JP5983066B2 - Toner and toner set - Google Patents

Description

  The present invention relates to a toner and a toner set.

  2. Description of the Related Art Conventionally, there has been known an image forming apparatus that forms a color toner image by developing a latent image formed on a photoreceptor using a plurality of color toners. An image formed by this image forming apparatus is reproduced in color by adhesion of color toner, which is a powder color material, but there is a problem that gloss changes depending on the content of the image. The “gloss” here is a specular gloss defined by the JIS standard “Specular Glossiness-Measurement Method” (JIS Z 8741-1997). In this specification, “60-degree gloss” is representative. ". In general, the gloss increases as the toner adhesion amount increases. On the other hand, the adhesion amount of color toner on the image varies depending on the location in the image for the purpose of reproducing the color. In general, the gloss of the solid portion of the image is high and the gloss of the halftone portion is low. As a result, unintended gloss unevenness occurs and the image quality is lowered.

In order to prevent the uneven gloss, an image using colorless and transparent clear toner as the fifth color toner in addition to the four color toners of Y (yellow), M (magenta), C (cyan), and K (black). A forming apparatus has been proposed (see, for example, Patent Documents 1 and 2). According to this image forming apparatus, the clear toner is adhered so that the total adhesion amount of the four color toners of Y, M, C, and K and the clear toner becomes constant, so that the reproduction color of the color toner is reduced. Independently, the gloss in the image can be made constant.
However, with these proposed technologies, the gloss of the image surface can be made uniform by means of attaching clear toner, but there is a limit to the gloss range that can be expressed, and high gloss like silver halide photography is expressed. There is a problem that is difficult.

Therefore, the color toner image formed on the recording medium is melted by being sandwiched and heated by a belt having a mirror-finished surface, and then cooled while the color toner image on the recording medium is sandwiched by the belt. A fixing unit that fixes the belt so as to peel off the toner image after the temperature of the toner becomes low and an image forming apparatus using the fixing unit have been proposed (for example, see Patent Document 3). In this proposed technique, an image having extremely high gloss and photographic gloss can be obtained by transferring the mirror surface shape of the belt to the toner side. Hereinafter, the principle of fixing in which the toner image sandwiched between the belts is heated and cooled and the belt is peeled off is referred to as a “cooling peeling principle”.
However, this proposed technique has the following two problems.
The first problem is related to the glossy reproduction range. In the above-described technique, a high glossiness of a solid portion can be reproduced independently of color reproduction by using a clear toner. Further, by providing a fixing device based on the cooling peeling principle, higher photographic gloss can be realized. However, on the contrary, the lower gloss is limited and a low gloss image cannot be realized. Recorded images with high gloss on the surface are used for photos of expensive products because of their high-class feel. However, an image mainly composed of characters and charts has a disadvantage that it is difficult to read because the surrounding illumination or the like is transferred if the gloss is high. On the contrary, a low gloss recording image is preferred for such an image. Therefore, realization of a low gloss image is also strongly desired.
The second problem is related to gloss adjustment at each location in the glossy image. When photographic gloss is produced by the above technique, the entire image becomes photographic gloss, and it is impossible to make the gloss low or high depending on the location in the image. In an actual image, the photographic image and the character chart image are often mixed in the image. In that case, it is desirable to set the glossiness individually. In addition, in the case of an image including a metal object as a subject, a metal texture can be obtained by making only the metal portion higher gloss than the surroundings. Also in this case, a technique for changing the glossiness of a part of an image is desired.

  Furthermore, the technique uses a belt having a mirror surface for high gloss, and there is a problem that the image forming apparatus becomes large.

  Therefore, it is desired to solve the above problems caused by toner. If the toner can achieve high gloss without using the cooling peeling principle, it can be applied to the image forming apparatus using clear toner to suppress gloss unevenness and reproduce gloss over a wide range. Become. As a general method for obtaining a toner capable of realizing high gloss, it is conceivable to lower the melt viscosity of the resin in the toner, but there is a problem that heat resistant storage stability is lowered.

  Therefore, the present situation is that there is a demand for a toner that has excellent heat-resistant storage stability and high gloss.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner having excellent heat-resistant storage stability and high gloss.

Means for solving the problems are as follows. That is,
The toner of the present invention contains at least a polyester resin,
The polyester resin has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹¹ (R ¹¹ Represents any one of a hydrogen atom and a sodium atom), and R ² and R ³ are each independently a single bond or a linear alkylene group having 1 to 8 carbon atoms. It indicates whether further ^-R 2 ^{-C-R 3} - carbon atoms is odd 3-9.

  According to the present invention, it is possible to solve the conventional problems described above, and to provide a toner having excellent heat-resistant storage stability and high gloss.

(toner)
The toner of the present invention contains at least a polyester resin, preferably further contains a crystalline polyester resin, and further contains other components as necessary.

<Polyester resin>
The polyester resin has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹¹ (R ¹¹ Represents any one of a hydrogen atom and a sodium atom), and R ² and R ³ are each independently a single bond or a linear alkylene group having 1 to 8 carbon atoms. It indicates whether further ^-R 2 ^{-C-R 3} - carbon atoms is odd 3-9.

  As said m, the even number of 4-8 is preferable, and the even number of 4-6 is more preferable.

The alkyl group having 1 to 3 carbon atoms in ^{R 1,} for example, a methyl group, an ethyl group, n- propyl group, etc. i- propyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
Examples of the alkoxy group having 1 to 3 carbon atoms in R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group. Among these, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

Examples of the linear alkylene group having 1 to 8 carbon atoms in R ² and R ³ include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,4-butylene group, 1, Examples include 5-pentylene group, 1,6-hexylene group, 1,7-heptylene group, 1,8-octylene group and the like. Among these, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a linear alkylene group having 2 to 4 carbon atoms is more preferable.

As carbon number of said -R < ² > -C-R < ³ >-, the odd number of 5-9 is preferable.

In the general formula (2), R ¹ is any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹¹ . , R ² and R ³ are each preferably a linear alkylene group having 1 to 4 carbon atoms from the viewpoint of better gloss.

The structural unit represented by the general formula (1) is obtained using, for example, a dicarboxylic acid represented by the following general formula (1-1), an alkyl ester thereof, or a halide thereof.
In the general formula (1-1), m is the same as m in the general formula (1).

  Examples of the alkyl ester include methyl ester and ethyl ester. Examples of the halide include chloride and fluoride.

  Examples of the dicarboxylic acid represented by the general formula (1-1) include succinic acid, adipic acid, sebacic acid, suberic acid, and dodecanedioic acid.

The structural unit represented by the general formula (2) is obtained using, for example, a diol represented by the following general formula (2-1).

In the general formula ^(2-1), R 1, ^{R 2,} and ^{R 3,} respectively, ^R 1, ^{R 2} in the general formula (2), and is the same as ^{R 3.}

  Examples of the diol represented by the general formula (2-1) include 1,3-propanediol, 1,5-pentanediol, 1,7-heptanediol, 1,9-nonanediol, 3-methyl- 1,5-pentanediol, 4-methyl-1,7-heptanediol, 5-methyl-1,9-nonanediol, 3-ethyl-1,5-pentanediol, 3-n-propyl-1,5- Examples include pentanediol, 3-methoxy-1,5-pentanediol, and 3-sulfo-1,5-pentanediol.

  The monomer composition of a conventional polyester resin for toner (particularly amorphous polyester resin) is that dicarboxylic acid is a combination of a flexible monomer (such as adipic acid) and a rigid monomer (such as isophthalic acid), and a diol Is a bisphenol A alkylene oxide adduct (for example, bisphenol A propylene oxide adduct). In this case, the presence of the rigid monomer in the entire system is high, a specific structure (morphology) as a resin is constructed, and melting at the time of fixing is insufficient, so that high gloss cannot be achieved. On the other hand, when only a flexible monomer is used for both the dicarboxylic acid and the diol (for example, sebacic acid and 1,6-hexanediol, etc.), the orientation between the molecular chains is increased and the crystallinity is expressed. Therefore, since the offset is remarkably easily generated, high gloss cannot be achieved.

The present inventors introduced a flexible monomer into both the dicarboxylic acid and the diol, and further added to the dicarboxylic acid a dicarboxylic acid having an even number of alkylene chains between the carboxylic acids at both ends (for example, adipic acid). The diol used is a diol having an odd number of alkylene chains between the hydroxyl groups at both ends (for example, 1,5-pentanediol), so that high gloss can be obtained while maintaining heat-resistant storage stability. I found it. This is presumably because the structure of the resin collapsed and the entire molecular skeleton was distorted due to the even-odd effect (a phenomenon in which the characteristics differ greatly depending on whether the alkyl chain length is even or odd) without lowering the melt viscosity.
Furthermore, it has been found that introducing a substituent such as a methyl group into the alkylene chain of the diol to give steric hindrance is effective in obtaining high gloss while maintaining heat-resistant storage stability.

