Image formation method, and toner

Abstract

To provide an image formation method that is the method for forming images onto a polyethylene terephthalate film, and enables obtaining images excellent in tight adhesion to the polyethylene terephthalate film.SOLUTION: Thanks to toner including crystalline polyester resin C and non-crystalline composite resin A in binder resin, the present invention is a method that forms images onto a polyethylene terephthalate film, in which the crystalline polyester resin C is a polycondensation of an alcohol component including more than 90 mol% of ethylene glycol, and a carboxylic acid component including 80 mol% of an aliphatic dicarboxylic acid having carbon atoms more than 10, and less than 16, and the non-crystalline composite resin A includes a polyester resin segment, and an addition polymerization resin segment that contains a constituent unit derived from vinyl monomer having a hydrocarbon group with carbon atoms more than 10, and less than 24.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an image forming method and a toner. [Background technology]

[0002] The diversification of print media has led to a demand for electrophotographic printing on print media other than paper. Polyethylene terephthalate film (hereinafter also referred to as PET film) is in high demand as a packaging film for frozen foods, retort foods, etc., due to its excellent heat resistance, cold resistance, and aroma preservation properties. On the other hand, PET film has a smoother substrate surface than paper, so the anchor effect is less likely to occur between the substrate and the coating film (image) formed by printing electrophotographic toner. Furthermore, PET film has a lower surface tension than paper, so the image does not wet the substrate as easily. As a result, there is a problem that the image does not adhere well to the PET film and is easily peeled off. Patent Document 1 discloses a toner containing a resin composition that contains a polymer (A) and a polyester resin (B), the polymer (A) being a modified product of a polymer (a) containing a specific structural unit with at least one of an unsaturated carboxylic acid and an anhydride thereof, for the purpose of providing a toner that can provide a print film having excellent adhesion to PET films and PP films and excellent storage stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2021-161177 A Summary of the Invention [Problem to be solved by the invention]

[0004] In food packaging, images need to be firmly attached to the printing film in order to prevent peeling of designs and ingredient labels. However, images formed by conventional image forming methods using toners do not have sufficient adhesion to polyethylene terephthalate films used as printing films. The present invention relates to a method for forming an image on a polyethylene terephthalate film, which is capable of obtaining an image having excellent adhesion to the polyethylene terephthalate film, and a toner capable of obtaining an image having excellent adhesion to the polyethylene terephthalate film. [Means for solving the problem]

[0005] The present inventors have found that an image formed on a polyethylene terephthalate film by a toner containing in combination a crystalline polyester resin which is a polycondensation product of an alcohol component containing at least a specific amount of ethylene glycol and a carboxylic acid component containing at least a specific amount of an aliphatic dicarboxylic acid having a specific number of carbon atoms, and an amorphous composite resin which contains a polyester resin segment and an addition polymerization resin segment which contains a structural unit derived from a vinyl monomer having a hydrocarbon group with a specific number of carbon atoms, has excellent adhesion to the polyethylene terephthalate film. The present invention relates to the following [1] and [2]. [1] A method for forming an image on a polyethylene terephthalate film using a toner containing a crystalline polyester resin C and an amorphous composite resin A in a binder resin, comprising: the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms; The amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms. Image forming method. [2] A toner for forming an image on a polyethylene terephthalate film, the toner comprising a crystalline polyester resin C and an amorphous composite resin A in a binder resin, the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms; The amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms. toner. Effect of the Invention

[0006] According to the present invention, there is provided a method for forming an image on a polyethylene terephthalate film, which can obtain an image having excellent adhesion to the polyethylene terephthalate film. Also, according to the present invention, there is provided a toner capable of obtaining an image having excellent adhesion to the polyethylene terephthalate film. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram showing an end face of a test piece used for evaluating adhesion in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] [Image forming method] The image forming method of the present invention is a method for forming an image on a polyethylene terephthalate film using a toner containing a crystalline polyester resin C and an amorphous composite resin A in a binder resin, in which the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms, and the amorphous composite resin A contains a polyester resin segment and an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms. In the following description, the "crystalline polyester resin C" may be simply referred to as "resin C" and the "amorphous composite resin A" may be simply referred to as "resin A." The toner used in the image forming method of the present invention may be simply referred to as "toner."

[0009] Although the detailed mechanism by which the image forming method of the present invention enables the formation of an image having high adhesion to a PET film is not clear, it is believed to be as follows. In the present invention, a toner containing a combination of a crystalline polyester resin C, which is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms, and an amorphous composite resin A containing an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms, is used. Since the hydrocarbon group having a specific carbon number in the amorphous composite resin A has an affinity for the aliphatic chain having a specific carbon number in the crystalline polyester resin C, it is considered that the crystalline polyester resin C is easily finely dispersed in the amorphous composite resin A in the toner and the crystallization of the crystalline polyester domain is promoted. Then, when the toner is heated and fixed on the PET film, the crystalline polyester resin C and the amorphous composite resin A are fixed in a compatible state, but after fixing, the crystalline polyester resin C is immediately finely dispersed and recrystallized due to the temperature drop of the toner, and the toner is fixed on the PET film via the crystalline polyester resin C, which has a high affinity with ethylene glycol, which is a PET component, and an image having high adhesion to the PET film is formed. It should be noted that the above-mentioned mechanism regarding the effect of the present invention is merely a presumption, and the present invention is not limited thereto.

[0010] The definitions of various terms used in this specification are given below. In the specification, the carboxylic acid component of the polyester resin includes not only the compound itself, but also anhydrides that decompose during the reaction to produce a carboxylic acid, and alkyl esters of each carboxylic acid (alkyl groups having 1 to 3 carbon atoms). Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (°C) / maximum endothermic peak temperature (°C)) in the measurement method described in the examples below. A crystalline resin is one with a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one in which no endothermic peak is observed, or, if observed, has a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted by the types and ratios of raw material monomers, as well as production conditions such as reaction temperature, reaction time, and cooling rate. With respect to hydrocarbon groups, the use of "iso" in parentheses refers to both the presence and absence of the prefix, and indicates normal when the prefix is ​​absent. "(Meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. By "styrenic compound" is meant unsubstituted or substituted styrene. The components contained in the toner used in the image forming method of the present invention (respective essential components) and the components that may be contained in the toner (respective optional components) may be used alone or in combination of two or more kinds.

[0011] An example of the image forming method of the present invention is an image forming method that includes, similarly to a conventionally known image forming method using a toner (toner for developing electrostatic images), an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image, a transfer step of transferring the toner image formed on the electrostatic latent image carrier to the surface of a polyethylene terephthalate film, and a fixing step of fixing the toner image transferred to the surface of the polyethylene terephthalate film.

[0012] <Toner> The toner used in the image forming method of the present invention contains, in the binder resin, a crystalline polyester resin C and an amorphous composite resin A. The term "binder resin" refers to the entire resin components contained in the toner. The term "resin components" refers to polymer components excluding the release agent, and preferably has a weight average molecular weight of 1,000 or more.

[0013] [Binder Resin] <Crystalline polyester resin C> The toner used in the image forming method of the present invention contains a crystalline polyester resin C in the binder resin. The crystalline polyester resin C is a polycondensation product of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms.

[0014] The alcohol component contains 90 mol % or more of ethylene glycol. In order to obtain an image having excellent adhesion to the PET film, the content of ethylene glycol in the alcohol component is preferably 95 mol % or more and 100 mol % or less, and preferably 100 mol %.

[0015] The alcohol component may include an α,ω-aliphatic diol other than ethylene glycol. Examples of the α,ω-aliphatic diols include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol.

[0016] The alcohol component may contain other alcohol components different from ethylene glycol and the above-mentioned α,ω-aliphatic diol. Examples of the other alcohol components include aliphatic diols other than ethylene glycol and the above-mentioned α,ω-aliphatic diols, aromatic diols, and trihydric or higher alcohols. These alcohol components may be used alone or in combination.

[0017] The carboxylic acid component contains 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms. The carbon number of the aliphatic dicarboxylic acid having 10 to 16 carbon atoms is preferably 12 or more and preferably 14 or less, from the viewpoint of obtaining an image having excellent adhesion to the PET film.

[0018] The aliphatic dicarboxylic acid having 10 to 16 carbon atoms is preferably an α,ω-aliphatic dicarboxylic acid represented by the following general formula (1). [ka] In general formula (1), L 1 represents an aliphatic group having 8 to 14 carbon atoms, and preferably represents an alkylene group. From the viewpoint of obtaining an image having excellent adhesion to a PET film, the number of carbon atoms of the aliphatic group is preferably 10 or more and preferably 12 or less. The alkylene group may be linear or branched, and is preferably linear.

[0019] Examples of the aliphatic dicarboxylic acid include sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecanedioic acid. Among these, 1,12-dodecanedioic acid and 1,14-tetradecanedioic acid are more preferable. These carboxylic acid components may be used alone or in combination.

[0020] From the viewpoint of obtaining an image having excellent adhesion to a PET film, the amount of the aliphatic dicarboxylic acid having 10 to 16 carbon atoms in the carboxylic acid component is preferably 85 mol % or more, more preferably 90 mol % or more, and even more preferably 95 mol % or more, and is 100 mol % or less.

