069] The present disclosure also relates to a toner set used in the above-mentioned adhesion method. The toner set has the above-mentioned first toner and second toner separately. The present disclosure may also provide a cartridge set. The cartridge set has a first process cartridge that contains the first toner and a second process cartridge that contains the second toner.

[0070] Next, the bonding device will be described. The bonding device is configured to store sheets such as paper as the adherend, and is equipped with an image forming unit as an image forming means, and a heating device as a bonding means. Bonding is performed by applying heat to a stack of sheets on which a powder adhesive pattern is formed. Since the printer is equipped with a printing device, it is also possible to print images by using toner instead of powder adhesive.

[0071] <Bonding method, bonding device, and operation> The overall configuration of the bonding device will be described with reference to Fig. 1. Fig. 1 is a schematic diagram showing the cross-sectional configuration of a bonding device according to an embodiment described later. 1, the bonding device has an image forming unit 1 and a post-processing unit 300. The image forming unit 1 is equipped with a sheet cassette 8 as a sheet storage unit that stores sheets P as recording materials, an image forming unit 1e as an image forming means, a fixing device 6 as a fixing means, and a housing 19 that houses these. The bonding device has a printing function of forming a toner image on the sheet P fed from the sheet cassette 8 by the image forming unit 1e, and producing a printed matter that has been subjected to a fixing process by the fixing device 6.

[0072] The size of the sheet is not particularly limited and may be changed appropriately according to the size of the bonding device to be used. In the examples described later, the maximum size of the sheet P in the conveying direction on which an image can be formed is A4 size (297 mm length x 210 mm width), and the image is formed by conveying the A4 size in the vertical direction. The sheet conveying speed is also not particularly limited, and is 300 mm / sec in the examples described later.

[0073] The sheet cassette 8 is inserted into the housing 19 at the bottom of the bonding device so as to be removable, and stores a large number of sheets P. The sheets P stored in the sheet cassette 8 are fed from the sheet cassette 8 by a sheet feed roller 8a serving as a sheet feed section, and are transported by a transport roller pair 8b. It is also possible to feed sheets set in the multi-tray 20 one by one.

[0074] The image forming unit 1e is a tandem-type electrophotographic unit equipped with four process cartridges 7y, 7m, 7c, and 7k, a scanner unit 2, and a transfer unit 3. A process cartridge is a unit in which multiple parts responsible for an image forming process are integrated into one unit that can be replaced.

[0075] Each of the process cartridges 7y, 7m, 7c, and 7k has a substantially common configuration except for the type of toner contained in the four toner containing sections Ky, Km, Kc, and Kk. That is, each of the process cartridges 7y, 7m, 7c, and 7k includes a photosensitive drum Dy, Dm, Dc, and Dk that is an image carrier, a charging roller Cy, Cm, Cc, and Ck that is a charger, and a toner containing section Ky, Km, Kc, and Kk that contains toner and supplies it to the photosensitive drum.

[0076] The four toner storage sections Ky, Km, Kc, and Kk store printing toners of yellow (Ty), magenta (Tm), cyan (Tc), and black (Tk), respectively, as toners for forming visible images on the sheet P. These toners for forming visible images can also be used as adhesive toners as powder adhesives for performing an adhesive process after printing.

[0077] The scanner unit 2 is disposed below the process cartridges 7y, 7m, 7c, and 7k and above the sheet cassette 8. The scanner unit 2 is an exposure unit that writes an electrostatic latent image by irradiating the photosensitive drums Dy, Dm, Dc, and Dk of the process cartridges 7y, 7m, 7c, and 7k with laser beams Jy, Jm, Jc, and Jk.

[0078] The transfer unit 3 includes a transfer belt 3a as an intermediate transfer body (secondary image carrier). The transfer belt 3a is a belt member wound around a secondary transfer inner roller 3b and a tension roller 3c, and its outer circumferential surface is in contact with the photosensitive drums of the process cartridges 7y, 7m, 7c, and 7k. The transfer belt 3a faces the photosensitive drums Dy, Dm, Dc, and Dk. On the inner circumferential side of the transfer belt 3a, primary transfer rollers Fy, Fm, Fc, and Fk are disposed at positions corresponding to the photosensitive drums Dy, Dm, Dc, and Dk. Also, a secondary transfer roller 5 as a transfer means is disposed at a position facing the secondary transfer inner roller 3b. A transfer nip 5n between the secondary transfer roller 5 and the transfer belt 3a is a transfer section (secondary transfer section) where a toner image is transferred from the transfer belt 3a to the sheet P. A fixing device 6 is disposed above the secondary transfer roller 5.

[0079] The fixing device 6 has a cylindrical fixing film (endless belt) 6a as a heating rotator, a pressure roller 6c as a pressure member, a heater 6b as a heating means that contacts the inner surface of the fixing film 6a, and the pressure roller 6c as a pressure rotator that forms a fixing nip 6n with the heater 6b via the fixing film 6a.

[0080] Next, the operation of the image forming unit 1 will be described with reference to Fig. 1 again. When data of an image such as an adhesive image pattern to be printed and a command to execute printing are input to the image forming unit 1, a control unit (not shown) of the bonding device starts a series of operations (image forming operations) for conveying the sheet P and forming an image on the sheet P. In the image forming operation, the sheets P are first fed one by one from the sheet cassette 8 and conveyed toward the transfer nip 5n via the conveying roller 8b.