In the general formula (1), when m is 1, the solvent solubility of the polyester resin is lowered, and the production of the toner becomes difficult. In the said General formula (1), when m is more than 10, the thermal characteristic of a polyester resin will fall and heat resistant storage property will worsen.
In the general formula (2), when —R ² —C—R ³ — has a carbon number of 1, the solvent solubility of the polyester resin is lowered, making it difficult to produce a toner. In the said General formula (2), when carbon number of -R < ² > -C-R < ³ >-exceeds 9, the thermal characteristic of a polyester resin will fall and heat resistant storage property will worsen.
In the general formula (2), if the R ¹ is a substituent having an aromatic ring such as a phenyl group, the contribution of the aromatic ring is too large, so that the structure is constructed and the melting is insufficient. High gloss cannot be obtained.

  The polyester resin further has at least one of a structural unit derived from a dicarboxylic acid component having an aromatic ring and a structural unit derived from a diol component having an aromatic ring, making the polyester resin less likely to exhibit crystallinity, This is preferable from the viewpoint of preventing the occurrence of offset.

The dicarboxylic acid component having an aromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include orthophthalic acid, isophthalic acid, terephthalic acid, alkyl esters thereof, and halides thereof. It is done.
Examples of the alkyl ester include methyl ester and ethyl ester. Examples of the halide include chloride and fluoride.
Among these, isophthalic acid is preferable in terms of good reactivity during synthesis and not giving excessive orientation to the polyester resin.

The diol component having an aromatic ring is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a diol obtained by adding alkylene oxide to bisphenols. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Examples of the diol obtained by adding alkylene oxide to the bisphenol include, for example, bisphenol A ethylene oxide 2 mol adduct, bisphenol A ethylene oxide 3 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3 Mole adducts and the like are mentioned.
There is no restriction | limiting in particular as addition mole number of the said alkylene oxide, According to the objective, it can select suitably, For example, 2.0 mol-3.0 mol etc. are mentioned.
Among these, bisphenol A ethylene oxide 2.2 mol adduct is preferable.

  The polyester resin is preferably produced without using a trivalent or higher carboxylic acid such as trimellitic acid. That is, the polyester resin preferably does not have a structural unit derived from a trivalent or higher carboxylic acid such as trimellitic acid. When the polyester resin is produced using a trivalent or higher carboxylic acid such as trimellitic acid, the resulting polyester resin may have a cross-linked structure, which may increase the melt viscosity and reduce the gloss. .

  There is no restriction | limiting in particular as content of the structural unit represented by the said General formula (1) with respect to the structural unit derived from the dicarboxylic acid component in the said polyester resin, Although it can select suitably according to the objective, 1 mass % To 50% by mass is preferable, 3% to 30% by mass is more preferable, and 5% to 20% by mass is particularly preferable.

  There is no restriction | limiting in particular as content of the structural unit derived from the dicarboxylic acid component which has the said aromatic ring with respect to the structural unit derived from the dicarboxylic acid component in the said polyester resin, Although it can select suitably according to the objective, 50 % By mass to 99% by mass is preferable, 70% by mass to 97% by mass is more preferable, and 80% by mass to 95% by mass is particularly preferable.

  There is no restriction | limiting in particular as content of the structural unit represented by the said General formula (2) with respect to the structural unit derived from the diol component in the said polyester resin, Although it can select suitably according to the objective, 1 mass % To 50% by mass is preferable, 3% to 35% by mass is more preferable, and 4% to 25% by mass is particularly preferable.

  There is no restriction | limiting in particular as content of the structural unit derived from the diol component which has the said aromatic ring with respect to the structural unit derived from the diol component in the said polyester resin, Although it can select suitably according to the objective, 50 mass% -99 mass% is preferable, 65 mass%-97 mass% is more preferable, 75 mass%-96 mass% is especially preferable.

  There is no restriction | limiting in particular as a weight average molecular weight of the said polyester resin, Although it can select suitably according to the objective, 4,000-15,000 are preferable and 4,000-10,000 are more preferable. If the weight average molecular weight is less than 4,000, the oligomer component may remain excessively and heat resistant storage stability may decrease, and if it exceeds 15,000, the melt viscosity increases and the gloss decreases. There are things to do.

  There is no restriction | limiting in particular as an acid value of the said polyester resin, Although it can select suitably according to the objective, 5 mgKOH / g or more is preferable and 10 mgKOH / g-45 mgKOH / g are preferable.

  There is no restriction | limiting in particular as content of the said polyester resin, Although it can select suitably according to the objective, 50 mass parts-100 mass parts are preferable with respect to 100 mass parts of the said toner, 60 mass parts-90 mass parts. Mass parts are more preferable, and 75 to 90 parts by mass are particularly preferable.

  The polyester resin is preferably an amorphous polyester resin.

<Crystalline polyester resin>
Since the crystalline polyester resin has high crystallinity, the crystalline polyester resin exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. By using the crystalline polyester resin having such characteristics together with the polyester resin, the heat-resistant storage stability due to the crystallinity is good until just before the melting start temperature, and the viscosity rapidly decreases due to melting of the crystalline polyester resin at the melting start temperature. (Sharp melt property) is caused, and it is compatible with the polyester resin, and the viscosity is suddenly lowered to fix the toner. Therefore, a toner having both good heat storage stability and low temperature fixability can be obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).

The crystalline polyester resin is obtained using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, or a derivative thereof.
In the present invention, as described above, the crystalline polyester resin uses a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. A polyester resin modified, for example, a prepolymer described later, and a resin obtained by crosslinking and / or elongation reaction of the prepolymer do not belong to the crystalline polyester resin.

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material. The number of carbon atoms is more preferably 12 or less.
The saturated aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose.However, the crystalline polyester resin obtained has high crystallinity and is excellent in sharp melt properties. 4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained.
These may be used individually by 1 type and may use 2 or more types together.

  The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. When the melting point is less than 60 ° C., the crystalline polyester resin is likely to melt at a low temperature and the heat-resistant storage stability of the toner may be reduced. When the melting point exceeds 80 ° C., the crystalline polyester resin is heated by heat at the time of fixing. Insufficient melting may reduce the low-temperature fixability.

The molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and many components have a low molecular weight. From the viewpoint that heat-resistant storage stability is lowered, the soluble content of orthodichlorobenzene of the crystalline polyester resin is determined by GPC measurement in terms of weight average molecular weight (Mw) 3,000 to 30,000, number average molecular weight (Mn). It is preferably 1,000 to 10,000 and Mw / Mn 1.0 to 10.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 5,000-15,000, number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.

  The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.

  The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and good charging characteristics, 0 mgKOH / G to 50 mgKOH / g are preferable, and 5 mgKOH / g to 50 mgKOH / g are more preferable.

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 2 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, 5 mass parts -15 mass parts is more preferable. When the content is less than 2 parts by mass, the low-temperature fixability may be inferior due to insufficient sharp melting by the crystalline polyester resin, and when it exceeds 20 parts by mass, the heat-resistant storage stability is reduced. In addition, image fogging may occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, a charge control agent, an external additive etc. are mentioned.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, for example, the above-mentioned polyester resin, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, or a polymer of its substitution product; styrene-p-chlorostyrene copolymer Polymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer Polymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, Styrene-acrylonitrile Polymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid copolymer, Styrene-maleic acid ester copolymer Styrene copolymers such as: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin , Modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type and may use 2 or more types together.
The master batch can be obtained by mixing the master batch resin and the colorant under high shearing force and kneading to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably, For example, waxes, waxes, etc. are mentioned.
Examples of the waxes and waxes include plant waxes, mineral waxes, and petroleum waxes. Examples of the plant wax include carnauba wax, cotton wax, wood wax, and rice wax. Examples of the animal wax include beeswax and lanolin. Examples of the mineral wax include ozokerite and cercin. Examples of the petroleum wax include paraffin, microcrystalline, and petrolatum.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. When the melting point is less than 60 ° C., the release agent is likely to melt at a low temperature, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature range, the release agent may not be sufficiently melted, resulting in fixing offset and image loss.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 8 parts by mass is more preferable. When the content is less than 2 parts by mass, the high-temperature offset resistance during fixing and the low-temperature fixability may be inferior. When the content exceeds 10 parts by mass, the heat-resistant storage stability is deteriorated, and image fogging occurs. Etc. may occur easily. When the content is within the more preferable range, it is advantageous in terms of improving image quality and improving fixing stability.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Is mentioned. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, LR-147 (made by Nippon Carlit Co., Ltd.), which is a boron complex.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too high, and the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density. . These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch or resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner base particles. You may let them.

