JP4053866B2 - Resin composition for toner and toner - Google Patents

Description

【００８５】
【表２】

【００８６】
【表３】

【００８７】
【発明の効果】
本発明によれば、低温定着性、耐高温オフセット性及び耐ブロッキング性に優れ、良好な発色を行うことができるトナー用樹脂組成物及びトナーを提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition for toner and a toner that are excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance and that can perform good color development.
[0002]
[Prior art]
A dry development method is frequently used as a method for developing an electrostatic image in electrophotography or the like. In the dry development system, the toner is usually charged by friction with iron powder, glass beads, etc., called a carrier, which adheres to the electrostatic latent image on the photoreceptor by electrical attraction, and then transferred onto the paper, It is fixed by a heating roller or the like and becomes a permanent visible image.
[0003]
As a fixing method, a heating roller method is generally used in which a toner image of a fixing sheet is passed through a surface of a heat fixing roller formed with a material having releasability with respect to a toner while being in pressure contact. ing.
[0004]
In this heat fixing roller method, there is a demand for a toner that can be fixed at a lower temperature in order to improve economy such as power consumption and to increase the copying speed.
However, when trying to improve the low-temperature fixability described above, an offset phenomenon in which a part of the toner adheres to the surface of the heat-fixing roller and retransfers to the paper is likely to occur, or the resins are subjected to various environments. There is a problem that a blocking phenomenon in which toner aggregates due to heat tends to occur.
[0005]
In order to solve these problems, Patent Document 1 discloses that a unit derived from terephthalic acid and a linear alkylene glycol having 2 to 6 carbon atoms as a binder resin of the toner is 50 mol% or more based on the total monomer units used. It has been proposed to use a crystalline polyester resin containing.
However, in this technique, since only the crystalline polyester resin is used, it is difficult to maintain the high-temperature offset resistance and the blocking resistance without impairing the low-temperature fixability because the temperature range capable of fixing is narrow.
[0006]
In Patent Document 2, as a toner binder resin, a trivalent or higher polyvalent monomer, an aromatic dicarboxylic acid, and an aliphatic alcohol containing 50 mol% or more of a branched aliphatic alcohol are polymerized. It has been proposed to use an amorphous polyester resin.
However, in this technique, only the amorphous polyester resin is used, so that the low-temperature fixability is not sufficient.
[0007]
Patent Document 3 and Patent Document 4 propose a toner containing two types of polyesters having different softening points as a resin for toner as a toner having an excellent balance between low-temperature fixability and high-temperature and high-temperature offset resistance.
However, the compatibility of the above two types of polyesters is not sufficient, and there is a problem that polyesters having a low softening point tend to cause blocking, or adhere to the fixing roller and cause filming. There was also a problem that the transparency of the resin was low because the solubility was not sufficient.
[0008]
Patent Document 5 proposes to use a block copolymer of a low-melting crystalline polyester and a high-melting crystalline polyester as a binder resin for the toner. However, this technique has a problem that a transparent resin cannot be obtained because the binder resin becomes a cloudy resin.
[0009]
Further, since the blocking phenomenon is likely to occur when the toner is exposed to a temperature higher than the glass transition temperature of the toner resin, studies are being made on a polyester resin for the toner that is less likely to cause the blocking phenomenon. As a polyester resin for toner that does not cause a blocking phenomenon, although the low-temperature fixing temperature is not so low, for example, Patent Document 6 shows that the polyester resin composition is effective as a specific composition. 7 shows that it is effective when the composition of the polyester resin is specified and the glass transition temperature is 45 to 70 ° C.
[0010]
However, although these techniques make it difficult for the blocking phenomenon to occur at room temperature, even if these toner resins are used, if the toner is exposed to a temperature near the glass transition temperature of the toner resin, the blocking phenomenon still occurs. There was a problem that.
[0011]
[Patent Document 1]
Japanese Patent No. 2988703
[Patent Document 2]
Japanese Patent No. 2704282
[Patent Document 3]
Japanese Patent Laid-Open No. 4-97366
[Patent Document 4]
JP-A-4-313760
[Patent Document 5]
Japanese Patent Publication No. 5-44032
[Patent Document 6]
JP-A-4-337774
[Patent Document 7]
Japanese Patent Laid-Open No. 10-36490
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition for toner and a toner that are excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance, and that can perform good color development.
[0013]
[Means for Solving the Problems]
The present invention contains a crystalline polymer having a melting point of 180 to 280 ° C. and an amorphous polyester having a glass transition temperature of 50 to 80 ° C. And the crystalline polymer includes crystalline polyamide. The toner resin composition. The present invention is described in detail below.
[0014]
The resin composition for a toner of the present invention contains a crystalline polymer having a melting point of 180 to 280 ° C. and an amorphous polyester having a glass transition temperature of 50 to 80 ° C.
In the present specification, the crystalline polymer means a polymer that exhibits a sharp and clear melting point peak when the differential heat is measured by a differential scanning calorimeter, and has a crystallinity of more than 10%. The polyester means a polyester having a crystallinity of 10% or less without showing a sharp and clear melting point peak when differential heat is measured by a differential scanning calorimeter.