[0081] In parallel with the feeding of the sheet P, the process cartridges 7y, 7m, 7c, and 7k are driven in sequence, and the photosensitive drums Dy, Dm, Dc, and Dk are rotated. At this time, the photosensitive drums Dy, Dm, Dc, and Dk are uniformly charged on their surfaces by the charging rollers Cy, Cm, Cc, and Ck. The scanner unit 2 also irradiates the photosensitive drums Dy, Dm, Dc, and Dk of the process cartridges 7y, 7m, 7c, and 7k with laser light modulated based on image data, forming electrostatic latent images on the surfaces of the photosensitive drums Dy, Dm, Dc, and Dk. Next, the electrostatic latent images on the photosensitive drums Dy, Dm, Dc, and Dk are developed into toner images by the toner carried by the developing rollers Hy, Hm, Hc, and Hk in the toner storage units Ky, Km, Kc, and Kk of the process cartridges 7y, 7m, 7c, and 7k.

[0082] The transfer belt 3a rotates in a counterclockwise direction (arrow V) in the figure. The toner images formed in the process cartridges 7y, 7m, 7c, and 7k are primarily transferred from the photosensitive drums Dy, Dm, Dc, and Dk to the transfer belt 3a by an electric field formed between the photosensitive drums Dy, Dm, Dc, and Dk and the primary transfer rollers Fy, Fm, Fc, and Fk.

[0083] The toner image carried by the transfer belt 3a and reaching the transfer nip 5n is secondarily transferred onto the conveyed sheet P by an electric field formed between the secondary transfer roller 5 and the inner secondary transfer roller 3b.

[0084] In the toner image formed on the sheet P after the secondary transfer, when the toner image contains all four color toners, black toner Tk is disposed at the position closest to the sheet P. Cyan toner Tc is disposed on the black toner Tk, magenta toner Tm is disposed on the cyan toner Tc, and yellow toner Ty is disposed at the position furthest from the sheet P.

[0085] Thereafter, the sheet P is conveyed to the fixing device 6 and subjected to a thermal fixing process. That is, when the sheet P passes through the fixing nip 6n, the toner image on the sheet P is heated and pressurized, so that the toners Ty, Tm, Tc, and Tk melt and then solidify to form a toner layer, thereby obtaining an image such as an adhesive image pattern fixed on the sheet P.

[0086] In the present disclosure, a first unfixed toner layer is formed on a first surface of the sheet using a first toner. A first unfixed toner layer is formed on the first unfixed toner layer, and a second unfixed toner layer is formed on the second unfixed toner layer using a second toner to form an image pattern such that the second unfixed toner layer is the surface. The formed image pattern is then fixed on the first surface of the sheet to form an adhesive image pattern. A first unfixed toner layer is also formed on the second surface of the sheet opposite to the first surface using the first toner, and a second unfixed toner layer is formed on the first unfixed toner layer using the second toner to form an image pattern such that the second unfixed toner layer is the surface, and after a fixing process, an adhesive image pattern may be formed on the second surface of the sheet. That is, an adhesive image pattern may be formed on both sides of the sheet. As long as the first toner and the second toner satisfy the formulas (1) and (2), a further toner layer may be provided, for example, between the sheet and the first unfixed toner layer within a range that does not impair the effects of the present disclosure.

[0087] In addition, as long as the first toner and the second toner satisfy the formulas (1) and (2), the first toner may contain toners of multiple colors, and the second toner may contain toners of multiple colors. In addition, as long as the first toner and the second toner satisfy the formulas (1) and (2), the first toner and the second toner may be toners of the same color.

[0088] The first toner is preferably a black toner Tk, and the second toner is preferably at least one selected from the group consisting of a cyan toner Tc, a magenta toner Tm, and a yellow toner Ty. Alternatively, for example, the first toner may be a cyan toner Tc, and the second toner may be at least one selected from the group consisting of a magenta toner Tm, and a yellow toner Ty. Alternatively, the first toner may be a magenta toner Tm, and the second toner may be a yellow toner Ty.

[0089] The switching guide 33 is a flap-shaped guide member for switching the conveying direction when a single-sided printing mode is selected in which an image is formed on one side of the sheet P, or a double-sided printing mode is selected in which images are formed on both sides of the sheet P. In the single-sided printing mode, the switching guide 33 conveys the sheet P to the pair of paper discharge rollers 34.

[0090] On the other hand, in the double-sided printing mode, the switching guide 33 conveys the sheet P to the switchback roller pair 35, which reverses its rotational direction after discharging the sheet P to the rear end, thereby conveying the sheet P to the double-sided conveying path 36 for double-sided printing. The sheet P conveyed to the double-sided conveying path 36 passes through the secondary transfer section and the fixing section again, so that an adhesive image pattern is formed on a second surface (unprinted sheet surface) opposite to the first surface of the sheet. Thereafter, the sheet P on which the image has been formed is conveyed by the switching guide 33 to the discharge roller pair 34, which conveys the sheet P to the post-processing unit 300 via an intermediate conveying unit 200 having conveying roller pairs 201 and 202.

[0091] The post-processing unit 300 is of a floor-standing type, and is equipped with a sheet alignment means at the bottom and a thermocompression bonding unit 51 as a booklet bonding device that heats and presses the aligned sheet stack for a predetermined period of time. In the embodiment described later, the sheet conveying speed of the intermediate conveying unit 200 and the post-processing unit 300 is 600 mm / sec. In the present disclosure, a plurality of sheets on which an adhesive image pattern is formed are stacked so that the second toner layers of the adhesive image pattern are in contact with each other to form a sheet bundle, and the adhesive image pattern in the sheet bundle is heated (preferably heated and pressurized) to bond the sheets together to obtain a booklet. The sheets can be bonded together by a thermocompression bonding unit 51.