[0021] The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid having 10 to 16 carbon atoms. Examples of the other carboxylic acid component include monovalent carboxylic acids such as stearic acid, aliphatic dicarboxylic acids having less than 10 or more than 16 carbon atoms, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and polyvalent carboxylic acids having three or more carboxylic acids. These carboxylic acid components may be used alone or in combination.

[0022] The equivalent ratio of the carboxyl groups of the carboxylic acid component to the hydroxyl groups of the alcohol component [COOH groups / OH groups] is preferably 0.7 or more, more preferably 0.8 or more, and is preferably 1.3 or less, more preferably 1.2 or less.

[0023] (Method for producing crystalline polyester resin C) The crystalline polyester resin C is produced by a method of polycondensing an alcohol component and a carboxylic acid component. During polycondensation, if necessary, an esterification catalyst such as tin(II) di(2-ethylhexanoate), dibutyltin oxide, or titanium diisopropoxybis(triethanolaminate) may be used in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component; or an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) may be used in an amount of 0.001 to 0.5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. When a monomer having an unsaturated bond such as fumaric acid is used in polycondensation, a radical polymerization inhibitor may be used, if necessary, in an amount of preferably 0.001 to 0.5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. An example of the radical polymerization inhibitor is 4-tert-butylcatechol. The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, and even more preferably 180° C. or higher, and is preferably 250° C. or lower, more preferably 240° C. or lower. The polycondensation may be carried out in an inert gas atmosphere.

[0024] (Physical properties of crystalline polyester resin C) From the viewpoint of obtaining an image having excellent adhesion to the PET film, the softening point of Resin C is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, and is preferably 105°C or lower, more preferably 100°C or lower, even more preferably 95°C or lower. From the viewpoint of obtaining an image having excellent adhesion to the PET film, the melting point of resin C is preferably 65°C or higher, more preferably 70°C or higher, even more preferably 75°C or higher, and is preferably 105°C or lower, more preferably 100°C or lower, even more preferably 95°C or lower.

[0025] The acid value of resin C is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, and preferably 25 mgKOH / g or less, more preferably 20 mgKOH / g or less, and even more preferably 15 mgKOH / g or less.

[0026] The softening point, melting point and acid value of the crystalline polyester resin C can be appropriately adjusted by the type and amount of the raw material monomer, as well as production conditions such as reaction temperature, reaction time and cooling rate, and are determined by the method described in the Examples below. When two or more types of crystalline polyester resin C are used in combination, it is preferable that the softening point, melting point and acid value obtained as a mixture thereof are each within the above-mentioned ranges.

[0027] <Amorphous composite resin A> In the present invention, the toner contains, as a binder resin, an amorphous composite resin A in addition to the above-mentioned crystalline polyester resin C. The amorphous composite resin A is an amorphous polyester resin containing a polyester resin segment and an addition polymerization resin segment containing a constituent unit derived from a vinyl monomer having a hydrocarbon group having from 10 to 24 carbon atoms.

[0028] The amorphous composite resin A is preferably a resin chemically bonded via a bireactive monomer capable of reacting with both the raw material monomer of the polyester resin segment and the raw material monomer of the addition polymerization resin segment.

[0029] The polyester resin segment is obtained by polycondensation of an alcohol component and a carboxylic acid component.

[0030] Examples of the alcohol component include alkylene oxide adducts of aromatic diols, aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, alkylene oxide adducts of aromatic diols are preferred from the viewpoint of obtaining an image with excellent adhesion to the PET film. The alkylene oxide adduct of an aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably an alkylene oxide adduct of formula (I):

[0031] [ka] (In the formula, OR 1 and R 2 O is an oxyalkylene group, and R 1 and R 2 each independently represents an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added and are each a positive number, and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, and more preferably 4 or less.

[0032] Examples of the alkylene oxide adduct of bisphenol A represented by formula (I) include a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. Among these, it is preferable to contain a propylene oxide adduct of bisphenol A. The content of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% or less, and even more preferably 100 mol%. The content of the propylene oxide adduct of bisphenol A in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol% or less, and even more preferably 100 mol%.

[0033] Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and 3-methyl-1,5-pentanediol. Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and adducts of hydrogenated bisphenol A with alkylene oxides having 2 to 4 carbon atoms (average number of moles added: 2 to 12). Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol. These alcohol components may be used alone or in combination of two or more.

[0034] Examples of the carboxylic acid component include dicarboxylic acids and polycarboxylic acids having three or more carboxylic acids. Examples of dicarboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids is preferred. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred. The amount of aromatic dicarboxylic acid in the carboxylic acid component is preferably 45 mol% or more, more preferably 50 mol% or more, even more preferably 55 mol% or more, and is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 65 mol% or less.

[0035] The aliphatic dicarboxylic acid preferably has 2 or more, more preferably 3 or more, and preferably has 30 or less, more preferably 20 or less.

[0036] Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, and succinic acid substituted with an aliphatic hydrocarbon group having from 1 to 20 carbon atoms. Examples of succinic acid substituted with an aliphatic hydrocarbon group having from 1 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. From the viewpoint of obtaining an image having excellent adhesion to the PET film, fumaric acid and sebacic acid are preferred, sebacic acid is more preferred, and a combination of fumaric acid and sebacic acid is even more preferred. The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 10 mol % or more, more preferably 20 mol % or more, even more preferably 25 mol % or more, and is preferably 45 mol % or less, more preferably 40 mol % or less, even more preferably 35 mol % or less.

[0037] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the amount of fumaric acid is preferably 30 mol % or more, more preferably 35 mol % or more, even more preferably 40 mol % or more, and is preferably 60 mol % or less, more preferably 55 mol % or less, even more preferably 50 mol % or less, in the aliphatic dicarboxylic acid of the carboxylic acid component.

[0038] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the amount of sebacic acid is preferably 40 mol % or more, more preferably 45 mol % or more, even more preferably 50 mol % or more, and is preferably 70 mol % or less, more preferably 65 mol % or less, even more preferably 60 mol % or less, in the aliphatic dicarboxylic acid of the carboxylic acid component.

[0039] An example of the alicyclic dicarboxylic acid is cyclohexanedicarboxylic acid.

[0040] The trivalent or higher polyvalent carboxylic acid is preferably an aromatic trivalent carboxylic acid, and trimellitic acid or its anhydride is preferred. When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid in the carboxylic acid component is preferably 3 mol % or more, more preferably 6 mol % or more, even more preferably 9 mol % or more, and is preferably 25 mol % or less, more preferably 20 mol % or less, even more preferably 15 mol % or less. These carboxylic acid components may be used alone or in combination of two or more.

[0041] The equivalent ratio of the carboxyl groups of the carboxylic acid component to the hydroxyl groups of the alcohol component [COOH groups / OH groups] is preferably 0.7 or more, more preferably 0.8 or more, and is preferably 1.3 or less, more preferably 1.2 or less.

[0042] From the viewpoint of obtaining an image having excellent adhesion to a PET film, the addition polymerization resin segment is an addition polymerization resin segment containing a constituent unit derived from a vinyl monomer having a hydrocarbon group having a carbon number of 10 to 24. The addition polymerization resin segment preferably further contains a constituent unit derived from a styrene-based compound.

[0043] From the viewpoint of obtaining an image having excellent adhesion to a PET film, the number of carbon atoms in the hydrocarbon group of the vinyl monomer having a hydrocarbon group is preferably 12 or more and preferably 22 or less, more preferably 18 or less.

[0044] Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, of which alkyl and alkenyl groups are preferred, and alkyl groups are more preferred. The hydrocarbon group may be either branched or linear. Examples of the raw material vinyl monomer of the addition polymerization resin segment having a hydrocarbon group include (meth)acrylic acid esters having a hydrocarbon group and olefins having a hydrocarbon group. Among these, from the viewpoint of obtaining an image having excellent adhesion to a PET film, (meth)acrylic acid esters having a hydrocarbon group are preferred. In the case of (meth)acrylic acid esters, the hydrocarbon group is the alcohol side residue of the ester.

[0045] Examples of (meth)acrylic acid esters having a hydrocarbon group include (iso)decyl (meth)acrylate, (iso)dodecyl (meth)acrylate (hereinafter also referred to as (iso)lauryl (meth)acrylate), (iso)palmityl (meth)acrylate, (iso)stearyl (meth)acrylate, (iso)behenyl (meth)acrylate, and the like. Of these, (iso)lauryl (meth)acrylate, (iso)stearyl (meth)acrylate, and (iso)behenyl (meth)acrylate are preferred, (iso)lauryl (meth)acrylate and (iso)stearyl (meth)acrylate are more preferred, and lauryl methacrylate and stearyl methacrylate are even more preferred.