[0015]
The lower limit of the melting point of the crystalline polymer is 180 ° C., and the upper limit is 280 ° C. When the temperature is lower than 180 ° C, the high temperature offset resistance is inferior. When the temperature exceeds 280 ° C, it is necessary to melt at a high temperature exceeding 280 ° C when mixed with the non-crystalline polyester. End up. A preferred lower limit is 200 ° C and a preferred upper limit is 240 ° C.
[0016]
Although it does not specifically limit as said crystalline polymer, Crystalline polyester or crystalline polyamide is preferable, More preferably, it consists of crystalline polyamide and crystalline polyester. By comprising the crystalline polyamide and the crystalline polyester, the high temperature offset resistance can be further improved by the synergistic effect of the two crystalline polymers.
[0017]
The crystalline polyester can be obtained by condensation polymerization of dicarboxylic acid and diol.
Examples of the dicarboxylic acid include o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, maleic acid, and itacone. Examples include acids, decamethylene carboxylic acids, anhydrides and lower alkyl esters thereof. Among these, terephthalic acid, naphthalenedicarboxylic acid, and anhydrides and lower alkyl esters thereof are preferably used for imparting crystallinity.
[0018]
Examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, triethylene glycol, and tetraethylene. Glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2, Aliphatic diols such as 5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxycyclo) Hexyl) alkylene oxide adducts of propane, 1,4-cyclohexane diol, alicyclic diols such as 1,4-cyclohexanedimethanol.
[0019]
Among these, the crystalline polyester is preferably polybutylene terephthalate obtained by polycondensing a monomer mixture containing terephthalic acid and 1,4-butanediol as main components. Since the polybutylene terephthalate has a high degree of crystallinity and excellent compatibility with amorphous polyester, the effect of improving high-temperature offset resistance is great.
[0020]
The crystalline polyamide is not particularly limited, and examples thereof include 6-nylon, 6,6-nylon, 4,6-nylon, 11-nylon, 12 nylon, and the like. Polymerized polyamide ester copolymers are also included. Of these, 6-nylon and 6,6-nylon are preferred because they have high crystal cohesion and are excellent in the effect of improving high-temperature offset resistance.
In addition, the polyamide ester block copolymer has a rubber elasticity, a long stress relaxation time, and excellent compatibility with the amorphous polyester, and therefore has a large effect of improving the high temperature offset resistance. More preferably, it is a polyamide ester block copolymer containing 6,6-nylon, and since the melting point is high, the effect of improving high-temperature offset resistance is particularly large.
Since the crystalline polyamide has a strong intermolecular cohesive force, the high temperature offset resistance can be exhibited only by using a small amount of the polyester, and the strength of the resin itself can be increased.
[0021]
The lower limit of the glass transition temperature of the non-crystalline polyester is 50 ° C., and the upper limit is 80 ° C. If it is less than 50 ° C., sufficient high-temperature offset resistance and blocking resistance cannot be obtained, and if it exceeds 80 ° C., low-temperature fixability is inferior. A preferred lower limit is 55 ° C and a preferred upper limit is 65 ° C.
[0022]
The non-crystalline polyester can be obtained by polycondensing a dicarboxylic acid and a diol. The amorphous polyester obtained by polycondensation of dicarboxylic acid and diol has a linear structure and has 2 terminals.
The glass transition temperature of non-crystalline polyester is such that aromatic dicarboxylic acids such as terephthalic acid improve the glass transition temperature, and long-chain aliphatic dicarboxylic acids such as sebacic acid and adipic acid have a glass transition temperature. Therefore, the target glass transition temperature can be achieved by appropriately combining these dicarboxylic acids. However, even if the desired glass transition temperature can be achieved by appropriately combining an aromatic dicarboxylic acid and a long-chain aliphatic dicarboxylic acid, the softening temperature tends to be too high.
Therefore, the non-crystalline polyester is preferably obtained by polymerizing a monomer mixture containing at least either a divalent bending monomer or a divalent branched monomer capable of introducing a bent molecular structure into the molecular chain. A polymer obtained by polymerizing a monomer mixture containing these divalent bending monomers and divalent branched monomers can easily achieve both a desired glass transition temperature and a low softening temperature, and is effective in crystallization. Can be suppressed.
[0023]
Examples of the divalent bending monomer include aromatic dicarboxylic acids in which the ortho position or the meta position is substituted with a carboxyl group, aromatic diols in which the ortho position or the meta position is substituted with a hydroxyl group, and many having a carboxyl group in an asymmetric position It is not limited to a dicarboxylic acid or a diol as long as it is a monomer capable of introducing a bent molecular structure into a polymer molecular chain such as a ring aromatic dicarboxylic acid or a polycyclic aromatic diol having a hydroxyl group at an asymmetric position. It may be an anhydride, a lower ester, a monohydroxymonocarboxylic acid, etc., for example, a dicarboxylic acid such as phthalic anhydride, o-phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, etc. Acids and their anhydrides and lower esters, salicylic acid, 3-hydroxy-2-naphthalene Monohydroxy monocarboxylic acids such as carboxylic acid, and diols catechol.
[0024]
The divalent branched monomer effectively suppresses crystallization of the polymer due to steric hindrance at the branched portion.