[0092] The sheet P conveyed from the intermediate conveying unit 200 is delivered to a pair of conveying rollers 21 of the post-processing unit 300. The conveying rollers 22 accelerate the sheet at a predetermined timing based on the time when the rear end passes the entrance sensor 27. When the sheet is discharged to the upper discharge tray 25, the sheet is decelerated to a predetermined discharge speed when the rear end of the sheet reaches between the transport roller 22 and the reversing roller 24 and is discharged to the upper discharge tray 25.

[0093] When sheets are bonded together to obtain a booklet, the bonded booklet is discharged from the lower discharge tray 37 via the thermocompression bonding unit 51. In this case, the sheet transport is temporarily stopped when the rear end of the sheet passes through the check valve 23, which is biased clockwise in the figure by a spring (not shown), and then the sheet is switched back and transported to the inner discharge rollers 26.

[0094] The sheet P conveyed from the internal discharge roller 26 is sent to the kick-out roller 29 via the intermediate conveying roller 28, and is conveyed to the intermediate stacking section 42. A vertical alignment reference plate 39 is disposed at the most downstream portion of the intermediate stacking section 42, and the sheet stack is aligned by abutting the end of the sheet in the conveying direction against this plate.

[0095] The sheet alignment method will be described with reference to Fig. 1 and Figs. 2A to 2D. Here, the longitudinal direction of the sheet P is defined as the Y direction, the lateral direction as the X direction, and the height direction as the Z direction. As shown in Fig. 2A, a half-moon roller 40 for pushing the sheet P that has passed through the kick-out rollers 29 onto the longitudinal alignment reference plate 39 is rotatably supported in the intermediate stacking section 42. The half-moon roller 40 transports the sheet towards the longitudinal alignment reference plate 39 at a predetermined timing. As shown in Fig. 2B, the transport pressure of the half-moon roller 40 is adjusted so that the roller slips on the sheet after the sheet comes into contact with the longitudinal alignment reference plate 39.

[0096] After the sheets reach the vertical alignment reference plate, an alignment operation is performed until the horizontal alignment jogger 41a hits the horizontal alignment reference plate 500 (dotted line) as shown in Fig. 2C, and the sheet stack is aligned in a predetermined position as shown in Fig. 2D. The operations in Fig. 2C and 2D are performed in a batch for each predetermined number of sheets in conjunction with the binding operation by the thermocompression bonding unit 51 as a sheet bonding means. The thermocompression bonding unit 51 creates a booklet with the left end bound or the right end bound by subjecting a sheet bundle made up of a plurality of sheets P to a thermocompression process. The sheet bundle that is aligned vertically and horizontally is subjected to a heating and pressurizing process by the thermocompression bonding unit 51, making it possible to create a booklet that is aligned with high precision.

[0097] In the present disclosure, the second toner layers of the adhesive image patterns formed on the same sheet or different sheets are superposed so as to contact each other. The sheet may be one sheet, or may be two or more sheets. It is preferable to superpose the fixed toner images of the adhesive image patterns formed on different sheets so as to contact each other. Then, the sheets are bonded together by heating the adhesive image pattern on the sheets, and a booklet can be obtained. Since the sheets are stacked so that the second toner layers come into contact with each other, the adhesive image pattern, in which the first toner layer and the second toner layer are laminated, forms at least two layers between the sheets (FIG. 6).

[0098] For example, a sheet bundle may be obtained by stacking a plurality of sheets each having an adhesive image pattern formed on both a first surface and a second surface. A sheet having an adhesive image pattern formed on a first surface and another sheet having an adhesive image pattern formed on a first surface may be superimposed so that the second toner layers are in contact with each other. By adopting the above-mentioned double-sided printing mode, it is possible to produce a sheet bundle. For example, a plurality of sheets having adhesive image patterns formed on both surfaces of the sheet are stacked, and a sheet having no adhesive image pattern formed on the front surface side of the sheet bundle is used. The number of sheets can be set arbitrarily.

[0099] It is preferable to heat the adhesive image pattern in the sheet stack to bond the sheets together, thereby obtaining a booklet as a finished product. It is preferable to heat the sheet stack from the side on which the adhesive image pattern is not formed. For example, the sheet stack is heated from the second surface side on the reverse side of the first surface. That is, it is preferable not to form an adhesive image pattern on the surface (second surface) of the sheet that forms the surface of the sheet bundle that can become the cover of the booklet.

[0100] The structure of the thermocompression bonding unit 51 will be further described. Fig. 3A is a cross-sectional view of the thermocompression bonding unit 51, in which an aluminum heating plate 502 is placed on a ceramic heater 501 incorporating a heating element as a heat source. In the examples described below, the dimensions of the ceramic heater are a thickness of 1.0 mm, a width of 8.0 mm, and a length of 350 mm. The ceramic heater 501 can be controlled to an arbitrary set temperature by a temperature detection means and a power application means supported by a heater support 503 (not shown).