[0046] From the viewpoint of obtaining an image having excellent adhesion to PET film, the content of structural units derived from vinyl monomers having a hydrocarbon group having 10 or more and 24 or less carbon atoms in Resin A is preferably 1 mass % or more, more preferably 2 mass % or more, even more preferably 3 mass % or more, and is preferably 10 mass % or less, more preferably 8 mass % or less, even more preferably 6 mass % or less. In order to obtain an image having excellent adhesion to PET film, the content of structural units derived from vinyl monomers having a hydrocarbon group having 10 to 24 carbon atoms in the addition polymerization resin segment is preferably 5 mass % or more, more preferably 10 mass % or more, even more preferably 15 mass % or more, and is preferably 50 mass % or less, more preferably 45 mass % or less, even more preferably 40 mass % or less.

[0047] The styrene-based compound may be substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof. Specific examples include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrenesulfonic acid, or a salt thereof, and preferably includes styrene, more preferably styrene. In the addition polymerization resin segment, the content of structural units derived from a styrene-based compound is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, from the viewpoint of obtaining an image having excellent adhesion to a PET film. Other than the above, examples of raw vinyl monomers that can be used for the addition polymerization resin segment include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic acid esters having a hydrocarbon group having 1 to 9 carbon atoms, such as methyl (meth)acrylate; (meth)acrylic acid aminoalkyl esters such as dimethylaminoethyl (meth)acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone.

[0048] As for the raw material vinyl monomer for the addition polymerization resin segment, from the viewpoint of obtaining an image having excellent adhesion to PET film, a combination of a vinyl monomer having a hydrocarbon group having from 10 to 24 carbon atoms and a styrene-based compound is preferable, a combination of an alkyl ester of (meth)acrylic acid having an alkyl group having from 10 to 24 carbon atoms and styrene is more preferable, and among these, a combination of stearyl (meth)acrylate or lauryl (meth)acrylate and styrene is even more preferable, and a combination of stearyl methacrylate or lauryl methacrylate and styrene is even more preferable. When a vinyl monomer having a hydrocarbon group with 10 or more and 24 or less carbon atoms is used in combination with a styrene-based compound, the mass ratio of the constituent units derived from the vinyl monomer having a hydrocarbon group with 10 or more and 24 or less carbon atoms in the addition polymerization resin segment to the constituent units derived from the styrene-based compound [constituent units derived from the vinyl monomer having a hydrocarbon group with 10 or more and 24 or less carbon atoms / constituent units derived from the styrene-based compound] is preferably 5 / 95 or more, more preferably 10 / 90 or more, even more preferably 15 / 85 or more, and is preferably 50 / 50 or less, more preferably 45 / 55 or less, even more preferably 40 / 60 or less, from the viewpoint of obtaining an image that has excellent adhesion to PET film.

[0049] The total content of the constituent units derived from vinyl monomers having a hydrocarbon group having 10 to 24 carbon atoms and the constituent units derived from styrene-based compounds in the addition polymerization resin segment is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, and even more preferably 100% by mass, from the viewpoint of obtaining an image that has excellent adhesion to PET film.

[0050] Resin A preferably has a constitutional unit derived from a bireactive monomer bonded to a polyester resin segment and an addition polymerization resin segment via a covalent bond. Examples of the bireactive monomer include addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, addition polymerizable monomers having at least one functional group selected from a hydroxyl group and a carboxyl group are preferred, and addition polymerizable monomers having a carboxyl group are more preferred. Examples of the addition polymerizable monomer having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, from the viewpoint of reactivity in both the polycondensation reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred. The amount of the structural units derived from the bireactive monomer is preferably 1 part by mol or more, more preferably 5 parts by mol or more, and even more preferably 8 parts by mol or more, relative to 100 parts by mol of the structural units derived from the alcohol component of the polyester resin segment of Resin A, and is preferably 30 parts by mol or less, more preferably 25 parts by mol or less, and even more preferably 20 parts by mol or less.

[0051] The content of the polyester resin segment in the resin A is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the total amount of the polyester resin segment and the addition polymerization resin segment. The constitutional unit derived from the bireactive monomer is defined as a polyester resin segment.

[0052] The content of the addition polymerization resin segment in Resin A is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, and preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, based on the total amount of the polyester resin segment and the addition polymerization resin segment.

[0053] The amount of the constitutional units derived from the bireactive monomer in the resin A is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, even more preferably 0.8 mass% or more, and is preferably 10 mass% or less, more preferably 7 mass% or less, even more preferably 4 mass% or less, based on the total amount of the polyester resin segment and the addition polymerization resin segment.

[0054] The total amount of polyester resin segments and addition polymerization resin segments in resin A is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and is 100% by mass or less, preferably 100% by mass.

[0055] The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer for the addition polymerization resin segment, the bireactive monomer, and the radical polymerization initiator, and the mass of the polyester resin segment, etc. is based on the mass excluding the mass of water generated by polycondensation. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is calculated by including it in the addition polymerization resin segment.

[0056] (Production of amorphous composite resin A) Resin A may be produced, for example, by a method including a step A of polycondensing an alcohol component and a carboxylic acid component, and a step B of addition polymerizing raw material monomers of the addition polymerization resin segment and a bireactive monomer. Step B may be carried out after step A, step B may be carried out after step A, or step A and step B may be carried out simultaneously. In step A, a part of the carboxylic acid component may be subjected to a polycondensation reaction, and then step B may be carried out, after which the remainder of the carboxylic acid component may be added to the polymerization system to further advance the polycondensation reaction.

[0057] In the step A, polycondensation may be carried out using an esterification catalyst and an esterification promoter, if necessary. When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation, a polymerization inhibitor may be used as necessary. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropoxybis(triethanolaminate). Examples of the esterification promoter that can be used together with the esterification catalyst include gallic acid (3,4,5-trihydroxybenzoic acid). When an esterification catalyst is used, the amount of the esterification catalyst used is preferably 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component which are the raw material monomers of the resin A. When an esterification promoter is used, the amount of the esterification promoter used is preferably 0.001 part by mass or more and 1 part by mass or less per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Furthermore, examples of the polymerization inhibitor include radical polymerization inhibitors such as 4-tert-butylcatechol. When a polymerization inhibitor is used, the amount of the polymerization inhibitor used is preferably 0.001 part by mass or more and 1 part by mass or less based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, and even more preferably 180° C. or higher, and is preferably 250° C. or lower, more preferably 240° C. or lower. The polycondensation may be carried out in an inert gas atmosphere.

[0058] Examples of the radical polymerization initiator for the addition polymerization in step B include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile). The amount of the radical polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the raw material monomer of the addition polymerization resin segment. The temperature of the addition polymerization is preferably 110° C. or higher, more preferably 130° C. or higher, and preferably 230° C. or lower, more preferably 220° C. or lower, and further preferably 210° C. or lower.

[0059] (Physical properties of amorphous composite resin A) From the viewpoint of obtaining an image having excellent adhesion to the PET film, the softening point of resin A is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, and is preferably 130°C or lower, and more preferably 120°C or lower. From the viewpoint of obtaining an image having excellent adhesion to a PET film, the glass transition temperature of Resin A is preferably 30° C. or higher, more preferably 40° C. or higher, even more preferably 45° C. or higher, and is preferably 80° C. or lower, more preferably 70° C. or lower, even more preferably 60° C. or lower.

[0060] The acid value of Resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, even more preferably 15 mgKOH / g or more, and is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, even more preferably 25 mgKOH / g or less. The softening point, glass transition temperature, and acid value of Resin A can be appropriately adjusted by the types and amounts of raw material monomers used, as well as production conditions such as reaction temperature, reaction time, and cooling rate, and these values ​​can be determined by the methods described in the examples. When two or more resins A are used in combination, the softening point, glass transition temperature and acid value of the resulting mixture are preferably within the above-mentioned ranges.

[0061] <Amorphous polyester resin B> In the present invention, the toner preferably contains, as a binder resin, an amorphous polyester resin B in addition to the above-mentioned crystalline polyester resin C and amorphous composite resin A, and more preferably the toner has a core-shell structure, the core portion contains the crystalline polyester resin C and the amorphous composite resin A, and the shell portion contains the amorphous polyester resin B. Hereinafter, the "amorphous polyester resin B" is also simply referred to as "resin B". Examples of resin B include amorphous polyester resins that do not contain an addition polymerization resin segment containing a constituent unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms, polyester resins, and modified polyester resins. Examples of modified polyester resins include urethane-modified polyester resins and epoxy-modified polyester resins. Among these, polyester resins are preferred.

[0062] From the viewpoint of obtaining an image having excellent adhesion to a PET film, the content of the binder resin in the toner is preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, and is preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less.

[0063] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the content of resin C in the binder resin is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less.

[0064] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the content of resin A in the binder resin is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less.

[0065] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the mass ratio of resin C to resin A in the binder resin [resin C / resin A] is preferably 3 / 97 or more, more preferably 6 / 94 or more, even more preferably 9 / 91 or more, even more preferably 15 / 85 or more, even more preferably 20 / 80 or more, even more preferably 25 / 75 or more, and is preferably 45 / 55 or less, more preferably 40 / 60 or less, even more preferably 35 / 65 or less.

[0066] From the viewpoint of obtaining an image having excellent adhesion to the PET film, the content of resin B in the binder resin is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less.