The divalent branched monomer is not particularly limited, and examples thereof include an aliphatic diol having a branched alkyl chain, an alicyclic diol having a branched alkyl chain, and the like. For example, 1,2-propanediol, 1,3 -Butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4 -Pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5- Aliphatic diols such as pentanediol; 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxycyclohexyl) Alicyclic diols such as alkylene oxide adducts of propane and the like. The alicyclic diol is preferably an alicyclic diol in which a plurality of alicyclic diols are linked by a branched alkylene chain.
Among them, the amorphous polyester obtained by polymerizing a monomer mixture mainly composed of terephthalic acid, neopentyl glycol, and ethylene glycol and / or 1,4-butanediol has excellent low-temperature fixability and transparency. To preferred.
[0025]
In addition, the non-crystalline polyester has a radial structure and / or a comb-shaped structure, and has an amorphous polyester having three or more ends, or a radial structure and / or a comb-shaped structure, and has three or more Also suitable are mixtures of non-crystalline polyesters having ends and polyesters of the above-mentioned linear structure. By having a radial structure and / or a comb structure, and having three or more ends, fluidity at the time of melting is improved, and low-temperature fixability is improved.
In such an amorphous polyester, it is preferable that a crosslinked structure is not formed, but it may be formed at a level that does not lower the low-temperature fixability.
As a method for producing such an amorphous polyester, for example, in the case of an amorphous polyester having a radial structure, a dicarboxylic acid and a diol are mixed with a trivalent or higher polyvalent carboxylic acid and a trivalent or higher polyvalent. It can be obtained by polycondensation by adding a polyfunctional monomer such as a monohydric alcohol.
[0026]
The trivalent or higher polyvalent carboxylic acid is not particularly limited. For example, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2, Examples include 4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and acid anhydrides thereof.
The trihydric or higher polyhydric alcohol is not particularly limited. For example, sorbitol, 1,2,3,6-hexanetetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3 , 5-trihydroxymethylbenzene and the like.
These polyfunctional monomers may be used alone or in combination of two or more.
[0027]
The preferable lower limit of the ratio of the polyfunctional monomer unit to the dicarboxylic acid unit is 0.05 mol%, and the preferable upper limit is 20 mol%. If it is less than 0.05 mol%, sufficient low-temperature fixability may not be obtained. When it exceeds 20 mol%, fluidity may deteriorate and low-temperature fixability may also deteriorate. A more preferred lower limit is 0.1 mol%, and a more preferred upper limit is 5 mol%.
[0028]
When a non-crystalline polyester having a radial structure and / or a comb structure and having three or more terminals obtained by polycondensation with a polyfunctional monomer is used, the preferred lower limit of the weight average molecular weight is 3000. The preferred upper limit is 18000. If it is less than 3000, the filming performance of the obtained toner may be inferior. If it exceeds 18000, the reaction of the polyfunctional monomer is difficult to control and the crosslinking reaction proceeds, and the resulting toner is fixed at low temperature. May be inferior. The weight average molecular weight can be controlled by adjusting the reaction time or adding a monofunctional monomer.
[0029]
The crystalline polymer and the non-crystalline polyester are preferably compatible. When the crystalline polymer and the non-crystalline polyester are compatible, the toner resin composition of the present invention becomes colorless and transparent, and can be suitably used as a color toner resin composition capable of performing good color development. In addition, since it has a high resin strength, it can be suitably used as a resin composition for a toner having excellent high-temperature offset resistance.
The term “compatible” refers to a state in which the crystalline polymer and the non-crystalline polyester are uniformly mixed. These may be completely compatible or partially compatible. .
[0030]
If the crystalline polyester is used as the crystalline polymer, and the crystalline polyester and the amorphous polyester have a common monomer component such as terephthalic acid as a constituent monomer, compatibility can be improved. it can. For example, the crystalline polyester is obtained by polymerizing a monomer mixture containing terephthalic acid and 1,4-butanediol as main components, while the amorphous polyester includes terephthalic acid, neopentyl glycol, and When a monomer mixture containing ethylene glycol and / or 1,4-butanediol as a main component is polymerized, they are well compatible.
[0031]
As the content of the crystalline polymer and the non-crystalline polyester in the resin composition for toner of the present invention, the preferred lower limit of the crystalline polymer content is 0.5% by weight, and the preferred upper limit is 30% by weight. In addition, the preferable lower limit of the content of the amorphous polyester is 99.5% by weight, and the preferable upper limit is 70% by weight.
When the content of the crystalline polymer is less than 0.5% by weight, the high temperature offset resistance may be inferior, and when it exceeds 30% by weight, the low temperature fixability may be inferior. A more preferred lower limit is 1% by weight, and a more preferred upper limit is 20% by weight.
[0032]
The toner resin composition of the present invention preferably further contains an amorphous polyester having a weight average molecular weight of 20,000 to 300,000, preferably 30,000 to 200,000. By blending such a high molecular weight amorphous polyester, the high temperature offset resistance of the resulting toner can be further improved. The blending amount of such a high molecular weight non-crystalline polyester is not particularly limited, but the preferred lower limit is 2% by weight and the preferred upper limit is 30% by weight with respect to the total toner resin composition. If it is less than 2% by weight, a sufficient effect of improving high-temperature offset resistance may not be obtained, and if it exceeds 30% by weight, the low-temperature fixability may be inferior.