-External additive-
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, fatty acid metal salts (for example, zinc stearate and aluminum stearate), metal oxides (for example, oxidation). Titanium, aluminum oxide, tin oxide, antimony oxide, etc.), hydrophobized titanium oxide, fluoropolymer, and the like.
Examples of the commercially available silica include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of commercially available titanium oxide include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (Fuji Titanium Industry Co., Ltd.). Company-made), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Commercially available products of the hydrophobized titanium oxide include, for example, T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T. , TAF-1500T (all manufactured by Fuji Titanium Industrial Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  Examples of the hydrophobic treatment method include a method of treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane.

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner. 3 mass parts-3 mass parts are more preferable.

  There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said external additive, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm-70 nm are more preferable. If the average particle size is less than 3 nm, the external additive may be buried in the toner and its function may not be exhibited effectively, and if it exceeds 100 nm, the surface of the photoreceptor may be damaged unevenly. .

  The toner may be used as a color toner containing the colorant, or may be used as a clear toner not containing the colorant.

<< Measurement of glass transition point of polyester resin >>
The glass transition point of the polyester resin can be measured by the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of a sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition point (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition point (Tg) and the base line using the analysis system in the TG-DSC system TAS-100 system. can do.

<< weight average molecular weight >>
In this specification, a weight average molecular weight (Mw) can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). As a column used for the measurement, TSKgel SuperHZM-H 15 cm inner diameter 3 μm (manufactured by Tosoh Corporation) is used. The resin to be measured is, for example, 0.15% by mass solution in tetrahydrofuran (THF) (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.), filtered through a 0.2 μm filter, and the filtrate is used as a sample. 50 μL to 200 μL of the THF sample solution is injected into a measuring device, and measurement is performed at a flow rate of 1 mL / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. Examples of the standard polystyrene sample include Pressure Chemical Co. Or Tosoh molecular weight of KK is ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ are used. An RI (refractive index) detector is used as the detector.

<< Method for measuring hydroxyl value of resin >>
The hydroxyl value of the resin can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are as follows.

〔Measurement condition〕
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

<< Measurement Method of Acid Value of Resin >>
The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case of an ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. If the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the above-described method for measuring the hydroxyl value of the resin.

  The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Method for Measuring Melting Point of Resin and Release Agent >>
The melting points of the resin and the release agent can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting points of the resin and the release agent can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is lowered from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, the DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).
From the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature increase can be selected, and the endothermic peak top temperature at the first temperature increase of the target sample can be obtained as the melting point. . Similarly, a DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.
In this specification, when there is no notice about melting | fusing point, let the endothermic peak top temperature at the time of the 2nd temperature rise be melting | fusing point of each object sample.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, granulation is performed by dispersing an oil phase containing the toner material containing the polyester resin in an aqueous medium. The method etc. are mentioned. An example of such a method for producing the toner is a known dissolution suspension method. The dissolution suspension method includes, for example, a toner material phase preparation step, an aqueous medium phase preparation step, an emulsification or dispersion preparation step, and an organic solvent removal step, and further includes other steps as necessary. The method of including is mentioned.

-Toner material phase (oil phase) preparation process-
The toner material phase preparation step includes at least the polyester resin, and if necessary, dissolves or disperses the toner material containing the crystalline polyester resin, the colorant, the release agent, and the like in an organic solvent. There is no particular limitation as long as it is a step of preparing a toner material dissolved or dispersed liquid (sometimes referred to as a toner material phase or an oil phase), and can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The volatile thing whose boiling point is less than 150 degreeC is preferable at the point of the ease of removal.
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable, and ethyl acetate is more preferable.
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, Although it can select suitably according to the objective, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, and 60 mass parts-140 mass parts. Mass parts are more preferable, and 80 to 120 parts by mass are particularly preferable.

-Aqueous medium phase (aqueous phase) preparation process-
The aqueous medium phase preparation step is not particularly limited as long as it is a step of preparing an aqueous medium phase containing styrene / acrylic resin fine particles in an aqueous medium, and can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. Among these, water is particularly preferable.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and can be appropriately selected according to the purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Is mentioned.
Examples of the alcohol include methanol, isopropanol, and ethylene glycol.
Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

The aqueous medium phase is prepared, for example, by dispersing the styrene / acrylic resin fine particles in the aqueous medium in the presence of an anionic surfactant.
The amount of the anionic surfactant and the styrene / acrylic resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. 0.5 mass%-10 mass% are preferable.

  The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl diaryl ether disulfonates, and dialkyl sulfosuccinates. Acid salts, alkyl phosphates, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salts, glyceryl borate fatty acid esters and the like.

  Examples of the styrene / acrylic resin fine particles include fine particles of a copolymer of styrene and a vinyl monomer. Examples of the copolymer of styrene and a vinyl monomer include, for example, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, Examples include styrene- (meth) acrylic acid copolymers.

-Emulsification or dispersion preparation process-
The emulsification or dispersion preparation step is a step for preparing an emulsification or dispersion by mixing and dissolving and dispersing and dissolving the toner material (toner material phase) and the aqueous medium phase. There is no restriction | limiting in particular, According to the objective, it can select suitably.
There is no restriction | limiting in particular as the method of emulsification thru | or dispersion | distribution, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser.

-Organic solvent removal process-
The organic solvent removing step is not particularly limited as long as it is a step of removing the organic solvent from the emulsified or dispersed liquid to obtain a desolvent slurry, and can be appropriately selected according to the purpose.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets of the emulsified or dispersed liquid, and (2) the emulsified or dispersed liquid is removed. Examples thereof include a method in which the organic solvent in the oil droplets of the emulsion or dispersion is completely removed by spraying in a dry atmosphere. When the organic solvent is removed, toner particles are formed.

-Other processes-
As said other process, a washing | cleaning process, a drying process, etc. are mentioned, for example.

-Cleaning process-
The washing step is not particularly limited as long as it is a step of washing the solvent-removed slurry with water after the organic solvent removing step, and can be appropriately selected depending on the purpose. Examples of the water include ion-exchanged water.

--- Drying process--
The drying step is not particularly limited as long as it is a step of drying the toner particles obtained in the washing step, and can be appropriately selected according to the purpose.

(Toner set)
The toner set of the present invention contains a color toner and a clear toner, and further contains other components as necessary.

<Color toner>
The color toner contains the polyester resin a, preferably contains a crystalline polyester resin, and further contains other components such as a colorant and a release agent as required.

-Polyester resin a-
The polyester resin a has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (3).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (3), n is an odd number of 3 to 9.

  The polyester resin a further has at least one of a structural unit derived from a dicarboxylic acid component having an aromatic ring and a structural unit derived from a diol component having an aromatic ring, which makes it difficult for the polyester resin to exhibit crystallinity. From the viewpoint of preventing the occurrence of offset.

There is no restriction | limiting in particular as a weight average molecular weight of the said polyester resin a, Although it can select suitably according to the objective, 4,000-15,000 are preferable and 4,000-10,000 are more preferable. If the weight average molecular weight is less than 4,000, the oligomer component may remain excessively and heat resistant storage stability may decrease, and if it exceeds 15,000, the melt viscosity increases and the gloss decreases. There are things to do.
When the polyester resin a has a weight average molecular weight of more than 10,000 and not more than 15,000, the glossiness of the clear toner and the gloss difference ΔGs are more excellent.

The polyester resin a is a polyester resin in which R ¹ of the structural unit represented by the general formula (2) is a hydrogen atom in the polyester resin of the toner of the present invention. Preferred embodiments and preferred embodiments of the content of each component are the same as those of the polyester resin in the toner of the present invention except that R ¹ of the structural unit represented by the general formula (2) is a hydrogen atom. is there.

  The crystalline polyester resin, the colorant, and the release agent in the color toner are not particularly limited and may be appropriately selected depending on the purpose. For example, the description is given in the description of the toner of the present invention. The same applies to the crystalline polyester resin, the colorant, and the release agent.

<Clear toner>
The clear toner contains the polyester resin b, preferably contains a crystalline polyester resin, and further contains other components such as a release agent, if necessary.