[0067] [Coloring Agent] The toner used in the image forming method of the present invention preferably contains a colorant, and when the toner has a core-shell structure, it is more preferable that the core portion contains a colorant. As the colorant, any dye, pigment, etc. used as a toner colorant can be used. Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment green B, rhodamine B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, disazo yellow, and pigment red 269. The toner may be either a black toner or a color toner other than black. From the viewpoint of image density, the content of the colorant in the toner is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less.

[0068] [Release Agent] The toner used in the image forming method of the present invention preferably contains a release agent, and when the toner has a core-shell structure, it is more preferable that the core portion contains a release agent. Examples of the release agent include polypropylene wax, polyethylene wax, polypropylene-polyethylene copolymer wax, hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and oxides thereof, ester waxes such as carnauba wax, montan wax, and deacidified waxes thereof, and fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, and fatty acid metal salts. These may be used alone or in combination of two or more.

[0069] The melting point of the release agent is preferably 60° C. or higher, more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 140° C. or lower, and further preferably 120° C. or lower. The content of the release agent in the toner is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less.

[0070] The toner may further contain additives such as a charge control agent, a magnetic powder, a flowability improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, an antiaging agent, and a cleaning property improver.

[0071] <Toner manufacturing method> The toner used in the image forming method of the present invention may be produced by any of the known methods such as melt kneading, emulsion phase inversion, suspension polymerization, emulsion aggregation, etc., and the emulsion aggregation method is preferred.

[0072] [Emulsification aggregation method] The emulsion aggregation method includes a step of aggregating and fusing resin particles, which contain resin C and resin A in the same or different particles, in an aqueous medium.

[0073] (Process for agglomerating resin particles) In the step of aggregating the resin particles, resin particles containing resin C and resin A in the same or different particles are aggregated in an aqueous medium to obtain aggregated particles 1. It is preferable to further aggregate a colorant and a release agent in addition to the resin particles, and it is preferable to mix a resin particle dispersion, a colorant particle dispersion, and a release agent particle dispersion, and aggregate these particles to obtain aggregated particles 1.

[0074] In the present invention, the aqueous medium used in the aqueous dispersion is a medium containing water as a main component, and the content of water in the aqueous medium is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and 100% by mass or less. As the water, deionized water, ion-exchanged water, or distilled water is preferable. Examples of components other than water that can form an aqueous medium together with water include organic solvents that dissolve in water, such as alkyl alcohols having 1 to 5 carbon atoms, dialkyl ketones having 3 to 5 carbon atoms, such as acetone and methyl ethyl ketone, and cyclic ethers, such as tetrahydrofuran. Among these, alkyl alcohols having 1 to 5 carbon atoms are preferred, and ethanol is more preferred.

[0075] <Method for producing resin particle dispersion> The resin particles of resin C and the resin particles of resin A may be prepared as an aqueous dispersion of resin particles containing resin C and resin A in the same or different particles.

[0076] Dispersion can be performed using a known method, but it is preferable to disperse by a phase inversion emulsification method. For example, the phase inversion emulsification method includes a method of adding an aqueous medium to an organic solvent solution of resin C and / or resin A or molten resin C and / or resin A to perform phase inversion emulsification. A method of adding an aqueous medium to an organic solvent solution of resin C and / or resin A to perform phase inversion emulsification is preferable. The organic solvent used for phase inversion emulsification is not particularly limited as long as it dissolves the resin C and the resin A and is water-soluble, and examples thereof include methyl ethyl ketone. A neutralizing agent may be added to the organic solvent solution. Examples of the neutralizing agent include basic substances. Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and nitrogen-containing basic substances such as ammonia, trimethylamine, and diethanolamine. Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred. The degree of neutralization of resin C and / or resin A constituting the resin particles is preferably 40 mol % or more, more preferably 45 mol % or more, even more preferably 50 mol % or more, and preferably 100 mol % or less, more preferably 80 mol % or less, even more preferably 70 mol % or less. The degree of neutralization of the resin C and / or the resin A constituting the resin particles can be calculated by the following formula. Degree of neutralization (mol%) = [{weight of neutralizing agent added (g) / equivalent weight of neutralizing agent} / [{weighted average acid value of resin constituting resin particle (mgKOH / g) × weight of resin constituting resin particle (g)} / (56 × 1000)]] × 100

[0077] While stirring the organic solvent solution or the molten resin C and / or resin A, the aqueous medium is gradually added to cause phase inversion. From the viewpoint of improving the dispersion stability of the resin particles containing resin C and / or resin A, the temperature of the organic solvent solution when the aqueous medium is added is preferably not less than the glass transition temperature of resin A, more preferably not less than 60°C, even more preferably not less than 70°C, and is preferably not more than 100°C, more preferably not more than 95°C, even more preferably not more than 90°C.

[0078] After the phase inversion emulsification, the organic solvent may be removed from the obtained dispersion by distillation or the like, if necessary. The resin particles may also be isolated by filtration or the like. It is preferable to use an aqueous dispersion of resin particles obtained by removing the organic solvent from the dispersion obtained after the phase inversion emulsification. In this case, the remaining amount of the organic solvent in the dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably substantially 0% by mass.

[0079] Volume median diameter D of resin particles in dispersion 50 is preferably 0.03 μm or more, more preferably 0.06 μm or more, even more preferably 0.09 μm or more, and is preferably 1 μm or less, more preferably 0.5 μm or less, even more preferably 0.2 μm or less. The CV value of the resin particles in the dispersion is preferably 10% or more, more preferably 20% or more, and is preferably 40% or less, more preferably 35% or less. Volume median diameter D of resin particles in dispersion 50 The CV value is measured by the method described in the Examples.

[0080] From the viewpoint of improving the productivity of the toner and the dispersion stability of the resin particle dispersion, the solid content concentration of the resin particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less. The solid content is the total amount of non-volatile components.

[0081] <<Method for producing colorant particle dispersion>> The colorant particles are preferably obtained as a dispersion of the colorant particles by dispersing the colorant and an aqueous medium using a dispersing machine such as a homogenizer, an ultrasonic dispersing machine, etc. From the viewpoint of improving the dispersion stability of the colorant, the dispersion is preferably carried out in the presence of a surfactant or an addition polymer (hereinafter, the addition polymer used to disperse the colorant is also referred to as "addition polymer E"). Examples of the surfactant include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. The addition polymer E preferably has a constituent unit derived from an addition polymerizable monomer a having an aromatic group, and further preferably contains at least one selected from the group consisting of an addition polymerizable monomer b having an ionic group, an addition polymerizable monomer c having a polyalkylene oxide group, and a macromonomer d. For the colorant particle dispersion using the addition polymer E, see JP2021-026129A.

[0082] From the viewpoint of image density of the printed matter, the content of the colorant in the colorant particle dispersion is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less. The solids concentration of the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less.

[0083] Volume median particle size D of colorant particles 50 From the viewpoint of improving the dispersibility of the colorant in the toner, the particle size is preferably 0.05 μm or more, more preferably 0.08 μm or more, and is preferably 0.4 μm or less, more preferably 0.3 μm or less, and further preferably 0.25 μm or less. From the viewpoint of improving the dispersibility of the colorant in the toner, the CV value of the colorant particles is preferably 10% or more, more preferably 15% or more, and is preferably 40% or less, more preferably 35% or less, and even more preferably 30% or less. Volume median particle size D of colorant particles 50 and CV values ​​are measured by the methods in the Examples.

[0084] <Production method of release agent particle dispersion> The release agent particle dispersion can be obtained by using a surfactant, but is preferably obtained by mixing the release agent and resin particles. By preparing the release agent particles using the release agent and resin particles, the release agent particles are stabilized by the resin constituting the resin particles, and it becomes possible to disperse the release agent in an aqueous medium without using a surfactant. It is considered that the release agent particle dispersion has a structure in which a large number of resin particles are attached to the surface of the release agent particles. The resin constituting the resin particles in which the release agent is dispersed is preferably a polyester resin, and it is more preferable to use a composite resin D having a polyester resin segment and an addition polymerization resin segment. For the release agent particle dispersion and the composite resin D, reference is made to JP 2021-182045 A. In addition, the aforementioned amorphous polyester resin A may be used.

[0085] Volume median particle size D of release agent particles 50 From the viewpoint of obtaining uniform aggregated particles 1 by aggregation, the average particle size is preferably 0.05 μm or more, more preferably 0.1 μm or more, even more preferably 0.2 μm or more, and is preferably 1 μm or less, more preferably 0.8 μm or less, even more preferably 0.6 μm or less. The CV value of the release agent particles is preferably 10% or more, more preferably 15% or more, and is preferably 40% or less, more preferably 35% or less, and further preferably 30% or less. Volume median particle size D of release agent particles 50 The CV value is measured by the method described in the Examples.