[0101] In the examples described later, the set temperature was adjusted so that the surface temperature of the pressure applying part A of the heating plate 502 was 200°C. By providing the pressure applying part A on the heating plate 502, the heat and pressure of the thermocompression bonding unit 51 can be concentrated only on the portion where the image pattern for adhesion is present, which is the binding position of the sheet stack, and heating and pressure processing can be performed efficiently. The ceramic heater is supported by a heater support 503 made of resin. The degree of heating and pressing may be appropriately changed depending on the melting characteristics of the toner. For example, the minimum temperature of the adhesive image pattern may be set to preferably 75 to 100° C., more preferably 78 to 90° C. The surface temperature of the pressing unit A may be set to, for example, 180 to 240° C.

[0102] The pressure lever 504 obtains power from a drive source (not shown) to press down the thermocompression bonding unit 51 in the -Z direction (downward) and apply pressure to the sheet stack. The pressure of the pressure lever 504 is transmitted via a metal stay 505 as a rigid body. In an embodiment described later, the pressure lever 504 applies a total pressure of 30 kgf to the sheet stack P. Here, 506 is a pressure plate made of silicone rubber with a thickness of 2.0 mm, which is a member for stably receiving the pressure. The pressure during pressure application may be sufficient to form a sheet stack, and the total pressure on the sheet stack P is preferably 25 to 50 kgf, and more preferably 28 to 40 kgf.

[0103] In the embodiment described later, the thermocompression bonding unit 51 presses the sheet stack for 2 seconds and then separates. 2 Up to five sheets P can be bonded at once. Fig. 3B shows the cross-sectional shape of the heating plate 502. In the embodiment described later, the pressure applying portion A has a flat portion of 1.0 mm and curved portions of R1.5 on both sides. The length of the heating plate 502 in the Y direction is 300 mm.

[0104] Also, as shown in FIG. 3A, after the adhesive process is performed once by the thermocompression bonding unit 51 (P1-1 to P1-5), as shown in FIG. 3C, the sheets P may be stacked in order on top of the sheets (P2-1 to P2-4), and P1-1 to 5 and P2-1 to 4 may be bonded together. This makes it possible to produce a product with a large number of booklets. In the embodiment described later, five sheets P are supplied the first time, and then a maximum of four sheets are supplied at a time, making it possible to produce a booklet of up to 50 sheets. During continuous operation, the sheets P are supplied to the thermocompression bonding unit 51, and the thermocompression bonding unit 51 repeats a lowering operation, a pressurizing operation (for two seconds), and an ascending operation, thereby enabling efficient booklet production.

[0105] After the bonding process by the thermocompression bonding unit 51 is completed, a bundle discharge guide (not shown) moves parallel from the standby position toward the sheet discharge port 45 to push out the booklet. A bundle discharge roller 38 is provided at the sheet discharge port 45. The bundle discharge guide stops at a position where the leading edge of the booklet slightly passes the bundle discharge roller 38 and returns to the standby position again. The bundle discharge roller 38 discharges the booklet received from the bundle discharge guide onto the lower discharge tray 37.

[0106] 4A is a schematic diagram showing a printing area S of an adhesive image pattern using toners Ty, Tm, Tc, and Tk in an embodiment described later. As shown by the hatched area, the printing area S of the adhesive image pattern is image-formed at the end of the long side of the sheet P, making it possible to produce a long bound booklet as an end product when the booklet is produced by the post-processing device. Here, in the embodiment described later, the width W of the printing area S of the adhesive image pattern is set to 4.0 mm. The shape of the printing area S may be appropriately changed so as to obtain a desired booklet. As shown in FIG. 4B, by forming the printing area S of the adhesive image pattern on a part of the long side end, it is also possible to produce a corner-fastened booklet as the final product. In the examples described later, the toner amount (laying amount) per unit area of ​​each single toner color used in the adhesive image pattern is 0.4 mg / cm. 2 For example, the toner amount of each of the first toner and the second toner on the sheet is 0.3 to 1.5 mg / cm. 2 is preferably 0.4 to 1.0 mg / cm 2 is more preferred.

[0107] The measurement methods for each physical property according to the present disclosure will be described below. <Method for measuring calorific value H> The calorific value H1 [J / g] of the first toner and the calorific value H2 [J / g] of the second toner are measured using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments) in accordance with ASTM D3418-82. The melting points of indium and zinc are used for temperature correction of the detector of the device, and the heat of fusion of indium is used for heat correction. Specifically, 3 mg of the toner to be measured is precisely weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference. In the measurement, the temperature is raised at a rate of 10°C / min within the measurement temperature range of 20 to 180°C, the temperature is kept at 180°C for 10 minutes, and the temperature is cooled from 180°C to 20°C at a rate of 10°C / min. A baseline (a line connecting the plot of 30°C and the plot of 180°C on the DSC curve) is drawn for the heat generation peak of the DSC curve in the temperature range of 30 to 180°C during this cooling (cooling down process), and the peak area in the range of 35°C to 75°C is taken as the heat generation amount H. The peak area is the integral value of the area sandwiched between the DSC curve and the baseline. The heat generation amount H when the first toner is measured is taken as H1, and the heat generation amount H when the second toner is measured is taken as H2.

[0108] <Method of measuring the content W of hydrocarbon wax contained in toner> The content W of the hydrocarbon wax per 100 parts by mass of the binder resin in the toner is calculated by the following procedure. First, the mass X1 of the tetrahydrofuran (THF) soluble matter in the toner, the mass X2 of the insoluble matter, and the incineration ash content X3 of the insoluble matter are determined. Next, the amount w of the hydrocarbon wax in the toner is determined. Also, the amount R of the binder resin in the toner is determined. From the values ​​of w and R, the content of the hydrocarbon wax per 100 parts by mass of the binder resin can be calculated.