-Polyester resin b-
The polyester resin b has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (4).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (4), R ⁴ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹² (R ¹² is hydrogen And R ⁵ and R ⁶ each independently represents a single bond or a linear alkylene group having 1 to 8 carbon atoms. Furthermore, the carbon number of —R ⁵ —C—R ⁶ — is an odd number of 3-9.

In the general formula (4), R ⁴ is any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹² . , R ⁵ and R ⁶ are each preferably a linear alkylene group having 1 to 4 carbon atoms from the viewpoint of better gloss.

  The polyester resin b further has at least one of a structural unit derived from a dicarboxylic acid component having an aromatic ring and a structural unit derived from a diol component having an aromatic ring, so that the polyester resin hardly exhibits crystallinity. From the viewpoint of preventing the occurrence of offset.

There is no restriction | limiting in particular as a weight average molecular weight of the said polyester resin b, Although it can select suitably according to the objective, 4,000-15,000 are preferable and 4,000-10,000 are more preferable. If the weight average molecular weight is less than 4,000, the oligomer component may remain excessively and heat resistant storage stability may decrease, and if it exceeds 15,000, the melt viscosity increases and the gloss decreases. There are things to do.
Further, when the weight average molecular weight of the polyester resin b is 4,000 or more and less than 5,000, the glossiness of the clear toner and the gloss difference ΔGs are more excellent.

In the polyester resin of the toner of the present invention, the polyester resin b is an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms, which is R ¹ of the structural unit represented by the general formula (2). , —NO ₂ , —NH ₂ , and —SO ₃ R ¹¹ (R ¹¹ represents one of a hydrogen atom and a sodium atom). Preferred embodiments of the present invention, preferred embodiments of the content of each component, and the like, R ¹ of the structural unit represented by the general formula (2) is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, -NO _2, -NH _2, and _-SO 3 ^{R 11 (R} 11 is. to represent any of a hydrogen atom, and sodium atom) represented by any of the polyester resin in the toner of the present invention Is the same as that.

  The crystalline polyester resin and the release agent in the color toner are not particularly limited and may be appropriately selected depending on the purpose. For example, the crystalline polyester described in the description of the toner of the present invention The same applies to the resin and the release agent.

  The method of using the toner set is not particularly limited and may be appropriately selected depending on the intended purpose. However, as described in JP-A No. 09-200551, Y (yellow), M (magenta), C A method in which a clear toner image is formed by an inverted signal of the cyan (Cyan) and Bk (black) image signals, and the clear toner is adhered so that the total adhesion amount of the color toner and the clear toner is constant. By doing so, it is possible to make the gloss in the image constant independently of the reproduction color of the color toner.

The toner set has excellent heat-resistant storage stability and high gloss. In addition, the clear toner provides higher gloss, so the spot-like high gloss at the location where the clear toner is fixed. Can be realized.
The spot-like high gloss may be required, for example, when reproducing an achromatic object having different gloss depending on a part. For example, when reproducing an eyeglass lens, a glass, or the like, it may be required to express an object only with gloss, and in that case, the difference in gloss can be expressed by spot-like high gloss by clear toner. Can reproduce objects.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

<Measurement of glass transition point of amorphous polyester resin>
The glass transition point of the amorphous polyester resin was measured by the following method using TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of a sample was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was left at 150 ° C. for 10 minutes, and the sample was cooled to room temperature and left for 10 minutes. Thereafter, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition point (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition point (Tg) and the base line using the analysis system in the TG-DSC system TAS-100 system. did.

<< Method for Measuring Melting Point of Resin and Release Agent >>
The melting points of the resin and the release agent were measured using a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting points of the resin and the release agent were measured by the following procedure.
First, about 5.0 mg of the target sample was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Next, the sample was heated from −80 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature was decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, a DSC curve was measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).
From the obtained DSC curve, the DSC curve at the first temperature increase was selected using the analysis program in the Q-200 system, and the endothermic peak top temperature at the first temperature increase of the target sample was determined as the melting point. Similarly, the DSC curve at the second temperature increase was selected, and the endothermic peak top temperature at the second temperature increase of the target sample was determined as the melting point. Among them, the endothermic peak top temperature at the second temperature rise was defined as the melting point of each target sample.

(Production Example 1-1)
<Synthesis of Amorphous Polyester Resin a1 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 1,5-pentanediol, 23 parts of isophthalic acid, 4 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted for 3 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain amorphous polyester resin a1. The obtained amorphous polyester resin a1 had a weight average molecular weight (Mw) of 5,600.

(Production Example 1-2)
<Synthesis of Amorphous Polyester Resin a2 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 1,7-heptanediol, 23 parts of isophthalic acid, 4 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin a2. The obtained amorphous polyester resin a2 had a weight average molecular weight (Mw) of 5,800.

(Production Example 1-3)
<Synthesis of Amorphous Polyester Resin a3 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 8 parts of 1,9-nonanediol, 23 parts of isophthalic acid, 4 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and reacted at 220 ° C. under normal pressure for 4 hours. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin a3. The obtained amorphous polyester resin a3 had a weight average molecular weight (Mw) of 6,200.

(Production Example 1-4)
<Synthesis of Amorphous Polyester Resin a4 (for Color Toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 1,5-pentanediol, 23 parts of isophthalic acid, 4 parts of succinic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted for 3 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain amorphous polyester resin a4. The obtained amorphous polyester resin a4 had a weight average molecular weight (Mw) of 5,400.

(Production Example 1-5)
<Synthesis of Amorphous Polyester Resin a5 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 63 parts of bisphenol A ethylene oxide 2.2 mol adduct, 10 parts of 1,5-pentanediol, 23 parts of isophthalic acid, 3 parts of sebacic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin a5. The obtained amorphous polyester resin a5 had a weight average molecular weight (Mw) of 5,300.

(Production Example 1-6)
<Synthesis of Amorphous Polyester Resin a6 (for Color Toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 63 parts of bisphenol A ethylene oxide 2.2 mol adduct, 10 parts of 1,5-pentanediol, 25 parts of isophthalic acid, 2 parts of dodecanedioic acid, and 2 parts of dibutyltin oxide was added and reacted at 220 ° C. for 4 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin a6. The obtained amorphous polyester resin a6 had a weight average molecular weight (Mw) of 6,300.

(Production Example 1-7)
<Synthesis of Amorphous Polyester Resin a7 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 51 parts of bisphenol A ethylene oxide 2.2 mol adduct, 6 parts of 1,5-pentanediol, 30 parts of isophthalic acid, 5 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and reacted at 220 ° C. for 7 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin a7. The obtained amorphous polyester resin a7 had a weight average molecular weight (Mw) of 14,700.

(Production Example 1-8)
<Synthesis of Amorphous Polyester Resin a8 (for Color Toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 68 parts of bisphenol A ethylene oxide 2.2 mol adduct, 14 parts of 1,5-pentanediol, 18 parts of isophthalic acid, 2 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 2 hours to obtain amorphous polyester resin a8. The obtained amorphous polyester resin a8 had a weight average molecular weight (Mw) of 4,100.

(Production Example 1-9)
<Synthesis of Amorphous Polyester Resin a9 (for Color Toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 1,6-hexanediol, 23 parts of isophthalic acid, 4 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and allowed to react at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin a9. The obtained amorphous polyester resin a9 had a weight average molecular weight (Mw) of 5,700.

(Production Example 1-10)
<Synthesis of Amorphous Polyester Resin a10 (for Color Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 1,5-hexanediol, 23 parts of isophthalic acid, 4 parts of tetradecanedioic acid, and 2 parts of dibutyltin oxide was added and reacted at 220 ° C. for 5 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin a10. The obtained amorphous polyester resin a10 had a weight average molecular weight (Mw) of 7,200.

(Production Example 1-11)
<Synthesis of Amorphous Polyester Resin a11 (for Color Toner)>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 69 parts of bisphenol A ethylene oxide 2.2 mol adduct, 8 parts of 1,11-dodecanediol, 23 parts of isophthalic acid, 4 parts of adipic acid, and dibutyl 2 parts of tin oxide was added and reacted at 220 ° C. for 5 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin a11. The obtained amorphous polyester resin a11 had a weight average molecular weight (Mw) of 7,300.

  Table 1 shows the monomer composition, weight average molecular weight, and glass transition point of the amorphous polyester resins a1 to a11 obtained above.

The unit of the blending amount of each monomer in Table 1 is part.

(Production Example 2-1)
<Synthesis of Amorphous Polyester Resin b1 (for Clear Toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 3-methyl-1,5-pentanediol, 23 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain an amorphous polyester resin b1. The obtained amorphous polyester resin b1 had a weight average molecular weight (Mw) of 5,400.