[0086] -Surfactants- In the step of aggregating the resin particles, when the dispersions of the respective particles are mixed to prepare a mixed dispersion, the process may be carried out in the presence of a surfactant from the viewpoint of improving the dispersion stability of the resin particles, the release agent particles, the colorant particles, etc. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates and alkyl ether sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers. When a surfactant is used, the total amount used is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total amount of the binder resin in the aggregated particles 1, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0087] -Flocculant- In the step of aggregating the resin particles, it is preferable to add an aggregating agent from the viewpoint of efficient aggregation. Examples of the flocculant include cationic surfactants such as quaternary salts, organic flocculants such as polyethyleneimine, and inorganic flocculants. Examples of the inorganic flocculant include inorganic metal salts such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, and calcium nitrate; inorganic ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium nitrate; and divalent or higher metal complexes. From the viewpoint of improving the coagulation properties and obtaining uniformly coagulated particles 1, inorganic coagulants having a valence of 1 to 5 are preferred, inorganic metal salts having a valence of 1 to 2 and inorganic ammonium salts are more preferred, inorganic ammonium salts are even more preferred, and ammonium sulfate is even more preferred.

[0088] For example, 10 parts by mass or more and 50 parts by mass or less of the aggregating agent is added to a mixed dispersion liquid containing resin particles, release agent particles, and colorant particles at 0° C. or more and 40° C. or less, relative to a total of 100 parts by mass of the binder resin in aggregated particles 1, and the resin particles, release agent particles, and colorant particles are aggregated in an aqueous medium to obtain aggregated particles 1. Furthermore, from the viewpoint of promoting aggregation, it is preferable to increase the temperature of the dispersion liquid after adding the aggregating agent.

[0089] Examples of a method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation terminator, a method of diluting the dispersion, etc. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping the aggregation by adding an aggregation terminator is preferred.

[0090] -Aggregation stopper- The aggregation terminator is preferably a surfactant, more preferably an anionic surfactant. Examples of the anionic surfactant include alkylbenzenesulfonate, alkyl sulfate, alkyl ether sulfate, polyoxyalkylene alkyl ether sulfate, arylsulfonate, and arylsulfonic acid formalin condensate, and are preferably an alkali metal salt of arylsulfonic acid formalin condensate, and more preferably a sodium salt of naphthalenesulfonic acid formalin condensate. These may be used alone or in combination. The aggregation terminator may be added in the form of an aqueous solution. The amount of the aggregation terminator added is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the binder resin in the aggregated particles 1 in order to reliably prevent unnecessary aggregation, and is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, in order to reduce the amount of the aggregation terminator remaining in the toner.

[0091] Volume median particle size D of aggregate 1 50 is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 7 μm or less.

[0092] In the present invention, it is preferable to have a step, after the step of aggregating the resin particles and before the step of fusing, of adhering and aggregating shell resin particles containing an amorphous resin to the obtained aggregated particles 1 as cores to obtain aggregated particles 2. By having the step of aggregating the shell resin particles, it is possible to obtain toner particles having a core-shell structure. The shell resin particles are preferably an amorphous resin, more preferably an amorphous polyester resin, still more preferably at least one selected from the above-mentioned resin A and resin B, and even more preferably resin B. The shell resin particle dispersion liquid can be obtained by the same method as the above-mentioned method for producing the resin particle dispersion liquid containing resin A and / or resin C. Furthermore, when the toner manufacturing method includes a step of aggregating shell resin particles, it is preferable to stop the aggregation in the step when the aggregated particles 2 have grown to an appropriate particle size for toner particles, and a method of stopping the aggregation by adding the above-mentioned aggregation terminator is preferable. The amount of the aggregation terminator added is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the binder resin in the aggregated particles 2 in order to reliably prevent unnecessary aggregation, and is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, in order to reduce residue in the toner. The mass ratio of the shell resin particles to the mass of the aggregated particles 1 [shell resin particles / aggregated particles 1] is, from the viewpoint of low-temperature fixing property of the toner, preferably 1 / 99 or more, more preferably 3 / 97 or more, even more preferably 5 / 95 or more, and is preferably 20 / 80 or less, more preferably 15 / 85 or less, even more preferably 10 / 90 or less.

[0093] (Fusing process) In the fusion step, for example, the aggregated particles 1 or the aggregated particles 2 are fused in an aqueous medium. By fusion, the particles contained in aggregated particles 1 or aggregated particles 2 are fused together to obtain fused particles. In the fusion step, from the viewpoint of improving the fusion properties of the aggregated particles 1 or 2 and from the viewpoint of improving the low-temperature fixing properties of the toner, the aggregated particles are maintained at a temperature equal to or higher than the glass transition temperature of the resin having the highest glass transition temperature among the amorphous polyester resins contained in the aggregated particles. The holding temperature when fusing the aggregated particles, from the viewpoint of improving the fusing property of the aggregated particles and improving the productivity of the toner, is preferably at least 2° C. higher, more preferably at least 3° C. higher, and even more preferably at least 5° C. higher than the glass transition temperature of the resin having the highest glass transition temperature among the amorphous polyester resins, and is preferably not higher than 30° C. higher, more preferably not higher than 25° C. higher, and even more preferably not higher than 20° C. higher than the glass transition temperature of the resin having the highest glass transition temperature among the amorphous polyester resins. In this case, the time for which the toner is maintained at a temperature equal to or higher than the glass transition temperature of the amorphous polyester resin is, from the viewpoint of improving the low-temperature fixing property of the toner, preferably 1 minute or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and is preferably 240 minutes or less, more preferably 180 minutes or less, even more preferably 120 minutes or less, even more preferably 90 minutes or less. It is preferable to maintain the temperature at the above temperature until the desired circularity is achieved.

[0094] The volume median particle size D of the fused particles obtained by fusion 50 is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 7 μm or less.

[0095] The circularity of the fused particles obtained by fusion is preferably 0.955 or more, more preferably 0.960 or more, and is preferably 0.990 or less, more preferably 0.985 or less, and further preferably 0.980 or less. The fusion is preferably terminated after the above-mentioned preferred circularity is reached. The circularity is measured by the method described in the Examples.

[0096] (Post-processing) After the fusion step, a post-treatment step may be performed, and the fused particles are isolated to obtain toner particles. Since the fused particles obtained in the fusion step are present in an aqueous medium, it is preferable to first perform solid-liquid separation. For the solid-liquid separation, a suction filtration method or the like is preferably used. It is preferable to wash the solid-liquid separation product. In this case, it is preferable to remove the surfactant added, and therefore it is preferable to wash the product with an aqueous medium at a temperature below the cloud point of the surfactant. It is preferable to wash the product several times. Next, drying is preferably performed. Examples of the drying method include vacuum low-temperature drying, vibration-type fluidized bed drying, spray drying, freeze drying, and flash jet drying.

[0097] [Toner Particles] The toner particles obtained by drying or the like can be used as they are as a toner for developing electrostatic images, but it is preferable to use the toner particles after surface treatment as described below as a toner for developing electrostatic images. Note that the content of each component contained in the toner described above is preferably the content in the toner particles.

[0098] Volume median particle size of toner particles D 50 From the viewpoint of obtaining a printed coating film (image) of good quality and from the viewpoint of further improving the cleaning properties of the toner, the thickness is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 7 μm or less.

[0099] The circularity of the toner particles is preferably 0.955 or more, more preferably 0.960 or more, from the viewpoint of obtaining a printed coating film (image) of good quality, and is preferably 0.990 or less, more preferably 0.985 or less, and even more preferably 0.980 or less, from the viewpoint of cleaning ability.

[0100] The CV value of the toner particles is preferably 10% or more, more preferably 12% or more, and even more preferably 14% or more, from the viewpoint of improving the productivity of the toner, and is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less, from the viewpoint of obtaining good image quality. Volume median particle size of toner particles D 50 The circularity and CV value can be measured by the method described in the Examples.

[0101] [External additives] The toner particles can be used as they are, but it is preferable to use the toner after adding a fluidizing agent or the like as an external additive to the surface of the toner particles. Examples of the external additive include inorganic particles such as hydrophobic silica, titanium oxide particles, alumina particles, cerium oxide particles, and carbon black, and polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin, among which hydrophobic silica is preferred. The external additive may be used alone or in combination of two or more. In addition, the same type of external additives with different particle sizes may be used in combination. When the toner particles are surface-treated using an external additive, the amount of the external additive added is, relative to 100 parts by mass of the toner particles, preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, even more preferably 4 parts by mass or less.

[0102] [Toner for developing electrostatic images] The toner for developing electrostatic images obtained as described above can be suitably used for forming images on polyethylene terephthalate films as a one-component developer or as a two-component developer mixed with a carrier.

[0103] [toner] The toner of the present invention contains a crystalline polyester resin C and an amorphous composite resin A in a binder resin, and is a toner for forming an image on a polyethylene terephthalate film, the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms; The amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment that includes a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 or more and 24 or less carbon atoms. The components contained in and the components which may be contained in the toner of the present invention, and the method for producing the toner of the present invention are similar to the components contained in and the components which may be contained in the toner used in the image forming method of the present invention, and the method for producing the toner used in the image forming method of the present invention, and therefore description thereof will be omitted.