[0033]
The method for producing the resin composition for toner of the present invention is not particularly limited. For example, the crystalline polymer and the non-crystalline polyester are separately mixed at a temperature equal to or higher than the melting point of the crystalline polymer. Etc.
[0034]
The toner resin composition of the present invention preferably contains a crystal nucleating agent. By containing the crystal nucleating agent, crystallization of the crystalline polymer component can be promoted. Although it does not specifically limit as said crystal nucleating agent, For example, metal oxides, such as zinc oxide, magnesium oxide, silicon oxide, iron (III) oxide, and titanium oxide; Calcium carbonate, magnesium carbonate, calcium silicate, lead silicate, Inorganic salts such as magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate and potassium titanate; organic acid salts such as calcium oxalate and sodium oxalate; clays such as talc, kaolin, clay mica and wollastonite It is done. In addition, the shape of the crystal nucleating agent is not particularly limited, and may be amorphous, in addition to a plate shape and a spherical shape.
[0035]
The acid value of the resin composition for a toner of the present invention is not particularly limited, but when the acid value is less than 10, a toner having excellent charge stability can be obtained, and when the acid value is 10 to 30 The toner has improved wettability, and a toner having excellent fixability and storage stability can be obtained.
[0036]
By using the resin composition for toner of the present invention, it is possible to produce a toner that is excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance and that can perform good color development.
In the resin composition for toner of the present invention, it is considered that a crystalline component based on a crystalline polymer having a high melting point is uniformly finely dispersed in an amorphous polyester on the nano order. It is considered that the presence of a small amount of a crystal component uniformly finely dispersed causes little decrease in viscosity at high temperatures, and exhibits good offset resistance without deteriorating low-temperature fixability and storage stability.
In addition, in order to develop such a nano-order uniform fine dispersion structure, it is very important that the compatibility between the crystalline polymer and the amorphous polyester is high, and the crystalline polymer is crystallized. A high degree is also important.
[0037]
On the other hand, in conventional polyester-based toners, a polyfunctional monomer having three or more functional groups is usually copolymerized to form a chemically cross-linked structure in the polymer, thereby maintaining high temperature offset resistance. However, in such a method, since there are components that do not dissolve in the polymer, unevenness is generated on the print surface after fixing with the fixing roll, so that the gloss is inferior and the low-temperature fixability is limited.
In the resin composition for toner of the present invention, a crystalline polymer having a high melting point capable of forming a physically crosslinked structure, an amorphous polyester having a glass transition temperature of 50 to 80 ° C. without forming a physically crosslinked structure, and In addition to improving the high temperature offset resistance, the gloss and the low temperature fixability can be improved. That is, by containing a polymer component that can form a physical cross-linked structure and a polymer component that does not form a physical cross-linked structure and has a glass transition temperature of 50 to 80 ° C., the polymer viscosity is increased. On the other hand, the offset property can be improved. On the other hand, it is considered that the viscosity of the polymer is lowered when the pressure is applied by the fixing roll, so that the smoothness of the printing surface is increased, the gloss is improved and the low temperature fixing property is improved.
[0038]
Using the resin composition for toner of the present invention as a binder resin, if necessary, for a toner comprising a release agent, a colorant, a charge control agent, a magnetic material, a rubbery polymer, and a styrene-acrylate copolymer A toner can be produced by mixing with a resin, a carrier, a cleaning property improving agent and the like. Such a toner is also one aspect of the present invention.
The toner of the present invention does not need to contain a release agent because it is excellent in both low-temperature fixability and high-temperature offset resistance by using the resin composition for toner of the present invention. When the toner of the present invention does not contain a release agent, the toner has further improved transparency.
[0039]
The release agent is not particularly limited, and examples thereof include olefin waxes such as polypropylene wax, polyethylene wax, microcrystalline wax, and oxidized polyethylene wax, and paraffin waxes; fats such as carnauba wax, sazol wax, and montanic ester wax. Desaturated carnauba wax; Saturated aliphatic acid wax such as baltimic acid, stearic acid, and montanic acid; Unsaturated aliphatic acid wax such as pracidic acid, eleostearic acid, and valinalic acid; Stearyl alcohol; Saturated alcohols and aliphatic alcohols such as aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, and melyl alcohol; polyhydric alcohols such as sorbitol Saturated fatty acid amide waxes such as linoleic acid amide, oleic acid amide, lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide Wax; Unsaturated acid amide wax such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide; m-xylene bisstearin Aromatic bisamide waxes such as acid amides and N, N'-distearylisophthalic acid amides; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; vinyl monomers such as styrene and acrylic acid Graft-modified wax obtained by graft polymerization of mer to polyolefin; Partial ester wax obtained by reacting fatty acid such as behenic monoglyceride with polyhydric alcohol; Methyl ester wax having hydroxyl group obtained by hydrogenating vegetable oil; Examples thereof include ethylene-vinyl acetate copolymer waxes having a high component content; long-chain alkyl acrylate waxes such as saturated stearyl acrylate waxes such as acrylic acid; aromatic acrylate waxes such as benzyl acrylate waxes. Of these, long-chain alkyl acrylate waxes and aromatic acrylate waxes are preferred because they are highly compatible with the toner resin composition and provide a highly transparent toner. These release agents may be used alone or in combination of two or more, but it is particularly preferable to use in combination of two or more release agents having a melting point of 30 ° C. or more.