(Production Example 2-2)
<Synthesis of amorphous polyester resin b2 (for clear toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 4-methyl-1,7-heptanediol, 23 parts of isophthalic acid, 4 parts of adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain an amorphous polyester resin b2. The obtained amorphous polyester resin b2 had a weight average molecular weight (Mw) of 5,700.

(Production Example 2-3)
<Synthesis of amorphous polyester resin b3 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 8 parts of 5-methyl-1,9-nonanediol, 23 parts of isophthalic acid, 4 parts of adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 4 hours under normal pressure. Next, the obtained reaction solution was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin b3. The obtained amorphous polyester resin b3 had a weight average molecular weight (Mw) of 6,400.

(Production Example 2-4)
<Synthesis of amorphous polyester resin b4 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 61 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 3-methyl-1,5-pentanediol, 23 parts of isophthalic acid, succinic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin b4. The obtained amorphous polyester resin b4 had a weight average molecular weight (Mw) of 5,400.

(Production Example 2-5)
<Synthesis of amorphous polyester resin b5 (for clear toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 63 parts of bisphenol A ethylene oxide 2.2 mol adduct, 10 parts of 3-methyl-1,5-pentanediol, 23 parts of isophthalic acid, sebacic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Next, the obtained reaction solution was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin b5. The obtained amorphous polyester resin b5 had a weight average molecular weight (Mw) of 5,400.

(Production Example 2-6)
<Synthesis of amorphous polyester resin b6 (for clear toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 63 parts of bisphenol A ethylene oxide 2.2 mol adduct, 10 parts of 3-methyl-1,5-pentanediol, 25 parts of isophthalic acid, dodecanedioic acid 2 parts and 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 4 hours under normal pressure. Next, the obtained reaction solution was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin b6. The obtained amorphous polyester resin b6 had a weight average molecular weight (Mw) of 6,600.

(Production Example 2-7)
<Synthesis of amorphous polyester resin b7 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 8 parts of 3-ethyl-1,5-pentanediol, 23 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Next, the obtained reaction solution was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin b7. The obtained amorphous polyester resin b7 had a weight average molecular weight (Mw) of 5,800.

(Production Example 2-8)
<Synthesis of amorphous polyester resin b8 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of bisphenol A ethylene oxide 2.2 mol adduct, 6 parts of 3-n-propyl-1,5-pentanediol, 23 parts of isophthalic acid, adipine 4 parts of acid and 2 parts of dibutyltin oxide were added and reacted at 220 ° C. under normal pressure for 4 hours. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin b8. The obtained amorphous polyester resin b8 had a weight average molecular weight (Mw) of 6,700.

(Production Example 2-9)
<Synthesis of amorphous polyester resin b9 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of bisphenol A ethylene oxide 2.2 mol adduct, 6 parts of 3-methoxy-1,5-pentanediol, 23 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 4 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain an amorphous polyester resin b9. The obtained amorphous polyester resin b9 had a weight average molecular weight (Mw) of 6,600.

(Production Example 2-10)
<Synthesis of Amorphous Polyester Resin b10 (for Clear Toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 69 parts of bisphenol A ethylene oxide 2.2 mol adduct, 4 parts of 3-sulfo-1,5-pentanediol, 23 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 4 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain an amorphous polyester resin b10. The obtained amorphous polyester resin b10 had a weight average molecular weight (Mw) of 6,500.

(Production Example 2-11)
<Synthesis of Amorphous Polyester Resin b11 (for Clear Toner)>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 51 parts of bisphenol A ethylene oxide 2.2 mol adduct, 4 parts of 5-methyl-1,9-nonanediol, 29 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 7 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain amorphous polyester resin b11. The obtained amorphous polyester resin b11 had a weight average molecular weight (Mw) of 14,500.

(Production Example 2-12)
<Synthesis of Amorphous Polyester Resin b12 (for Clear Toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 68 parts of bisphenol A ethylene oxide 2.2 mol adduct, 14 parts of 3-methyl-1,5-pentanediol, 18 parts of isophthalic acid, adipic acid 2 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Next, the reaction solution was reacted for 2 hours under reduced pressure of 10 mmHg to 15 mmHg to synthesize amorphous polyester b12. The obtained amorphous polyester resin b12 had a weight average molecular weight (Mw) of 4,200.

(Production Example 2-13)
<Synthesis of amorphous polyester resin b13 (for clear toner)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 65 parts of bisphenol A ethylene oxide 2.2 mol adduct, 12 parts of 3-methyl-1,6-hexanediol, 28 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 4 hours under normal pressure. Next, the obtained reaction solution was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin b13. The obtained amorphous polyester resin b13 had a weight average molecular weight (Mw) of 6,800.

(Production Example 2-14)
<Synthesis of amorphous polyester resin b14 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 68 parts of bisphenol A ethylene oxide 2.2 mol adduct, 4 parts of 3-methyl-1,5-pentanediol, 29 parts of isophthalic acid, tetradecanedioic acid 4 parts and 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 5 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain an amorphous polyester resin b14. The obtained amorphous polyester resin b14 had a weight average molecular weight (Mw) of 7,300.

(Production Example 2-15)
<Synthesis of amorphous polyester resin b15 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 68 parts of bisphenol A ethylene oxide 2.2 mol adduct, 4 parts of 6-methyl-1,11-dodecanediol, 29 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. under normal pressure for 5 hours. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours to obtain an amorphous polyester resin b15. The obtained amorphous polyester resin b15 had a weight average molecular weight (Mw) of 7,100.

(Production Example 2-16)
<Synthesis of Amorphous Polyester Resin b16 (for Clear Toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 68 parts of bisphenol A ethylene oxide 2.2 mol adduct, 4 parts of 3-phenyl-1,5-pentanediol, 29 parts of isophthalic acid, adipic acid 4 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain an amorphous polyester resin b16. The obtained amorphous polyester resin b16 had a weight average molecular weight (Mw) of 5,400.

(Production Example 2-17)
<Synthesis of amorphous polyester resin b17 (for clear toner)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 69 parts of bisphenol A ethylene oxide 2.2 mol adduct, 5 parts of 3-phenyl-1,5-pentanediol, 29 parts of isophthalic acid, 3 parts of glutaric acid 3 And 2 parts of dibutyltin oxide were added and reacted at 220 ° C. for 3 hours under normal pressure. Subsequently, the obtained reaction liquid was reacted under reduced pressure of 10 mmHg to 15 mmHg for 3 hours to obtain amorphous polyester resin b17. The obtained amorphous polyester resin b17 had a weight average molecular weight (Mw) of 5,100.

  Table 2 shows the monomer composition, weight average molecular weight, and glass transition point of the amorphous polyester resins b1 to b17 obtained above.

The unit of the amount of each monomer in Table 2 is parts.

(Production Example 3)
<Synthesis of crystalline polyester resin>
1,6-hexanediol 1,260 g, ethylene glycol 120 g, fumaric acid 1400 g, trimellitic anhydride 350 g, tin octylate 3.5 g and hydroquinone 1.5 g were added to a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. In a four-liter flask with a capacity of 5 liters, and reacted at 160 ° C. for 5 hours, then heated to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour. A resin was obtained. The crystalline polyester resin had a melting point of 89 ° C.

(Production Example 4)
<Synthesis of styrene / acrylic resin fine particles>
In a reaction vessel equipped with a stir bar and a thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries, Ltd.) 16 parts, styrene 83 parts, methacrylic acid When 83 parts, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and styrene / acryl resin fine particles (a copolymer of styrene / methacrylic acid / butyl acrylate / methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion of [styrene / acrylic resin fine particle dispersion] was obtained.

Example 1
<Manufacture of toner set a>
<< Manufacture of color toner a >>
-Preparation of master batch (MB) (for color toner)-
1,000 parts of water, 540 parts of carbon black (Printex 35, manufactured by Degussa, DBP oil absorption = 42 mL / 100 g, pH = 9.5), and 1,200 parts of amorphous polyester resin a1 were added to a Henschel mixer (Japan). Coke Industry Co., Ltd.). The obtained mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain [Masterbatch].

-Preparation of toner material phase (oil phase) (for color toner)-
In a beaker, 100 parts of amorphous polyester resin a1 and 130 parts of ethyl acetate were added and stirred to dissolve. Carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.), WA-05TS, manufactured by Toa Kasei Co., Ltd.) 10 parts, and [Masterbatch] 10 3 using a bead mill (Ultra Visco Mill, manufactured by IMEX Co., Ltd.) under the condition that 80% by volume of zirconia beads having a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / s, and a diameter of 0.5 mm were filled. After passing, a raw material solution was prepared and stirred, and then [oil phase (for color toner)], which was a solution or dispersion of the toner material, was prepared.