[0104] The present invention includes the following aspects. <1> A toner for forming an image on a polyethylene terephthalate film, the toner comprising a crystalline polyester resin C and an amorphous composite resin A in a binder resin, the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms; The amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms. toner. <2> The polyester resin segment in the amorphous composite resin A is a polycondensate of an alcohol component containing 80 mol % or more of a polyoxypropylene adduct of bisphenol A and a carboxylic acid component. <1> The toner according to claim 1. <3> the polyester resin segment in the amorphous composite resin A is a polycondensate of an alcohol component containing 80 mol % or more of a polyoxypropylene adduct of bisphenol A and a carboxylic acid component containing an aliphatic dicarboxylic acid; The aliphatic dicarboxylic acid contains sebacic acid, and the content of sebacic acid in the aliphatic dicarboxylic acid is 40 mol% or more. <1> or <2> The toner according to claim 1. <4> The content of the addition polymerization resin segment in the amorphous composite resin A is 5% by mass or more and 30% by mass or less with respect to the total amount of the polyester resin segment and the addition polymerization resin segment. <1> ~ <3> 2. The toner according to claim 1 . <5> The crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 12 to 16 carbon atoms. <1> ~ <4> 2. The toner according to claim 1 . <6> In the binder resin, the mass ratio of the crystalline polyester resin C to the amorphous composite resin A (crystalline polyester resin C / amorphous composite resin A) is 3 / 97 or more and 45 / 55 or less. <1> ~ <5> 2. The toner according to claim 1 . <7> <1> ~ <6> 2. An image forming method, comprising forming an image on a polyethylene terephthalate film by using the toner according to any one of claims 1 to 11. EXAMPLES

[0105] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Each property value was measured and evaluated by the following methods. In the notation "alkylene oxide (X)" and the like, the number X in parentheses means the average number of moles of alkylene oxide added.

[0106] <Measurement method> [Softening point, crystallinity index, melting point and glass transition temperature of resin] (1) Softening point Using a flow tester "CFT-500D" (Shimadzu Corporation), 1 g of sample was heated at a temperature increase rate of 6°C / min, while applying a load of 1.96 MPa with the plunger, and extruding the sample from a nozzle with a diameter of 1 mm and a length of 1 mm. The plunger descent amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point. (2) Crystallinity index Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of sample was weighed into an aluminum pan and cooled to 0°C at a rate of 10°C / min. The sample was then left to stand for 1 minute, and then heated to 180°C at a rate of 10°C / min to measure the amount of heat. The temperature of the peak with the largest peak area among the observed endothermic peaks was taken as the endothermic maximum peak temperature (1), and the crystallinity index was calculated by (softening point (°C)) / (endothermic maximum peak temperature (1) (°C)). (3) Melting point and glass transition temperature Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and cooled from that temperature to 0°C at a rate of 10°C / min. The sample was then heated at a rate of 10°C / min, and the amount of heat was measured. Among the endothermic peaks observed, the temperature of the peak with the largest peak area was taken as the maximum endothermic peak temperature (2). In the case of a crystalline resin, this peak temperature was taken as the melting point. In the case of an amorphous resin, when a peak was observed, the temperature of the peak was taken as the glass transition temperature. When no peak was observed but a step was observed, the temperature at the intersection of the tangent showing the maximum slope of the curve at the step and an extension of the baseline on the low temperature side of the step was taken as the glass transition temperature.

[0107] [Acid value of resin] The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070: 1992. The measurement solvent was a mixed solvent of acetone and toluene (acetone:toluene=1:1 (volume ratio)).

[0108] [Melting point of release agent] Using a differential scanning calorimeter "Q100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then cooled from 200°C to 0°C at a rate of 10°C / min. The sample was then heated at a rate of 10°C / min, the amount of heat was measured, and the maximum endothermic peak temperature was taken as the melting point.

[0109] [Volume median particle diameter D of resin particles, colorant particles, and release agent particles 50 and CV value] (1) Measuring device: Laser diffraction type particle size measuring device "LA-920" (manufactured by Horiba Ltd.) (2) Measurement conditions: Put the sample dispersion in a measurement cell, add distilled water, and measure the volume median particle size D at a concentration where the absorbance is in the appropriate range. 50 The volume average particle diameter Dv was measured, and the CV value was calculated according to the following formula. CV value (%) = (Standard deviation of particle size distribution / Volume average particle size Dv) x 100

[0110] [Solid Content Concentration of Resin Particle Dispersion, Colorant Particle Dispersion, and Release Agent Particle Dispersion] Using an infrared moisture meter "FD-230" (Kett Electric Laboratory Co., Ltd.), the moisture content (mass%) of 5 g of the measurement sample was measured at a drying temperature of 150°C and measurement mode 96 (monitoring time 2.5 minutes, moisture content fluctuation range 0.05%). The solid content concentration was calculated according to the following formula. Solid concentration (mass%) = 100-moisture (mass%)

[0111] [Volume median particle diameter of agglomerated particles D 50 〕 Volume median particle size of agglomerated particles D 50 was measured as follows: Measuring instrument: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter, Inc.) Aperture diameter: 50μm Analysis software: "Multisizer (registered trademark) III version 3.51" (Beckman Coulter, Inc.) Electrolyte: "Isoton (registered trademark) II" (manufactured by Beckman Coulter, Inc.) Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte to adjust the concentration so that the particle size of 30,000 particles can be measured in 20 seconds. Then, 30,000 particles are measured again, and the volume median particle size D is calculated from the particle size distribution. 50 asked for.

[0112] [Circularity of fused particles] The circularity of the fused particles was measured under the following conditions. Measurement equipment: Flow-type particle image analyzer "FPIA-3000" (Sysmex Corporation) Preparation of dispersion: A dispersion of fused particles was prepared by diluting with deionized water to a solids concentration of 0.001 to 0.05% by mass. Measurement mode: HPF measurement mode

[0113] [Volume median particle size of toner particles D 50 and CV value] Volume median particle size of toner particles D 50 was measured as follows: The measurement device, aperture diameter, analysis software, and electrolyte were determined based on the volume median particle diameter D 50 The same one used in the measurement was used. Dispersion: Polyoxyethylene lauryl ether "EMULGEN (registered trademark) 109P" (manufactured by Kao Corporation, HLB (hydrophile-lipophile balance) = 13.6) was dissolved in the electrolyte to obtain a dispersion with a concentration of 5 mass %. Dispersion conditions: 10 mg of a measurement sample of dried toner particles was added to 5 mL of the dispersion liquid, and dispersed for 1 minute using an ultrasonic disperser. Thereafter, 25 mL of the electrolyte was added, and the mixture was further dispersed for 1 minute using an ultrasonic disperser to prepare a sample dispersion liquid. Measurement conditions: The sample dispersion is added to 100 mL of the electrolyte to adjust the concentration so that the particle size of 30,000 particles can be measured in 20 seconds. Then, 30,000 particles are measured and the volume median particle size D is calculated from the particle size distribution. 50 and volume average particle size D V asked for. The CV value (%) was calculated according to the following formula. CV value (%) = (Standard deviation of particle size distribution / Volume average particle size D V ) x 100

[0114] <Resin manufacturing> [Production of crystalline polyester resin] Manufacturing Example C1 (Manufacturing of Resin C-1) The inside of a 10L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was replaced with nitrogen, and the raw material monomers of the polyester resin shown in Table 1 were added. The reaction system was heated to 135°C while stirring, and then held at 135°C for 3 hours, and then heated from 135°C to 200°C over 10 hours. Then, 10g of tin(II) di(2-ethylhexanoate) was added to the reaction system, and the reaction system was further held at 200°C for 1 hour, after which the pressure in the flask was reduced and the reaction system was held under a reduced pressure of 8kPa for 1 hour, to obtain Resin C-1, a crystalline polyester resin. The physical properties are shown in Table 1.

[0115] Production Examples C2 to C4 (Production of Resins C-2 to C-4) Resins C-2 to C-4 were obtained in the same manner as in Production Example C1, except that the types and amounts of raw material monomers for the polyester resin were changed as shown in Table 1. The physical property values ​​are shown in Table 1.

[0116] Production Examples C'5 and C'6 (Production of Resins C'-5 and C'-6) Resins C'-5 and C'-6 were obtained in the same manner as in Production Example C1, except that the types and amounts of raw material monomers for the polyester resin were changed as shown in Table 1. The physical properties are shown in Table 1.

[0117] [Table 1]

[0118] [Production of amorphous polyester resin] Production Example A1 (Production of Resin A-1) The inside of a 10L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 4367g of propylene oxide (2.2) adduct of bisphenol A, 1098g of terephthalic acid, 32g of tin (II) di(2-ethylhexanoate), and 3.2g of gallic acid (3,4,5-trihydroxybenzoic acid) were added. The reaction system was heated to 235°C under a nitrogen atmosphere while stirring, and then maintained at 235°C for 5 hours. The pressure in the flask was then reduced and maintained at 8kPa for 1 hour. After that, the pressure was returned to atmospheric pressure, and the mixture was cooled to 160°C. While maintaining the temperature at 160°C, a mixture of 1070g of styrene, 267g of stearyl methacrylate, 144g of acrylic acid, and 160g of dibutyl peroxide was added dropwise to the reaction system over 3 hours. After that, the reaction system was kept at 160°C for 30 minutes, then heated to 200°C, and the pressure in the flask was further reduced and kept at 8kPa for 1 hour. After that, the pressure was returned to atmospheric pressure, and the mixture was cooled to 190°C, and 174g of fumaric acid, 378g of sebacic acid, 240g of trimellitic anhydride, and 3.2g of 4-tert-butylcatechol were added, and the temperature was raised to 210°C at 10°C / hr, and then the reaction was continued at 4kPa until the desired softening point, to obtain Resin A-1. The physical properties are shown in Table 2.