[0109] Specifically, 1.5 g of toner is weighed out and placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 x 100 mm, manufactured by Advantec Toyo Co., Ltd.) and set in a Soxhlet extractor. Extraction is performed for 20 hours using 200 mL of tetrahydrofuran (THF) as a solvent, with the reflux speed being such that the solvent extraction cycle occurs once every 5 minutes. After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40°C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and the mass of the extraction residue calculated by subtracting the mass of the cylindrical filter paper is taken as the mass X2 (g) of the tetrahydrofuran (THF) insoluble matter in the toner. The mass X1 (g) of the tetrahydrofuran (THF) soluble matter in the toner is calculated from the following formula (A). X1=1.5-X2 (A)

[0110] Next, the content X3 (g) of components other than the resin component is calculated by the following procedure. 1.5 g of toner is precisely weighed into a pre-weighed 30 mL magnetic crucible. The magnetic crucible is placed in an electric furnace and heated at 900°C for 3 hours, cooled in the electric furnace, cooled at room temperature in a desiccator for at least 1 hour, and then incinerated. The mass of the crucible containing the residual ash is weighed, and the mass of the crucible is subtracted to calculate the incineration residual ash X3 (g).

[0111] The extract obtained by the above procedure is filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. This sample solution is used for measurements under the following conditions. Equipment: HLC8320 GPC (detector: RI) (Tosoh Corporation) Column: Shodex LF-404, 2 columns of LF-404 (Showa Denko) Eluent: tetrahydrofuran (THF) Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml The total area S of the molecular weight distribution of the tetrahydrofuran (THF) soluble matter in the obtained toner and the peak area P1 derived from the hydrocarbon wax having a molecular weight corresponding to the wax identified by the method for identifying the molecular structure of the hydrocarbon wax contained in the toner described below are measured. The amount w of the hydrocarbon wax in the toner can be calculated from the following formula (B). w=(X1×P1 / S) ={(1.5-X2)×P1 / S} (B)

[0112] In addition, the total area S of the molecular weight distribution of the tetrahydrofuran (THF) soluble matter in the toner and the area P derived from the total wax were calculated by the above GPC. W From this, the amount R of the binder resin in the toner can be calculated using the following formula (R). R = {X1 + (X2 - X3)} - (X1 × P W / S) ···(R) From the amount w of the resulting hydrocarbon wax and the amount R of the binder resin, the content W of the hydrocarbon wax per 100 parts by mass of the binder resin can be calculated.

[0113] <Method for identifying the molecular structure of hydrocarbon wax contained in toner> First, the hydrocarbon wax is isolated from the toner by the following separation procedure. The toner is dispersed in ethanol, which is a poor solvent for the toner, and the temperature is raised to a temperature above the melting point of the wax. Pressure may be applied at this time if necessary. The wax that has exceeded its melting point by this procedure is melted and extracted into the ethanol. The wax can be separated from the toner by heating and, if pressure is applied, by performing solid-liquid separation while still under pressure. The extract is then dried and solidified to obtain a wax, which can be separated by molecular weight to isolate the hydrocarbon wax. Next, the molecular structure of the isolated hydrocarbon wax is identified using a pyrolysis gas chromatography mass spectrometer (hereafter referred to as pyrolysis GC / MS) and NMR.

[0114] Specifically, the following operations are performed. (1) 50 mg of toner is accurately weighed into an 8 mL glass sample bottle, 1 mL of deuterated chloroform is added, the bottle is capped, and the toner is dispersed and dissolved for 1 hour using an ultrasonic disperser. The toner is then filtered through a 0.4 μm membrane filter, and the filtrate is collected. At this time, the deuterated chloroform insoluble matter remains on the membrane filter. (2) Regarding the filtrate: 1 H-NMR measurement is carried out, and the spectra are assigned to each of the constituent monomers of the hydrocarbon wax and the ester wax. (3) Analyze the wax using pyrolysis GC / MS. If necessary, methylation or other derivatization is performed to calculate the molecular weight of the hydrocarbon wax. (NMR measurement conditions) Equipment: Bruker AVANCE 500 manufactured by Bruker Biospin Co., Ltd. Measurement nuclei: 1 H Measurement frequency: 500.1MHz Number of times: 16 Measurement temperature: room temperature (Measurement conditions for pyrolysis GC / MS) Pyrolysis equipment: Japan Analytical Industry Co., Ltd. TPS-700 Thermal decomposition temperature: Optimum value between 400℃ and 600℃ GC / MS equipment: ISQ manufactured by Thermo Fisher Scientific Co., Ltd. Column: "HP5-MS" (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm (GC / MS conditions) Filler requirements: InletTemp:250℃ Split Flow: 50mL / min GC heating conditions: 40℃ (5min) → 10℃ / min (300℃) → 300℃ (20min) EXAMPLES

[0115] The present disclosure will be described in more detail below with reference to Production Examples and Examples, which are not intended to limit the present disclosure in any way. Note that "parts" and "%" in the formulations of the Examples and Comparative Examples are all by mass unless otherwise specified.

[0116] <Production of Toner 1> (Preparation of Polymerizable Monomer Composition 1) Styrene 60.0 parts Carbon black 10.0 parts The above materials were placed in an attritor (manufactured by Nippon Coke and Engineering Co., Ltd.) and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours, after which the zirconia particles were removed to prepare a colorant dispersion in which the pigment was dispersed.