The size of the release agent in the toner is not particularly limited, but the major axis is preferably 2 μm or less.
[0040]
The colorant is not particularly limited. For example, carbon black such as furnace black, lamp black, thermal black, acetylene black, channel black, aniline black, phthalocyanine blue, quinoline yellow, lamp black, rhodamine-B, azo pigment Perylene pigment, perinone pigment, anthraquinone pigment, dioxazine pigment, isoindoline pigment, isoindolinone pigment, selenium pigment, indico pigment, quinophthalone, diketopyrrolopyrrole, quinacridone and the like.
The preferred lower limit of the blending amount of these colorants is usually 1 part by weight with respect to 100 parts by weight of the toner resin composition, and the preferred upper limit is 10 parts by weight.
[0041]
There are two types of charge control agents, positive charge and negative charge. Examples of the charge control agent for positive charge include nigrosine dyes, ammonium salts, pyridinium salts, and azines. Examples of the charge control agent for negative charge include chromium complexes and iron complexes. Among these, an acid-modified charge control agent is suitable, and when it is salicylic acid-modified, it crosslinks with the toner resin composition and develops rubber elasticity. Metal complexes of alkyl-substituted salicylic acid such as di-tert-butylsalicylic acid chromium complex and di-tert-butylsalicylic acid zinc complex are preferable because they are colorless or light-colored and do not affect the color tone of the toner. As the charge control agent, a charge control resin (CCR) can also be suitably used. Examples of the charge control resin include a styrene acrylic polymer obtained by copolymerization of a monomer containing a quaternary ammonium salt, an organic fluorine-based monomer, a sulfonic acid group-containing monomer, a phenylmaleimide monomer, and the like.
The preferred lower limit of the amount of these charge control agents is usually 0.1 parts by weight with respect to 100 parts by weight of the toner resin composition, and the preferred upper limit is 10 parts by weight.
[0042]
As said magnetic body, brand name "TAROX BL series" (made by Titanium Industry Co., Ltd.), brand name "EPT series", brand name "MAT series", brand name "MTS series" (all made by Toda Kogyo Co., Ltd.) , Product name "DCM series" (manufactured by Dowa Iron Powder Co., Ltd.), product name "KBC series", product name "KBI series", product name "KBF series", product name "KBP series" (all manufactured by Kanto Denka Kogyo Co., Ltd.) ), Trade name “Bayoide E series” (manufactured by Bayer AG), and the like.
[0043]
Examples of the rubbery polymer include natural rubber, polyisoprene rubber, polybutadiene rubber, nitrile rubber (acrylonitrile-butadiene copolymer), chloroprene rubber, butyl rubber, acrylic rubber, polyurethane elastomer, silicone rubber, and ethylene-propylene copolymer. , Ethylene-propylene-diene copolymer, chlorosulfinated polyethylene, ethylene vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, chlorinated polyethylene, epichlorohydrin rubber, nitrile isoprene Synthetic rubber such as rubber, elastomer such as polyester elastomer, urethane elastomer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, steel Down - ethylene butylene - styrene block copolymer, styrene - ethylene propylene - block copolymer of an aromatic hydrocarbon and a conjugated diene hydrocarbon such as styrene block copolymers. In addition, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, etc. may be mixed with the block copolymer, and these hydrogenated substances may be mixed.
Further, a rubbery polymer comprising a block copolymer of an aromatic hydrocarbon having a polar group such as a hydroxyl group, a carboxyl group, an aldehyde group, a sulfonyl group, a cyano group, a nitro group, or a halogen group and a conjugated diene is used as a toner. It is preferable because of its excellent affinity with. These block copolymers having polar groups at the ends can be obtained by living polymerization.
The rubbery polymer can improve the resin strength of the resin contained in the toner. Therefore, the toner containing the rubber-like polymer can prevent the filming phenomenon of the toner, and a toner suitable for the non-magnetic one-component toner requiring high resin strength can be obtained.
[0044]
Examples of the carrier include simple metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth, alloys, oxides, and ferrites. The surface of the carrier may be oxidized. Carrier surface is polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone polymer, polyester, di-tert-butylsalicylic acid metal complex, styrenic polymer, acrylic polymer, polyamide, polyvinyl butyral, nigrosine base May be coated with a functional dye, silica powder, alumina powder or the like. By coating the carrier, preferable triboelectric chargeability can be imparted to the carrier.
[0045]
The cleaning property improving agent is not particularly limited as long as the fluidity of the toner is improved by mixing with the toner particles. When the fluidity of the toner is improved, the toner is less likely to adhere to the cleaning blade. For example, fluorine polymer powder such as vinylidene fluoride polymer, acrylic polymer powder such as acrylic ester polymer, fatty acid metal salt powder such as zinc stearate, calcium stearate, lead stearate, zinc oxide powder, titanium oxide powder, etc. Examples thereof include metal oxide powder, fine powder silica powder, silica powder surface-treated with a silane coupling agent, titanium coupling agent, silicon oil, and the like, fumed silica, and the like. In addition, as the cleaning property improver, a sphere having a particle diameter of 0.05 to 0.5 μm made of an acrylic polymer, a styrene polymer, or the like can be suitably used.