-Preparation of aqueous medium phase (aqueous phase)-
660 parts of water, 25 parts of [styrene / acrylic resin fine particle dispersion], 25 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 60 parts of ethyl acetate Were mixed and stirred to obtain an [aqueous phase] that was a milky white liquid.

-Preparation of emulsion or dispersion-
150 parts of the obtained [aqueous phase] is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 100 parts were added and mixed for 10 minutes to obtain an [emulsified slurry] which was an emulsified or dispersed liquid.

-Removal of organic solvent-
[Emulsion slurry] 100 parts was charged in a flask equipped with a degassing pipe, a stirrer and a thermometer, and the solvent was removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. [Solvent slurry] Got.

-Washing-
[Solvent removal slurry] The entire amount was filtered under reduced pressure to obtain a filter cake, and then 300 parts of ion-exchanged water was added to the filter cake, followed by mixing and redispersion (at 12,000 rpm for 10 minutes) with a TK homomixer. After filtration. To the obtained filter cake, 300 parts of ion exchange water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered three times. The conductivity of the redispersed slurry was [Washing slurry] was obtained when it became 0.1 μS / cm or more and 10 μS / cm or less.

-Heat treatment-
The obtained [washing slurry] was heated in a flask with a stirrer and a thermometer at 50 ° C. for 60 minutes with stirring at a stirring peripheral speed of 20 m / min, followed by filtration to obtain [filter cake].

-Drying-
The obtained [filter cake] was dried at 45 ° C. for 48 hours in a forward air dryer and sieved with a mesh having an opening of 75 μm to obtain toner base particles a.

-External treatment-
To 100 parts of the toner base particles a, 0.6 part of hydrophobic silica having an average particle diameter of 100 nm (UFP35, manufactured by Denki Kagaku Kogyo Co., Ltd.) and titanium oxide having an average particle diameter of 20 nm (MT150IB, manufactured by Teika Co., Ltd.) 1.0 part and 0.8 part of hydrophobic silica fine powder (HDK2000H, manufactured by Clariant Japan KK) having an average particle diameter of 15 nm were mixed with a Henschel mixer to obtain a color toner a.

<< Manufacture of clear toner a >>
In the preparation of the emulsified or dispersed liquid in the production of the color toner a, the same procedure as in the production of the color toner a was performed except that [oil phase (for color toner)] was changed to [oil phase (for clear toner)] below. A clear toner a was obtained.

-Preparation of toner material phase (oil phase) (for clear toner)-
In a beaker, 100 parts of amorphous polyester resin b1 and 130 parts of ethyl acetate were placed and stirred to dissolve. Next, 10 parts of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.) WA-05TS, manufactured by Toa Kasei Co., Ltd.) was charged, and a bead mill (Ultra Visco Mill) , Manufactured by Imex Co., Ltd.), and a raw material solution is prepared by three passes under the condition that 80% by volume of zirconia beads having a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / s, and a diameter of 0.5 mm are filled. After stirring, a [oil phase (for clear toner)] which is a solution or dispersion of the toner material was obtained.

<Evaluation of toner>
<< Heat resistant storage stability >>
After leaving 20 g of toner in an environment of a temperature of 40 ° C. and a humidity of 70% for 2 weeks, the toner is passed through a 75 mesh sieve, and after applying vibration with an amplitude of 1 mm, the amount of toner remaining on the sieve (aggregated toner) Amount) was measured and evaluated according to the following evaluation criteria. The results are shown in Table 4.
[Evaluation criteria]
A: Aggregated toner amount is less than 0.3 mg B: Aggregated toner amount is 0.3 mg or more and less than 0.5 mg Δ: Aggregated toner amount is 0.5 mg or more and less than 1.0 mg X: Aggregated toner amount is 1.0 mg or more

<< Clear Toner Glossiness >>
The glossiness of the obtained clear toner was evaluated as follows.
Using Ricoh's full-color MFP Imagio NeoC600Pro with a solid image on a cardboard transfer paper (copying paper <135> manufactured by Ricoh Co., Ltd.) with a toner adhesion of 0.85 ± 0.1 mg / cm ² The image gloss after fixing was measured using an apparatus in accordance with the conditions described in JIS Z8741 (60 ° specular gloss), and evaluated according to the following evaluation criteria. The results are shown in Table 4.
[Evaluation criteria]
◎: 60% or more ○: 50% or more and less than 60% △: 40% or more and less than 50% ×: less than 40%

<< Gloss Difference ΔGs >>
The difference in gloss between the obtained clear toner and color toner was evaluated as follows.
Using Ricoh's full-color MFP Imagio NeoC600Pro with a solid image on a cardboard transfer paper (copying paper <135> manufactured by Ricoh Co., Ltd.) with a toner adhesion of 0.85 ± 0.1 mg / cm ² After fixing, the image gloss after fixing was measured using an apparatus in accordance with the conditions described in JIS Z8741 (60 ° specular gloss). Then, the gloss difference between the gloss F of the portion where only the color toner is fixed and the gloss C of the portion where the clear toner is fixed on the color toner is ΔGs (C−F), and the following evaluation criteria are used. The results are shown in Table 4.
[Evaluation criteria]
◎: 30% or more ○: 20% or more and less than 30% △: 10% or more and less than 20% ×: Less than 10%

(Example 2)
<Manufacture of toner set b>
<< Production of Color Toner b >>
In the production of the color toner a of Example 1, the color toner b was obtained in the same manner as in the production of the color toner a of Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a2. It was.

<< Manufacture of clear toner b >>
In the production of the clear toner a of Example 1, the clear toner b was obtained in the same manner as the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced by the amorphous polyester resin b2. It was.

The obtained color toner b and clear toner b were evaluated in the same manner as in Example 1. The results are shown in Table 4.
In the obtained color toner b and clear toner b, the melt viscosity is lowered by making the methylene chain of the amorphous polyester resin longer than the methylene chain of the amorphous polyester resin of Example 1, and the heat resistant storage stability is Although it is slightly inferior to the toner set a, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 3)
<Manufacture of toner set c>
<< Manufacture of color toner c >>
In the production of the color toner a of Example 1, the color toner c was obtained in the same manner as the production of the color toner a of Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a3. It was.

<< Manufacture of clear toner c >>
In the production of the clear toner a of Example 1, the clear toner c was obtained in the same manner as the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b3. It was.

The obtained color toner c and clear toner c were evaluated in the same manner as in Example 1. The results are shown in Table 4.
In the obtained color toner c and clear toner c, the melt viscosity is lowered by making the methylene chain of the amorphous polyester resin longer than the methylene chain of the amorphous polyester resin of Example 1, and the heat resistant storage stability is Although it is slightly inferior to the toner set a, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

Example 4
<Manufacture of toner set d>
<< Manufacture of color toner d >>
In the production of the color toner a in Example 1, the color toner d was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a4. It was.

<< Manufacture of clear toner d >>
In the production of the clear toner a in Example 1, the clear toner d was obtained in the same manner as in the production of the clear toner a in Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b4. It was.

The obtained color toner d and clear toner d were evaluated in the same manner as in Example 1. The results are shown in Table 4.
In the obtained color toner d and clear toner d, the melt viscosity is increased by making the methylene chain of the amorphous polyester resin shorter than the methylene chain of the amorphous polyester resin of Example 1, and the glossiness is Although slightly inferior to toner set a, the problem could be sufficiently achieved.

(Example 5)
<Manufacture of toner set e>
<< Manufacture of color toner e >>
In the production of the color toner a of Example 1, the color toner e was obtained in the same manner as in the production of the color toner a of Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a5. It was.

<< Manufacture of clear toner e >>
In the production of the clear toner a of Example 1, the clear toner e was obtained in the same manner as the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b5. It was.

The obtained color toner e and clear toner e were evaluated in the same manner as in Example 1. The results are shown in Table 4.
In the obtained color toner e and clear toner e, the melt viscosity is lowered by making the methylene chain of the amorphous polyester resin longer than the methylene chain of the amorphous polyester resin of Example 1, and the heat resistant storage stability is Although it is slightly inferior to the toner set a, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 6)
<Manufacture of toner set f>
<< Production of Color Toner f >>
In the production of the color toner a in Example 1, the color toner f was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a6. It was.