[0117] The following materials were then added to the colorant dispersion: Styrene 15.0 parts ・20.0 parts n-butyl acrylate Hexanediol diacrylate 0.5 parts Polyester resin 4.0 parts (Polymerization product of terephthalic acid and 2 moles of propylene oxide adduct of bisphenol A, weight average molecular weight Mw=10000, acid value=8.2mgKOH / g) Hydrocarbon wax (melting point: 79°C) 5.0 parts Ethylene glycol distearate 15.0 parts Next, in the dissolving / dispersing step, the above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare a polymerizable monomer composition.

[0118] (Preparation of aqueous medium 1) 11.2 parts of sodium phosphate (12-hydrate) was added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. The mixture was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining the stirring, an aqueous calcium chloride solution in which 7.4 parts of calcium chloride (2-hydrate) was dissolved in 10.0 parts of ion-exchanged water was added to the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, and aqueous medium 1 was prepared.

[0119] (granulation process) While maintaining the temperature of the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12,500 rpm, the polymerizable monomer composition was added to the aqueous medium 1, and 8.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring device at 12,500 rpm.

[0120] (Polymerization process) The high-speed agitator was replaced with a propeller-equipped agitator, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining the temperature at 70°C. The temperature was then further increased to 85°C and heated for 2.0 hours to carry out polymerization. The temperature was then increased to 98° C. and heated for 3.0 hours to remove residual monomers. The temperature was then decreased to 55° C. and maintained at 55° C. for 5.0 hours while continuing to stir. The temperature was then decreased to 25° C. Ion-exchanged water was added to adjust the toner particle concentration in the dispersion to 30.0% by mass, and toner particle dispersion 1 in which toner particles 1 were dispersed was obtained.

[0121] (Cleaning process) The toner particle dispersion 1 was adjusted to pH 1.5 with 1 mol / L hydrochloric acid and stirred for 1.0 hour, and then washed with ion-exchanged water, filtered, and dried to obtain toner particles 1. The physical properties of the obtained toner particles 1 are shown in Table 2.

[0122] (External addition process) Next, silica fine particles (number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) that had been hydrophobized using dimethyl silicone oil (20% by mass) were added to 100 parts of toner particles 1 as an external additive. 2 The mixture was mixed for 15 minutes at 3000 rpm using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) to obtain Toner 1. The jacket temperature of the Henschel mixer was set to 10° C., and the peripheral speed of the rotary blades was set to 38 m / sec.

[0123] <Production of toner 2 to 27> Toners 2 to 27 were obtained in the same manner as in the production of toner 1, except that the type of colorant and the amount of added hydrocarbon wax were changed as shown in Table 1. The physical properties of the obtained toners are shown in Table 2. [Table 1] [Table 2]

[0124] In the table, H (J / g) indicates the calorific value H.

[0125] The evaluation was performed using the bonding device shown in FIG. 1 described above. Example 1 was prepared by filling the process cartridge 7k with toner 1 and the process cartridge 7y with toner 18. No toner was filled in any cartridges other than the two-color cartridges 7k and 7y. Examples 2 to 20 and Comparative Examples 1 to 10 were prepared by filling the process cartridges 7y, 7m, and 7c with each toner in the combinations shown in Table 3. Similarly, in Examples 2 to 20 and Comparative Examples 1 to 10, no toner was filled in any cartridges other than the two-color cartridges containing the first toner and the second toner.

[0126] In this embodiment, when the thermocompression bonding unit 51 bonds a stack of sheets, the minimum toner temperature (temperature of the bonding image pattern) when bonding a maximum of five sheets at once is set to 80° C. In detail, as shown in FIG 3A, the surface temperature of the heating plate and the set temperature of the temperature detection means are set so that the toner temperature between P1-4 and P1-5 is 80° C. when bonding P1-1 to P1-5 at once. [Table 3]

[0127] <Adhesive strength evaluation results> Table 4 shows the results of evaluating the adhesive strength of the toner sets of Examples 1 to 20 and Comparative Examples 1 to 10 in Table 3. The method for evaluating the adhesive strength will be described with reference to the schematic diagrams of FIGS. 5A and 5B. First, five booklets were produced as shown in FIG. 3A using the adhesive device and thermocompression bonding unit 51 shown in FIG. 1. The adhesive image patterns on the sheets P1-1 to P1-5 will be described with reference to FIG. 6, taking the portions P1-4 to P1-5 as representative examples. In FIG. 6, the adhesive image patterns ( The first toner and the second toner are laminated on the first sheet (P1-5 side), and the first toner and the second toner are laminated in the adhesive image pattern on the back side of the sheet (P1-4 side). During the adhesive process, the lamination order is as shown in Figure 6. Adhesive image patterns are formed between the other sheets in the same way. At this time, the thermocompression unit produced a booklet for strength testing with a single heating and pressure process.