[0046]
The toner of the present invention preferably has a peak at a position where the weight average molecular weight is 2000 or less when measured by gel permeation chromatography. This improves the fixability. The toner of the present invention preferably has a peak at a position where the weight average molecular weight is 10,000 or more when measured by gel permeation chromatography. Thereby, water resistance improves.
[0047]
The particle diameter of the toner of the present invention is not particularly limited, but particularly high image quality can be obtained when it is 5 μm or less.
The moisture content of the toner of the present invention is not particularly limited, but a preferred lower limit is 0.01% by weight and a preferred upper limit is 0.2% by weight. If it is less than 0.01% by weight, production becomes difficult due to problems in production, and if it exceeds 0.2% by weight, sufficient charging stability may not be obtained.
The repose angle of the toner of the present invention is not particularly limited, but the preferred lower limit of the repose angle at 23 ° C. and 60% humidity is 1 degree, and the preferred upper limit is 30 degrees. If it is less than 1 degree, handling of the toner may be difficult, and if it exceeds 30 degrees, the fluidity of the toner may be insufficient. The angle of repose of the toner can be measured by, for example, a powder tester (for example, PT-N type manufactured by Hosokawa Micron Corporation).
[0048]
The surface roughness of the toner of the present invention is not particularly limited, but a preferred lower limit is 0.01 μm and a preferred upper limit is 2 μm. If it is less than 0.01 μm, it may be difficult to perform printing, and if it exceeds 2 μm, the surface gloss of the resulting image may be insufficient. The surface roughness can be measured by a method defined in JIS B 0601 as a method for measuring the arithmetic average roughness (Ra) of a printed portion of an image printed using the toner of the present invention.
[0049]
When the toner of the present invention is used for an application that is particularly required to have excellent surface gloss, the viscosity of the toner of the present invention is preferably 100 mPa · s, and the preferred upper limit is 50,000. mPa · s. If it is less than 100 mPa · s, the storage stability may be inferior, and if it exceeds 50,000 mPa · s, sufficient surface gloss may not be obtained. A more preferable upper limit is 10,000 mPa · s.
[0050]
Since the resin for toner of the present invention can exhibit good fixability in a wide range from low temperature to high temperature, a toner excellent in both low temperature fixability, high temperature offset resistance and blocking resistance can be obtained. Since the time from when the switch is turned on until printing is possible can be shortened, it is economical, and furthermore, the clearness of the image can be maintained even when the temperature of the roller is lowered. The speed can be increased. Since the toner resin of the present invention is colorless and transparent, a desired color can be easily adjusted.
[0051]
In addition, the toner of the present invention may be fixed by a fixing roller to which a release oil is applied, but can exhibit good fixability even if the release oil is not applied to the fixing roller.
In addition, the crystalline polymer and non-crystalline polyester used in the toner resin composition of the present invention have good fixability in a wide range from low temperature to high temperature without being crosslinked or blended with a high molecular weight resin separately. And a toner excellent in both low-temperature fixability, high-temperature offset resistance, and blocking resistance can be obtained. A toner using such a resin composition for a non-crosslinked toner is more easily pulverized than a toner using a toner resin containing a high molecular weight resin, exhibits sharp melting characteristics, and provides a glossy fixed image. .
[0052]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[0053]
Example 1
<Production of polyamide (polyamide ester copolymer)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 95 moles of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 70 mol of neopentylene glycol as a divalent branched monomer component, 50 mol of ethylene glycol as other diol, 6-nylon (Toyobo Co., Ltd .: T-850) corresponds to 60% by weight of the resulting polyesteramide A theoretical amount was added, 0.05 mol of titanium tetrabutoxide (TBB) was charged as an esterification condensation catalyst, and an esterification reaction was carried out at 200 ° C. while distilling off generated water and methanol from a distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column. After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. Condensation reaction was performed and free diol generated by the condensation reaction was distilled out of the reaction system to obtain a polyamide ester copolymer.
[0054]
<Manufacture of non-crystalline polyester>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentylene glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst The esterification reaction was carried out at 200 ° C. while distilling the produced water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.
[0055]
<Production of Toner Resin Composition and Toner>
10 parts by weight of the obtained polyamide ester copolymer and 90 parts by weight of amorphous polyester were melt-kneaded to obtain a resin composition for toner.
Henschel mixer is sufficient to add 100 parts by weight of the obtained resin composition for toner, 1 part by weight of a charge control agent (TN-105: manufactured by Hodogaya Chemical Co., Ltd.), 5 parts by weight of magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax. And then kneaded at 130 ° C., cooled and coarsely pulverized. Thereafter, it was finely pulverized by a jet mill (Lab Jet: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a toner powder having an average particle size of about 8 to 12 μm. Further, this toner powder was classified by a classifier (MDS-2: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a fine toner powder having an average particle size of about 10 μm. Toner was manufactured by uniformly mixing (externally adding) 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) to 100 parts by weight of the toner fine powder.