[0119] Production Example A2 (Production of Resin A-2) Resin A-2 was obtained in the same manner as in Production Example A1, except that the amount of raw material monomer for the polyester resin segment and the type and amount of raw material monomer for the addition polymerization segment were changed as shown in Table 2. The physical properties are shown in Table 2.

[0120] Production Example A'3 (Production of Resin A'-3) Resin A'-3 was obtained in the same manner as in Production Example A1, except that the amount of raw material monomer for the polyester resin segment and the type and amount of raw material monomer for the addition polymerization segment were changed as shown in Table 2. The physical properties are shown in Table 2.

[0121] Production Example A'4 (Production of Resin A'-4) The raw monomers of polyester resin except trimellitic anhydride shown in Table 2 were placed in a 10 L stainless steel kettle equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple. The mixture was reacted at 230°C for 8 hours under a nitrogen atmosphere, and then reacted under a reduced pressure of 1.3 kPa to 2.0 kPa for 4 hours. After adding trimellitic anhydride, the mixture was reacted at 180°C until the desired softening point was reached, yielding resin A'-4. The physical properties are shown in Table 2.

[0122] Manufacturing Example B1 (Manufacturing of Resin B-1) In a 10 L stainless steel kettle equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, the raw material monomers of the polyester resin, except for trimellitic anhydride, shown in Table 2, were placed. The mixture was reacted at 230°C for 8 hours under a nitrogen atmosphere, and then reacted under a reduced pressure of 1.3 kPa to 2.0 kPa for 4 hours. After adding trimellitic anhydride, the mixture was reacted at 180°C until the desired softening point was reached, yielding Resin B-1. The physical properties are shown in Table 2.

[0123] Manufacturing Example D1 (Manufacturing of Resin D-1) The inside of a 10L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was replaced with nitrogen, and 3450g of a propylene oxide (2.2) adduct of bisphenol A, 655g of terephthalic acid, 24g of tin (II) di(2-ethylhexanoate), and 2.4g of gallic acid (3,4,5-trihydroxybenzoic acid) were added, and the reaction system was heated to 235°C while stirring under a nitrogen atmosphere, and then maintained at 235°C for 5 hours, after which the pressure in the flask was reduced and maintained at 8kPa for 1 hour. After that, the pressure was returned to atmospheric pressure, and then cooled to 160°C, and a mixture of 2133g of styrene, 533g of stearyl methacrylate, 114g of acrylic acid, and 320g of dibutyl peroxide was added dropwise over 3 hours while maintaining the temperature at 160°C. The reaction system was then held at 160°C for 30 minutes, then heated to 200°C, and the pressure in the flask was further reduced and held at 8kPa for 1 hour. After that, the pressure was returned to atmospheric pressure, and the mixture was cooled to 190°C, 582g of succinic acid was added, and the mixture was heated to 210°C at 10°C / hr, and then reacted at 4kPa until the desired softening point was reached, yielding Resin D-1. The physical properties are shown in Table 2. Although resin D-1 is included in resin A, it is used to disperse the release agent, and therefore is referred to as "resin D-1" for convenience.

[0124] [Table 2]

[0125] [Production of Resin Particle Dispersion] Production Example X1 (Production of Resin Particle Dispersion X-1) In a 3 L vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, 350 g of amorphous polyester resin A-1, 150 g of crystalline polyester resin C-1, and 500 g of methyl ethyl ketone were placed and dissolved for 2 hours at 73° C. A 5% by mass aqueous solution of sodium hydroxide was added to the resulting solution so that the degree of neutralization with respect to the acid value of the resin was 60 mol%, and the mixture was stirred for 30 minutes. Next, while maintaining the temperature at 73°C, 1000g of deionized water was added over 60 minutes while stirring at 200 r / min to cause phase inversion emulsification. While maintaining the temperature at 73°C, the methyl ethyl ketone was distilled off under reduced pressure to obtain a dispersion. Thereafter, while continuing to stir, the dispersion was cooled to 30°C, and deionized water was added so that the solid concentration became 25% by mass, thereby obtaining resin particle dispersion X-1. The physical properties are shown in Table 3.

[0126] Production examples X2 to X6 (manufacture of resin particle dispersions X-2 to X-6) Resin particle dispersions X-2 to X-6 were obtained in the same manner as in Production Example X1, except that the amorphous polyester resin and the crystalline polyester resin were changed as shown in Table 3. Table 3 shows the physical property values.

[0127] Production Example X7 (Production of Resin Particle Dispersion X-7) Resin particle dispersion X-7 was obtained in the same manner as in Production Example X1, except that the amount of amorphous polyester resin A-1 was changed to 400 g and the amount of crystalline polyester resin C-1 was changed to 100 g. The physical properties are shown in Table 3.

[0128] Production Example X8 (Production of Resin Particle Dispersion X-8) Resin particle dispersion X-8 was obtained in the same manner as in Production Example X1, except that the amount of amorphous polyester resin A-1 was changed to 450 g and the amount of crystalline polyester resin C-1 was changed to 50 g. The physical properties are shown in Table 3.

[0129] Production Examples X'9 to X'12 (Production of Resin Particle Dispersions X'-9 to X'-12) Resin particle dispersions X'-9 to X'-12 were obtained in the same manner as in Production Example X1, except that the amorphous polyester resin and the crystalline polyester resin were changed as shown in Table 3. The physical property values ​​are shown in Table 3.

[0130] Production Example Y1 (Production of Resin Particle Dispersion Y-1) 500 g of Resin B-1 and 500 g of methyl ethyl ketone were placed in a 3 L vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, and dissolved for 2 hours at 73° C. A 5% by mass aqueous solution of sodium hydroxide was added to the resulting solution so that the degree of neutralization with respect to the acid value of Resin B-1 was 60 mol%, and the mixture was stirred for 30 minutes. Next, while maintaining the temperature at 73°C, 1000g of deionized water was added over 60 minutes while stirring at 200r / min (circumferential speed 63m / min) to cause phase inversion emulsification. While maintaining the temperature at 73°C, the methyl ethyl ketone was distilled off under reduced pressure to obtain a dispersion. Thereafter, while continuing to stir, the dispersion was cooled to 30°C, and deionized water was added so that the solid concentration became 25% by mass, thereby obtaining resin particle dispersion Y-1. The physical properties are shown in Table 3.

[0131] Production Example P1 (Production of Resin Particle Dispersion P-1) Resin particle dispersion P-1 was obtained in the same manner as in Production Example Y1, except that Resin B-1 was changed to Resin D-1. Physical property values ​​are shown in Table 3.

[0132] [Table 3]

[0133] [Preparation of Release Agent Particle Dispersion] Production Example W1 (Production of Release Agent Particle Dispersion W-1) Into a 1 L beaker, 120 g of deionized water, 86 g of resin particle dispersion P-1, and 40 g of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 75°C) were added, and the mixture was melted by maintaining the temperature at 90 to 95°C and stirred to obtain a molten mixture. The obtained molten mixture was dispersed for 20 minutes using an ultrasonic homogenizer "US-600T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.) while maintaining the temperature at 90 to 95°C, and then cooled to room temperature (20°C). Deionized water was added to the obtained dispersion to adjust the solid content to 20 mass%, thereby obtaining release agent particle dispersion W-1. The volume median particle diameter D of the release agent particles in release agent particle dispersion W-1 was 50The diameter was 0.47 μm and the CV value was 27%.

[0134] Production Example W2 (Production of Release Agent Particle Dispersion W-2) Release agent particle dispersion W-2 was obtained in the same manner as in Production Example W1, except that the type of release agent was changed to Fischer-Tropsch wax "FNP-00 90" (manufactured by Nippon Seiro Co., Ltd., melting point 90°C). 50 The diameter was 0.45 μm and the CV value was 28%.

[0135] [Preparation of Colorant Particle Dispersion] Production Example E1 (Production of Colorant Particle Dispersion E-1) In a 1 L beaker, 100 g of copper phthalocyanine pigment "ECB-301" (manufactured by Dainichiseika Chemicals Co., Ltd.), 35 g of polyoxyethylene (13) distyrenated phenyl ether "Emulgen A-60" (manufactured by Kao Corporation, nonionic surfactant), and 300 g of deionized water were mixed and dispersed for 1 hour at room temperature (20°C) with a stirring blade rotation speed of 8000 rpm using a homomixer "TKAGI HOMOMIXER 2M-03" (manufactured by Tokushu Kika Kogyo Co., Ltd.), and then the mixture was treated for 15 passes at a pressure of 150 MPa using a "Microfluidizer M-110EH" (manufactured by Microfluidics Co., Ltd.), and then passed through a 200 mesh filter. Deionized water was added so that the solid concentration was 20 mass%, to obtain a colorant particle dispersion E-1. The volume median particle diameter D of the obtained colorant particles was 50 The thickness was 0.12 μm and the CV value was 21%.