[0128] Then, P1-1 to P1-3 were peeled off and removed from the resulting booklet, leaving two booklets with only P1-4 and P1-5 bonded together. Then, the two booklets consisting of P1-4 and P1-5 were cut out to have dimensions of width (H) 20 mm and length (L) 50 mm as shown in Figure 5A, to prepare a test piece E including the bonded part S. Next, as shown in FIG. 5B, the P1-4 side of this test piece E was held by an upper holding member, and the P1-5 side was held by a lower holding member. A digital force gauge M (Nidec-Shimpo Corporation, FGP-2) was also connected to the upper holding member. The digital force gauge was then gradually raised upward, and the peel force when the adhesive portion S peeled off was measured by the digital force gauge, and the peak peel force value was recorded. Each measurement was performed five times, and the average value was taken as the adhesive strength of the adhesive portion S. Based on the obtained adhesive strength, evaluation was performed according to the following criteria. (Evaluation Criteria) A: Adhesive strength 1.50N / cm or more B: Adhesive strength 1.25N / cm or more and less than 1.50N / cm C: Adhesive strength 1.00N / cm or more and less than 1.25N / cm D: Adhesive strength less than 1.00N / cm

[0129] The reason for measuring the adhesive strength between P1-4 and P1-5 here is that this is the area farthest from the heating plate compared to the other adhesive points, making it difficult to supply heat to it and making adhesive strength an issue. The sheet P used in this measurement is "Vitality Multipurpose Printer Paper (Xerox)" with an LTR size (279 mm x 216 mm) and a basis weight of 90 g / m 2 "

[0130] <Evaluation results of high temperature offset resistance> Table 4 shows the results of evaluation of the high temperature offset resistance of the toner sets of Examples 1 to 20 and Comparative Examples 1 to 10 in Table 3. The high-temperature offset resistance was evaluated using the adhesion device shown in FIG. 1. The evaluation was performed in a normal temperature and normal humidity (25°C / 50% RH) environment, with a process speed of 320 mm / sec, and by changing the fixing temperature. The toner sets of Examples 1 to 20 and Comparative Examples 1 to 10 in Table 3 were used, and the first toner laydown amount and the second toner laydown amount were both 0.4 mg / cm. 2 By doing so, the toner amount of the solid image formed by stacking the first toner and the second toner is 0.8 mg / cm 2The image was formed so that the image was fixed by the fixing device 6 of the bonding device, and a fixed image was obtained. The transfer material was plain paper (LETTER size XEROX 4200 paper, manufactured by XEROX Corporation, 75 g / m 2 The hot offset resistance was evaluated by visually inspecting the fixed image. The hot offset resistance was evaluated according to the following criteria based on the temperature at which high-temperature offset occurred. (Evaluation Criteria) A: No offset occurs at 210℃ B: Offset occurs at temperatures between 200℃ and 210℃ C: Offset occurs below 200℃ [Table 4]

[0131] <Evaluation Results of High Temperature Offset Resistance of First Toner Alone> Table 5 shows the results of evaluating the high temperature offset resistance of the first toner alone. The high-temperature offset resistance was evaluated by changing the process speed of the bonding device shown in FIG. 1 and by the following method.

[0132] Using process cartridges filled with toners 1, 2, 7, 10, and 14 used in the evaluation of adhesive strength, solid images (toner loading amount: 0.4 mg / cm) were printed at a process speed of 400 mm / sec under normal temperature and humidity (25°C / 50% RH) conditions, with different fixing temperatures. 2 The transfer material was plain paper (LETTER size XEROX 4200 paper, manufactured by XEROX, 75 g / m 2 ) was used. The hot offset resistance was evaluated visually. Based on the temperature at which hot offset occurred, the evaluation was made according to the following criteria. (Evaluation Criteria) A: No offset occurs at 210℃ B: Offset occurs at temperatures between 200℃ and 210℃ C: Offset occurs below 200℃ [Table 5]

[0133] The present disclosure relates to the following methods and compositions: (Method 1) A bonding method comprising the steps of: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the amount of heat generated in the first toner is H1 [J / g] and the amount of heat generated in the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 (1) H1 <h2 ···(2)However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; the amount of heat generated in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A bonding method characterized by: (Method 2) The bonding method according to Method 1, further comprising a step of heating the fixed toner images of the adhesive image patterns formed on different sheets in an overlapping state to bond the sheets together to obtain the bonded product. (Method 3) The bonding method according to method 1 or 2, wherein the difference between H2 and H1 (H2-H1) is 1.5 or more [J / g]. (Method 4) The image forming method according to any one of Methods 1 to 3, wherein H1 is 2.0 to 18.0 [J / g]. (Method 5) The adhesion method according to any one of Methods 1 to 4, wherein the first toner and the second toner contain wax. (Method 6) The adhesion method according to any one of Methods 1 to 5, wherein the first toner is a black toner containing carbon black. (Configuration 7) A toner set for use in the adhesion method, comprising: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the toner set has the first toner and the second toner separately, the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the amount of heat generated in the first toner is H1 [J / g] and the amount of heat generated in the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 (1) H1< / h2> <h2 ···(2)However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; the amount of heat generated in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A toner set comprising: (Configuration 8) 8. The toner set according to configuration 7, wherein the difference between H2 and H1 (H2-H1) is 1.5 [J / g] or more. (Configuration 9) The toner set according to the seventh or eighth aspect, wherein H1 is 2.0 to 18.0 [J / g]. (Configuration 10) 10. The toner set according to any one of configurations 7 to 9, wherein the first toner is a black toner containing carbon black. (Configuration 11) 1. An adhesive device comprising: The bonding device comprises: means for forming a first unfixed toner layer on a first surface of the sheet with a first toner; a means for forming a second unfixed toner layer on the first unfixed toner layer by using a second toner; Heat is applied from the surface of the second unfixed toner layer, and the first unfixed toner layer and the second unfixed toner layer are heated. a means for fixing the unfixed toner layer of the sheet to form an adhesive image pattern on the sheet; and a means for heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the amount of heat generated in the first toner is H1 [J / g] and the amount of heat generated in the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 ···(1) H1< / h2> <h2 ···(2)However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; the amount of heat generated in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A bonding device characterized by: (Configuration 12) A method for producing an adhesive product, comprising the steps of: The production method comprises the steps of: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the amount of heat generated in the first toner is H1 [J / g] and the amount of heat generated in the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 (1) H1< / h2> <h2 ···(2)However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180°C for 10 minutes, followed by a cooling step of cooling from 180°C to 20°C at a rate of 10°C / min; the amount of heat generated in the range of 35°C to 75°C at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A method for producing a bonded article, comprising the steps of: (Configuration 13) A bonding method comprising the steps of: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; A second unfixed toner layer is formed on the first unfixed toner layer using a second toner. A process of a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, the first toner and the second toner contain a hydrocarbon wax; When the content of the wax per 100 parts by mass of the binder resin in the first toner is W1 [parts by mass] and the content of the wax per 100 parts by mass of the binder resin in the second toner is W2 [parts by mass], W1 and W2 satisfy the following formulas (3) and (4): 5.8≦W2≦13.1 (3) W1 <w2 ···(4) A bonding method characterized by:< / w2> < / h2>