[0056]
(Example 2)
<Production of crystalline polyester>
In a 60 L reaction vessel, a distillation tower, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were installed according to a conventional method. Under a nitrogen gas atmosphere, 100 moles of terephthalic acid as a dicarboxylic acid component, 1, 120 mol of 4-butanediol and 0.05 mol of titanium tetrabutoxide (TBB) were charged as an esterification condensation catalyst, and the esterification reaction was carried out at 220 ° C. while distilling water and methanol produced from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. The condensation reaction was performed and the free diol produced by the condensation reaction was distilled out of the reaction system to obtain a high melting crystalline polyester.
[0057]
<Production of non-crystalline polyester (A) (for blending)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentylene glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst The esterification reaction was carried out at 200 ° C. while distilling the produced water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester (A).
[0058]
<Production of amorphous polyester (B) (for blending)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 10 mol of acid, 60 mol of neopentylene glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst are produced at 200 ° C. The esterification reaction was carried out while distilling water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester (B).
[0059]
<Production of Toner Resin Composition and Toner>
10 parts by weight of the obtained high melting crystalline polyester, 80 parts by weight of the amorphous polyester (A) and 20 parts by weight of the amorphous polyester (B) were melt-kneaded to obtain a resin composition for toner.
Henschel mixer is sufficient to add 100 parts by weight of the obtained resin composition for toner, 1 part by weight of a charge control agent (TN-105: manufactured by Hodogaya Chemical Co., Ltd.), 5 parts by weight of magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax. And then kneaded at 130 ° C., cooled and coarsely pulverized. Thereafter, it was finely pulverized by a jet mill (Lab Jet: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a toner powder having an average particle size of about 8 to 12 μm. Further, this toner powder was classified by a classifier (MDS-2: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a fine toner powder having an average particle size of about 10 μm. Toner was manufactured by uniformly mixing (externally adding) 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) to 100 parts by weight of the toner fine powder.
[0060]
(Example 3)
A toner resin composition and a toner were obtained in the same manner as in Example 2 except that the amount of the crystalline polyester blended was 30 parts by weight in the production of the toner resin composition.
[0061]
Example 4
<Production of crystalline polyester>
In a 60 L reaction vessel, a distillation tower, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were installed according to a conventional method. Under a nitrogen gas atmosphere, 100 moles of terephthalic acid as a dicarboxylic acid component, 1, 120 mol of 4-butanediol and 0.05 mol of titanium tetrabutoxide (TBB) were charged as an esterification condensation catalyst, and the esterification reaction was carried out at 220 ° C. while distilling water and methanol produced from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. The condensation reaction was performed and the free diol produced by the condensation reaction was distilled out of the reaction system to obtain a high melting crystalline polyester.
[0062]
<Production of non-crystalline polyester (A) (for blending)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentyl glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, 1 mol of pentaerythritol as a polyfunctional monomer, titanium tetrabutoxide (as an esterification condensation catalyst) TBB) 0.05 mol was charged, and the esterification reaction was carried out at 200 ° C. while distilling water and methanol produced from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester (A).
[0063]
<Production of amorphous polyester (B) (for blending)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 10 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentyl glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst The esterification reaction was carried out at 200 ° C. while distilling the produced water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester (B).
[0064]
<Production of Toner Resin Composition and Toner>
30 parts by weight of the obtained crystalline polyester, 70 parts by weight of the amorphous polyester (A) and 30 parts by weight of the amorphous polyester (B) were melt-kneaded to obtain a resin composition for toner.
Henschel mixer is sufficient to add 100 parts by weight of the obtained resin composition for toner, 1 part by weight of a charge control agent (TN-105: manufactured by Hodogaya Chemical Co., Ltd.), 5 parts by weight of magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax. And then kneaded at 130 ° C., cooled and coarsely pulverized. Thereafter, it was finely pulverized by a jet mill (Lab Jet: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a toner powder having an average particle size of about 8 to 12 μm. Further, this toner powder was classified by a classifier (MDS-2: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a fine toner powder having an average particle size of about 10 μm. Toner was manufactured by uniformly mixing (externally adding) 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) to 100 parts by weight of the toner fine powder.
[0065]
(Example 5)
In the production of the amorphous polyester (A), a resin composition for toner is obtained in the same manner as in Example 4, except that 2.5 mol of trimellitic anhydride is used as the polyfunctional monomer instead of 1 mol of pentaerythritol. And a toner was produced.
[0066]
(Example 6)
<Production of polyamide (polyamide ester copolymer)>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 95 moles of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 70 mol of neopentylene glycol as the divalent branched monomer component, 50 mol of ethylene glycol as the other diol, and 6-nylon (T-850: manufactured by Toyobo Co., Ltd.) correspond to 15% by weight of the produced polyesteramide. The theoretical amount, 0.05 mol of titanium tetrabutoxide (TBB) was charged as an esterification condensation catalyst, and the esterification reaction was carried out at 200 ° C. while distilling off the generated water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. Condensation reaction was performed and free diol generated by the condensation reaction was distilled out of the reaction system to obtain a polyamide ester copolymer.
[0067]
<Manufacture of polybutylene terephthalate (PBT)>
In a 60 L reaction vessel, a distillation tower, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were installed according to a conventional method. Under a nitrogen gas atmosphere, 100 moles of terephthalic acid as a dicarboxylic acid component, 1, 120 mol of 4-butanediol and 0.05 mol of titanium tetrabutoxide (TBB) were charged as an esterification condensation catalyst, and an esterification reaction was performed at 200 ° C. while distilling water and methanol produced from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A polybutylene terephthalate was obtained by performing a condensation reaction and distilling the free diol generated by the condensation reaction out of the reaction system.