<< Manufacture of clear toner f >>
A clear toner f was obtained in the same manner as in the production of the clear toner a in Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b6 in the production of the clear toner a in Example 1. It was.

The obtained color toner f and clear toner f were evaluated in the same manner as in Example 1. The results are shown in Table 4.
In the obtained color toner f and clear toner f, the melt viscosity is lowered by making the methylene chain of the amorphous polyester resin longer than the methylene chain of the amorphous polyester resin of Example 1, and the heat resistant storage stability is Although it is slightly inferior to the toner set a, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 7)
<Manufacture of toner set g>
<< Color Toner g >>
The color toner a of Example 1 was used as the color toner g.

<< Manufacture of Clear Toner g >>
In the production of the clear toner a of Example 1, the clear toner g was obtained in the same manner as the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b7. It was.

The obtained color toner g and clear toner g were evaluated in the same manner as in Example 1. The results are shown in Table 4.
The melt viscosity is lowered by changing the substituent of the methylene chain in the amorphous polyester resin for clear toner from the methyl group to the ethyl group in Example 1 to increase the steric hindrance, and the heat-resistant storage stability is slightly higher than that of the toner set a. Although it is inferior, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 8)
<Manufacture of toner set h>
<< Color Toner h >>
The color toner a of Example 1 was used as the color toner h.

<< Manufacture of clear toner h >>
A clear toner h was obtained in the same manner as in the production of the clear toner a in Example 1, except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b8 in the production of the clear toner a in Example 1. It was.

The obtained color toner h and clear toner h were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By changing the substituent of the methylene chain in the amorphous polyester resin for clear toner from the methyl group to the propyl group in Example 1 to increase the steric hindrance, the melt viscosity is lowered, and the heat-resistant storage stability is slightly higher than that of the toner set a. Although it is inferior, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

Example 9
<Manufacture of toner set i>
<< Color Toner i >>
The color toner a of Example 1 was used as the color toner i.

<< Manufacture of Clear Toner i >>
A clear toner i was obtained in the same manner as in the production of the clear toner a in Example 1, except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b9 in the production of the clear toner a in Example 1. It was.

The obtained color toner i and clear toner i were evaluated in the same manner as in Example 1. The results are shown in Table 4.
The melt viscosity is lowered by changing the substituent of the methylene chain in the amorphous polyester resin for clear toner from the methyl group to the methoxy group in Example 1 to increase the steric hindrance, and the heat-resistant storage stability is slightly higher than that of the toner set a. Although it is inferior, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 10)
<Manufacture of toner set j>
<< Color Toner j >>
The color toner a of Example 1 was used as the color toner j.

<< Manufacture of clear toner j >>
In the production of the clear toner a of Example 1, the clear toner j was obtained in the same manner as in the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b10. It was.

The obtained color toner j and clear toner j were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By changing the substituent of the methylene chain in the amorphous polyester resin for clear toner from the methyl group to the sulfo group in Example 1 to increase the steric hindrance, the melt viscosity is lowered, and the heat storage stability is slightly higher than that of the toner set a. Although it is inferior, the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 11)
<Manufacture of toner set k>
<< Manufacture of color toner k >>
In the production of the color toner a in Example 1, the color toner k was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a7. It was.

<< Manufacture of clear toner k >>
The clear toner a of Example 1 was used as the clear toner k.

The obtained color toner k and clear toner k were evaluated in the same manner as in Example 1. The results are shown in Table 4.
The melt viscosity is increased by making the weight average molecular weight of the amorphous polyester resin for color toner larger than the weight average molecular weight of the amorphous polyester resin for color toner of Example 1, and the glossiness of the color toner is determined by the toner set a Although it is slightly inferior to the above, the heat-resistant storage stability is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 12)
<Manufacture of toner set 1>
<< Color toner l >>
The color toner a of Example 1 was used as the color toner l.

<< Manufacture of Clear Toner I >>
In the production of the clear toner a of Example 1, the clear toner l was obtained in the same manner as in the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b11. It was.

The obtained color toner 1 and clear toner 1 were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By increasing the weight average molecular weight of the amorphous polyester resin for clear toner to be larger than the weight average molecular weight of the amorphous polyester resin for clear toner of Example 1, the melt viscosity increases, and glossiness and The gloss difference is slightly inferior to that of toner set a, but the problem can be sufficiently achieved.

(Example 13)
<Manufacture of toner set m>
<< Manufacture of color toner m >>
In the production of the color toner a of Example 1, the color toner m was obtained in the same manner as in the production of the color toner a of Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a7. It was.

<< Manufacture of clear toner m >>
A clear toner m was obtained in the same manner as in the production of the clear toner a in Example 1, except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b11 in the production of the clear toner a in Example 1. It was.

The obtained color toner m and clear toner m were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By making the weight average molecular weight of both the amorphous polyester resin for color toner and the amorphous polyester resin for clear toner larger than the weight average molecular weight of the amorphous polyester resin of Example 1, the melt viscosity is increased and the glossiness is increased. Although it is slightly inferior to the toner set a, the heat-resistant storage stability is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Example 14)
<Manufacture of toner set n>
<< Manufacture of color toner n >>
In the production of the color toner a in Example 1, the color toner n was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a8. It was.

<< Manufacture of clear toner n >>
The clear toner a of Example 1 was used as the clear toner n.

The obtained color toner n and clear toner n were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By making the weight average molecular weight of the amorphous polyester resin for color toners smaller than the weight average molecular weight of the amorphous polyester resin for color of Example 1, the melt viscosity is lowered, the heat resistant storage stability of the color toner, and the color toner The gloss difference from the clear toner is slightly inferior to that of the toner set a, but the problem can be sufficiently achieved.

(Example 15)
<Manufacture of toner set o>
<< Color Toner o >>
The color toner a of Example 1 was used as the color toner o.

<< Manufacture of clear toner o >>
In the production of the clear toner a of Example 1, the clear toner o was obtained in the same manner as in the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b12. It was.

The obtained color toner o and clear toner o were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By making the weight average molecular weight of the amorphous polyester resin for clear toner smaller than the weight average molecular weight of the amorphous polyester resin for clear toner of Example 1, the melt viscosity is lowered. Although slightly inferior to a, the glossiness and the difference in gloss between the color toner and the clear toner can sufficiently achieve the problem.

(Example 16)
<Manufacture of toner set p>
<< Manufacture of color toner p >>
In the production of the color toner a in Example 1, the color toner p was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a8. It was.

<< Manufacture of clear toner p >>
In the production of the clear toner a of Example 1, the clear toner p was obtained in the same manner as in the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced by the amorphous polyester resin b12. It was.

The obtained color toner p and clear toner p were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By making the weight average molecular weight of both the amorphous polyester resin for color toner and the amorphous polyester resin for clear toner smaller than the weight average molecular weight of the amorphous polyester resin of Example 1, the melt viscosity is lowered and the heat resistant storage stability is reduced. Is slightly inferior to the toner set a, but the glossiness is superior to that of the toner set a, and the gloss difference between the color toner and the clear toner can sufficiently achieve the problem.

(Comparative Example 1)
<Manufacture of toner set q>
<< Production of Color Toner q >>
In the production of the color toner a of Example 1, the color toner q was obtained in the same manner as in the production of the color toner a of Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a9. It was.

<< Manufacture of clear toner q >>
A clear toner q was obtained in the same manner as in the production of the clear toner a in Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b13 in the production of the clear toner a in Example 1. It was.

The obtained color toner q and clear toner q were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By making the methylene chain of the diol component of the amorphous polyester resin an even number, the melt viscosity increased, the desired glossiness could not be obtained, and there was no prospect of improvement.

(Comparative Example 2)
<Manufacture of toner set r>
<< Manufacture of color toner r >>
In the production of the color toner a in Example 1, the color toner r was obtained in the same manner as in the production of the color toner a in Example 1 except that the amorphous polyester resin a1 was replaced with the amorphous polyester resin a10. It was.

<< Manufacture of clear toner r >>
In the production of the clear toner a of Example 1, the clear toner r was obtained in the same manner as the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b14. It was.

The obtained color toner r and clear toner r were evaluated in the same manner as in Example 1. The results are shown in Table 4.
The melt viscosity was lowered by extending the methylene chain of the dicarboxylic acid component in the amorphous polyester resin, and the glossiness was able to sufficiently achieve the problem, but the heat-resistant storage stability was not expected to be improved.

(Comparative Example 3)
<Manufacture of toner set s>
<< Production of Color Toners >>
In the production of the color toner a of Example 1, the color toner s is obtained in the same manner as in the production of the color toner a of Example 1 except that the amorphous polyester resin a1 is replaced with the amorphous polyester resin a11. It was.