Claims

1. A bonding method comprising the steps of: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the heat generation amount of the first toner is H1 [J / g] and the heat generation amount of the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 ... (1) H1<H2...(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180° C. for 10 minutes, followed by a cooling step of cooling from 180° C. to 20° C. at a rate of 10° C. / min; the amount of heat generated in the range of 35° C. to 75° C. at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A bonding method characterized by:

2. 2. The bonding method according to claim 1, further comprising the step of heating the fixed toner images of the adhesive image patterns formed on different sheets in an overlapping state to bond the sheets together, thereby obtaining the bonded product.

3. 3. The bonding method according to claim 1, wherein the difference between H2 and H1 (H2-H1) is 1.5 [J / g] or more.

4. The bonding method according to claim 1 or 2, wherein the H1 is 2.0 to 18.0 [J / g].

5. 3. The method of claim 1, wherein the first toner and the second toner comprise a wax.

6. 3. The adhesion method according to claim 1, wherein the first toner is a black toner containing carbon black.

7. A toner set for use in the adhesion method, comprising: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the toner set has the first toner and the second toner separately, the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the heat generation amount of the first toner is H1 [J / g] and the heat generation amount of the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 ... (1) H1<H2...(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180° C. for 10 minutes, followed by a cooling step of cooling from 180° C. to 20° C. at a rate of 10° C. / min; the amount of heat generated in the range of 35° C. to 75° C. at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A toner set comprising:

8. 8. The toner set according to claim 7, wherein the difference between H2 and H1 (H2-H1) is 1.5 [J / g] or more.

9. 9. The toner set according to claim 7, wherein the H1 is 2.0 to 18.0 [J / g].

10. 9. The toner set according to claim 7, wherein the first toner is a black toner containing carbon black.

11. 1. An adhesive device comprising: The bonding device comprises: means for forming a first unfixed toner layer on a first surface of the sheet with a first toner; a means for forming a second unfixed toner layer on the first unfixed toner layer by using a second toner; a means for applying heat from the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a means for heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the heat generation amount of the first toner is H1 [J / g] and the heat generation amount of the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 ... (1) H1<H2...(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180° C. for 10 minutes, followed by a cooling step of cooling from 180° C. to 20° C. at a rate of 10° C. / min; the amount of heat generated in the range of 35° C. to 75° C. at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A bonding device characterized by:

12. A method for producing an adhesive product, comprising the steps of: The production method comprises the steps of: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, When the heat generation amount of the first toner is H1 [J / g] and the heat generation amount of the second toner is H2 [J / g], H1 and H2 satisfy the following formulas (1) and (2): 6.0≦H2≦24.0 ... (1) H1<H2...(2) However, H1 and H2 are (i) a temperature increasing step of increasing the temperature from 20° C. to 180° C. at a rate of 10° C. / min; and (ii) holding at 180° C. for 10 minutes, followed by a cooling step of cooling from 180° C. to 20° C. at a rate of 10° C. / min; the amount of heat generated in the range of 35° C. to 75° C. at the exothermic peak of the DSC curve obtained in the cooling step after passing through the cooling step; A method for producing a bonded article, comprising the steps of:

13. A bonding method comprising the steps of: The bonding method comprises: forming a first unfixed toner layer on a first side of the sheet using a first toner; forming a second unfixed toner layer on the first unfixed toner layer using a second toner; a step of heating the surface of the second unfixed toner layer to fix the first unfixed toner layer and the second unfixed toner layer to the sheet, thereby forming an adhesive image pattern on the sheet; and a step of heating the sheets in a state in which the image patterns for adhesion formed on the same sheet or different sheets are superimposed on each other to adhere the sheets together to obtain an adhered product; having the adhesive image pattern has a fixed toner image derived from the second unfixed toner layer on a surface thereof, the first toner and the second toner contain a hydrocarbon wax; When the content of the wax per 100 parts by mass of the binder resin in the first toner is W1 [parts by mass] and the content of the wax per 100 parts by mass of the binder resin in the second toner is W2 [parts by mass], W1 and W2 satisfy the following formulas (3) and (4): 5.8≦W2≦13.1 ... (3) W1<W2...(4) A bonding method characterized by:

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