[0136] Example 1 <Production of Toner 1> Into a 3 L four-neck flask equipped with a dehydration tube, a stirrer, and a thermocouple, 500 g of resin particle dispersion X-1, 49 g of release agent particle dispersion W-1, 49 g of release agent particle dispersion W-2, and 63 g of colorant particle dispersion E-1 were added and mixed at a temperature of 25° C. Next, while stirring the mixture, a solution obtained by dissolving 40 g of ammonium sulfate in 570 g of deionized water and adding a 4.8 mass % potassium hydroxide aqueous solution to adjust the pH to 8.2 was added dropwise over 10 minutes at 25° C., and the temperature was then raised to 58° C. over 2 hours to measure the volume median particle diameter D of the aggregated particles. 50 The temperature was maintained at 58° C. until the particle size reached 6.5 μm, thereby obtaining a dispersion of aggregated particles 1. The obtained dispersion of aggregated particles 1 was cooled to 55° C., and while maintaining the temperature at 55° C., 48 g of resin particle dispersion Y-1 was added over 90 minutes, thereby obtaining a dispersion of aggregated particles 2 in which resin particles were aggregated to aggregated particles 1. To the obtained dispersion liquid of aggregated particles 2, 50 g of sodium salt of naphthalenesulfonic acid formalin condensate "DEMOL MS" (manufactured by Kao Corporation, effective concentration 20% by mass) and 1500 g of deionized water were added. Thereafter, the temperature was raised to 75°C over 1 hour, and the temperature was maintained at 75°C until the circularity reached 0.970, thereby obtaining a dispersion liquid of fused particles in which aggregated particles 2 were fused. The obtained dispersion of fused particles was cooled to 30°C, and the solid content was separated by suction filtration, washed with deionized water at 25°C, and then suction filtered at 25°C for 2 hours. The solid content was then vacuum dried at 33°C for 24 hours using a vacuum constant temperature dryer "DRV622DA" (manufactured by ADVANTEC Corporation), to obtain toner particles having a core-shell structure. The physical properties of the toner particles are shown in Table 4. 100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and 1.0 part by mass of hydrophobic silica "Cabosil (registered trademark) TS720" (manufactured by Cabot Japan Co., Ltd., number average particle size: 0.012 μm) were placed in a Henschel mixer and stirred, and the mixture was passed through a 150 mesh sieve to obtain toner 1.

[0137] [Image adhesion evaluation] The obtained toner 1 was used to form an image on a printing film, and the adhesion was evaluated as follows. A PET film "FE-2001♯25" (manufactured by Futamura Chemical Co., Ltd.) cut to A4 size was used as the printing film, and the corona-treated surface of the printing film was printed using a commercially available printer "Microline (registered trademark) 5400" (manufactured by Oki Data Corporation) until the toner adhesion amount on the film was 0.43 to 0.45 mg / cm. 2 A solid image was printed without fixing, leaving a margin of 5 mm from the top of the film lengthwise, and a length of 50 mm. Next, the same printer was prepared with a temperature-variable fixing unit, the fixing unit temperature was set to 105°C, and the toner was fixed in A4 portrait at a speed of 3 seconds per sheet, obtaining a PET film print (equivalent to 20 sheets per minute in A4 portrait). The solid image portion of the obtained PET film print was cut to a size of 15 mm x 70 mm, and a strong double-sided tape "Nistack NW-K15" (manufactured by Nichiban Co., Ltd.) 15 mm x 50 mm was attached to it, and the corona-treated surface of PET film "FE-2001♯25" cut to 15 mm x 70 mm was attached to the other surface to prepare a test specimen with the edge shown in Figure 1. Note that in order to make it easier to understand the layering order of the film, image, and tape, the thickness ratios of the film, image, and tape shown in Figure 1 have been changed from those of the actual test specimen. The prepared test pieces were subjected to a T-peel test at a constant speed (10 mm / min) using a Tensilon universal testing machine "AND STB-1225L" (manufactured by Orientec Co., Ltd.), and peeling occurred at the interface between the printing film and the toner coating (image). The peel strength at this time was evaluated as adhesion. The evaluation results are shown in Table 4. The higher the value, the better the adhesion.

[0138] Examples 2 to 8, Comparative Examples 1 to 4 (Production of Toners 2 to 8 (Examples) and Toners 9 to 12 (Comparative Examples) and Evaluation of Image Adhesion) Toners 2 to 12 were obtained in the same manner as in Example 1, except that the resin particle dispersion in Example 1 was changed as shown in Table 4. The physical property values ​​of the obtained toner particles and the evaluation results of the adhesion of test pieces produced using Toners 2 to 12 are shown in Table 4.

[0139] Comparative Example 5 The adhesion was evaluated in the same manner as in Example 1, except that the printing film was changed to a biaxially oriented polypropylene film (PP film) "FOR♯25" (manufactured by Futamura Chemical Co., Ltd.) in Example 1. The evaluation results are shown in Table 4.

[0140] Comparative Example 6 The adhesion was evaluated in the same manner as in Example 1, except that the printing film was changed to a nylon film "ON#25" (manufactured by Unitika Ltd.). The evaluation results are shown in Table 4.

[0141] [Table 4]

[0142] The images formed on a polyethylene terephthalate film using a toner containing a crystalline polyester resin C, which is a polycondensate of an alcohol component containing 90 mol % or more of ethylene glycol and a carboxylic acid component containing 80 mol % or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms in the binder resin, and an amorphous composite resin A containing a polyester resin segment and an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 10 to 24 carbon atoms, have excellent adhesion (Examples 1 to 8). In contrast, when a toner containing a crystalline polyester resin produced using 1,4-butanediol as an alcohol component and the amorphous composite resin A specified in the present invention is used (Comparative Example 1), and when a toner containing an amorphous polyester not containing an addition polymerization resin segment specified in the present invention is used (Comparative Example 4), the image formed on a polyethylene terephthalate film has poor adhesion. In addition, when a toner containing a crystalline polyester resin produced using adipic acid (an aliphatic dicarboxylic acid having 6 carbon atoms) and stearic acid as carboxylic acid components is used (Comparative Example 2), and when a toner containing an amorphous composite resin containing an addition polymerization resin segment containing a structural unit derived from a vinyl monomer having a hydrocarbon group having 8 carbon atoms is used (Comparative Example 3), the image formed on a polyethylene terephthalate film has low adhesion. In addition, the image formed on a polypropylene film or a nylon film by the toner used in the image forming method of the present invention has poor adhesion (Comparative Examples 5 and 6). [Explanation of symbols]

[0143] 1. Printing film 2 Images 3 Double-sided tape 4. PET film

Claims

1. A method for forming an image on a polyethylene terephthalate film using a toner containing a crystalline polyester resin C and an amorphous composite resin A in a binder resin, The crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol% or more of ethylene glycol and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms. Amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment containing a constituent unit derived from a vinyl monomer having a hydrocarbon group with 10 to 24 carbon atoms. Image forming method.

2. The image forming method according to claim 1, wherein the polyester resin segment in amorphous composite resin A is a polycondensate of an alcohol component containing 80 mol% or more of a polyoxypropylene adduct of bisphenol A and a carboxylic acid component.

3. The polyester resin segment in amorphous composite resin A is a polycondensate of an alcohol component containing 80 mol% or more of a polyoxypropylene adduct of bisphenol A and a carboxylic acid component containing an aliphatic dicarboxylic acid. The image forming method according to claim 1, wherein the aliphatic dicarboxylic acid contains sebacic acid, and the content of sebacic acid in the aliphatic dicarboxylic acid is 40 mol% or more.

4. The image forming method according to claim 1, wherein the content of the addition polymerization resin segment in the amorphous composite resin A is 5% by mass or more and 30% by mass or less, relative to the total amount of the polyester resin segment and the addition polymerization resin segment.

5. The image forming method according to claim 1, wherein the crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol% or more of ethylene glycol and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 12 to 16 carbon atoms.

6. The image forming method according to any one of claims 1 to 5, wherein the mass ratio of crystalline polyester resin C to amorphous composite resin A in the binder resin (crystalline polyester resin C / amorphous composite resin A) is 3 / 97 or more and 45 / 55 or less.

7. A toner for forming an image on a polyethylene terephthalate film, comprising a crystalline polyester resin C and an amorphous composite resin A in the binder resin, The crystalline polyester resin C is a polycondensate of an alcohol component containing 90 mol% or more of ethylene glycol and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid having 10 to 16 carbon atoms. Amorphous composite resin A includes a polyester resin segment and an addition polymerization resin segment containing a constituent unit derived from a vinyl monomer having a hydrocarbon group with 10 to 24 carbon atoms. toner.

Images