<< Manufacture of Clear Toners >>
A clear toner s was obtained in the same manner as in the production of the clear toner a in Example 1, except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b15 in the production of the clear toner a in Example 1. It was.

The obtained color toner s and clear toner s were evaluated in the same manner as in Example 1. The results are shown in Table 4.
The melt viscosity was lowered by increasing the methylene chain of the diol component in the amorphous polyester resin, and the glossiness was able to sufficiently achieve the problem, but the heat resistant storage stability was not expected to be improved.

(Comparative Example 4)
<Manufacture of toner set t>
<< Manufacture of color toner t >>
The color toner a of Example 1 was used as the color toner t.

<< Manufacture of clear toner t >>
A clear toner t was obtained in the same manner as in the production of the clear toner a in Example 1 except that the amorphous polyester resin b1 was replaced with the amorphous polyester resin b16 in the production of the clear toner a in Example 1. It was.

The obtained color toner t and clear toner t were evaluated in the same manner as in Example 1. The results are shown in Table 4.
Changing the substituent of the methylene chain in the amorphous polyester resin for clear toner from the methyl group to the phenyl group in Example 1 increases the melt viscosity and impairs the glossiness of the clear toner, as well as the color toner and the clear toner. There was no prospect of improvement.

(Comparative Example 5)
<Manufacture of toner set u>
<< Manufacture of color toner u >>
The color toner a of Example 1 was used as the color toner u.

<< Manufacture of clear toner u >>
In the production of the clear toner a of Example 1, the clear toner u was obtained in the same manner as in the production of the clear toner a of Example 1 except that the amorphous polyester resin b1 was replaced by the amorphous polyester resin b17. It was.

The obtained color toner u and clear toner u were evaluated in the same manner as in Example 1. The results are shown in Table 4.
By setting the number of carbon atoms of the acid monomer and alcohol monomer in the non-crystalline polyester resin for clear toner to an odd number, the melt viscosity increases and the glossiness of the clear toner is impaired. There was no difference, and there was no prospect of improvement.

  Table 3 shows the resin characteristics of the toner sets of Examples 1 to 16 and Comparative Examples 1 to 5.

The number of methylene groups (m in the general formula (1)) in the dicarboxylic acid component of the amorphous polyester resin is 2 or 4, and the number of methylene groups in the diol component (for example, —R ² —C—R in the general formula (2)) ^{When the} number of ^3- carbons was 5 and the substituent (for example, R ¹ in the general formula (2)) was a methyl group, the heat resistant storage stability was more excellent (for example, Example 1, 4, 12, 13, 14).
When the number of methylene groups in the diol component of the amorphous polyester resin (for example, the carbon number of —R ² —C—R ³ — in the general formula (2)) is 7 or 9, the glossiness of the clear toner, and ΔGs Resulted in better results (eg, Examples 2 and 3).
When the number of methylene groups (m in the general formula (1)) in the dicarboxylic acid component of the amorphous polyester resin was 8 or 10, the glossiness of the clear toner and ΔGs were more excellent (for example, implementation) Examples 5, 6).
When the substituent in the diol component of the amorphous polyester resin (for example, R ¹ in the general formula (2)) is an ethyl group, an n-propyl group, a methoxy group, or a sulfo group, the glossiness of the clear toner, and ΔGs was more excellent (for example, Examples 7 to 10).
When the weight average molecular weight of the amorphous polyester resin used for the color toner is high (over 10,000 to 15,000 or less) and the weight average molecular weight of the amorphous polyester resin used for the clear toner is 4,000 to 10,000. Resulted in better ΔGs (eg, Example 11).
When the weight average molecular weight of the amorphous polyester resin used for the clear toner is low (4,000 or more and less than 5,000), the glossiness and ΔGs of the clear toner are more excellent (for example, Example 15). 16).

Aspects of the present invention are as follows, for example.
<1> containing at least a polyester resin,
The polyester resin has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹¹ (R ¹¹ Represents any one of a hydrogen atom and a sodium atom), and R ² and R ³ are each independently a single bond or a linear alkylene group having 1 to 8 carbon atoms. It indicates whether further ^-R 2 ^{-C-R 3} - carbon atoms is odd 3-9.
<2> In General Formula (2), R ¹ is any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ^11. In the toner according to <1>, R ² and R ³ are both linear alkylene groups having 1 to 4 carbon atoms.
<3> The polyester resin further includes at least one of a structural unit derived from a dicarboxylic acid component having an aromatic ring and a structural unit derived from a diol component having an aromatic ring. The toner is described.
<4> The toner according to any one of <1> to <3>, wherein the polyester resin has a weight average molecular weight of 4,000 to 15,000.
<5> The toner according to any one of <1> to <4>, further including a crystalline polyester resin.
<6> Contains color toner and clear toner,
The color toner contains at least a polyester resin a;
The clear toner contains at least a polyester resin b;
The polyester resin a has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (3),
In the toner set, the polyester resin b has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (4).
However, in said general formula (1), m represents the even number of 2-10. In the general formula (3), n is an odd number of 3 to 9. In the general formula (4), R ⁴ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ¹² (R ¹² is hydrogen And R ⁵ and R ⁶ each independently represents a single bond or a linear alkylene group having 1 to 8 carbon atoms. Furthermore, the carbon number of —R ⁵ —C—R ⁶ — is an odd number of 3-9.
<7> In General Formula (4), R ⁴ is any one of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, —NO ₂ , —NH ₂ , and —SO ₃ R ^12. The toner set according to <6>, wherein R ⁵ and R ⁶ are both linear alkylene groups having 1 to 4 carbon atoms.
<8> From the above <6> to <7, wherein the polyester resin a and the polyester resin b further include at least one of a structural unit derived from a dicarboxylic acid component having an aromatic ring and a structural unit derived from a diol component having an aromatic ring. The toner set according to any one of the above.
<9> The toner set according to any one of <6> to <8>, wherein the polyester resin a and the polyester resin b have a weight average molecular weight of 4,000 to 15,000.

Japanese Patent No. 3146367 Japanese Patent Laid-Open No. 9-200551 JP 2007-163902 A

Claims (7)

Contains at least a polyester resin,
The polyester resin has a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), a structural unit derived from a dicarboxylic acid component having an aromatic ring, an aromatic ring toner characterized in that it have a structural unit derived from a diol component having.

However, in said general formula (1), m represents the even number of 2-10. In formula (2), ^{R 1} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms,及 Beauty _-SO 3 ^{R 11 (R} 11 represents a hydrogen atom And R ² and R ³ each independently represents a single bond or a linear alkylene group having 1 to 8 carbon atoms, and the number of carbon atoms of R ² and R ³ is The sum is an even number from 2 to 8 . In the general formula (2), ^{R 1} is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, are either 及 beauty _-SO 3 ^{R 11, R 2} and ^{R 3} are both The toner according to claim 1, wherein the toner is a linear alkylene group having 1 to 4 carbon atoms. The toner according to claim 1, wherein the polyester resin has a weight average molecular weight of 4,000 to 15,000. Contains color toner and clear toner,
The color toner contains at least a polyester resin a;
The clear toner contains at least polyester resin b,
The polyester resin a is a structural unit represented by the following general formula (1) and the following general formula (3
A structural unit represented by
The polyester resin b is a structural unit represented by the following general formula (1) and the following general formula (4
A toner set having a structural unit represented by:
However, in said general formula (1), m represents the even number of 2-10. In the general formula (3), n
Is an odd number of 3-9. In the general formula (4), R ⁴ Is an alkyl group having 1 to 3 carbon atoms, charcoal
A prime number 1-3 alkoxy group, and -SO ₃ R ¹² (R ¹² Represents a hydrogen atom. ) And R ⁵ And R ⁶ Each independently represents a linear alkylene group having 1 to 8 carbon atoms; ^Five And R ⁶ The total number of carbon atoms is an even number of 2-8. In the general formula (4), R ⁴ Is an alkyl group having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms.
Si group and -SO ₃ R ¹² R ⁵ And R ⁶ The toner set according to claim 4, wherein both are linear alkylene groups having 1 to 4 carbon atoms. Polyester resin a and polyester resin b are further dicarboxylic acid components having an aromatic ring
At least of structural units derived from diol components having aromatic rings and aromatic units
The toner set according to claim 4, wherein the toner set has a deviation. The weight average molecular weights of the polyester resin a and the polyester resin b are 4,000 to 15,
The toner set according to claim 4, which is 000.