[0068]
<Manufacture of non-crystalline polyester>
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid as a dicarboxylic acid component and isophthalic acid as a bending monomer component 5 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentylene glycol as a divalent branched monomer component, 60 mol of ethylene glycol as another diol, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst The esterification reaction was carried out at 200 ° C. while distilling the produced water and methanol from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.
[0069]
<Production of Toner Resin Composition and Toner>
15 parts by weight of the obtained polyamide ester copolymer, 3 parts by weight of polybutylene terephthalate, and 85 parts by weight of amorphous polyester were melt-kneaded to obtain a resin composition for toner.
Henschel mixer is sufficient to add 100 parts by weight of the obtained resin composition for toner, 1 part by weight of a charge control agent (TN-105: manufactured by Hodogaya Chemical Co., Ltd.), 5 parts by weight of magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax. And then kneaded at 130 ° C., cooled and coarsely pulverized. Thereafter, it was finely pulverized by a jet mill (Lab Jet: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a toner powder having an average particle size of about 8 to 12 μm. Further, this toner powder was classified by a classifier (MDS-2: manufactured by Nippon Pneumatic Co., Ltd.) to obtain a fine toner powder having an average particle size of about 10 μm. Toner was manufactured by uniformly mixing (externally adding) 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) to 100 parts by weight of the toner fine powder.
[0070]
(Examples 7 and 8)
A toner resin composition and a toner were produced in the same manner as in Example 6 except that the toner resin composition was changed to the composition shown in Table 2.
[0071]
(Comparative Example 1)
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 99 mol of terephthalic acid and 1 mol of trimellitic acid are used as dicarboxylic acid components. , 105 mol of bisphenol A propylene oxide adduct as the diol component, 0.05 mol of dibutyltin oxide as the esterification condensation catalyst were charged, and the esterification reaction was carried out at 200 ° C. while distilling water and methanol produced from the distillation column. It was. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.
A toner was produced in the same manner as in Example 1 except that only the obtained non-crystalline polyester was used as a toner resin.
[0072]
(Comparative Example 2)
In the production of the amorphous polyester (A), the resin composition for toner and the toner were prepared in the same manner as in Example 4 except that the blending amount of ethylene glycol was 30 mol and the blending amount of pentaerythritol was 30 mol. Manufactured.
[0073]
(Comparative Example 3)
A distillation column, water separator, nitrogen gas inlet tube, thermometer and stirrer are installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 99 mol of terephthalic acid and 1 mol of trimellitic acid are used as dicarboxylic acid components. , 105 mol of bisphenol A propylene oxide adduct as the diol component, 0.05 mol of dibutyltin oxide as the esterification condensation catalyst were charged, and the esterification reaction was carried out at 200 ° C. while distilling water and methanol produced from the distillation column. It was. The esterification reaction was completed when water and methanol no longer distilled from the distillation column.
After completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation tower is closed, the line from the vacuum pump is opened, the inside of the reaction system is reduced to 0.7 kPa or less, 240 ° C., and the stirring rotation speed is 60 rpm. A condensation reaction was performed and the free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.
A toner was produced in the same manner as in Example 6 except that the obtained amorphous polyester was used as a resin composition for toner.
[0074]
(Evaluation)
The toner produced in each example and comparative example was evaluated by the following method. The results are shown in Tables 1-3.
[0075]
[Molecular weight and molecular weight distribution]
(1) Crystalline polyester
As a GPC measuring apparatus, HTR-C manufactured by Nihon Millipore Limited was used, and HFIP-806M (2 pieces) manufactured by Showa Denko Co., Ltd. were connected in series to the column, and the weight average molecular weight was measured. The measurement conditions were a temperature of 40 ° C., a sample having a 0.1 wt% hydroxyfluoroisopropanol (HFIP) solution (passed through a 0.45 μm filter), an injection volume of 100 μL, and a carrier solvent having a TFA of 0.1 per liter. HFIP containing 68 g was used. Standard polystyrene was used as a calibration sample.
(2) Amorphous polyester and polyester block copolymer
As a GPC measuring device, HTR-C manufactured by Nihon Millipore Limited is used, and KF-800P (1), KF-806M (2), KF-802.5 (1) manufactured by Showa Denko K.K. Were connected in series and the weight average molecular weight was measured. The measurement conditions were as follows: the temperature was 40 ° C., the sample was a 0.2 wt% THF solution (passed through a 0.45 μm filter), the injection amount was 100 μL, the carrier solvent was THF, and standard polystyrene was used as the calibration sample.
(3) Resin composition for toner and toner
As a GPC measuring device, HTR-C manufactured by Nihon Millipore Limited is used, and KF-800P (1), KF-806M (2), KF-802.5 (1) manufactured by Showa Denko K.K. Were used in series to measure molecular weight and molecular weight distribution. The measurement conditions were as follows: the temperature was 40 ° C., the sample was a 0.2 wt% THF solution (passed through a 0.45 μm filter), the injection amount was 100 μL, the carrier solvent was THF, and standard polystyrene was used as the calibration sample.
[0076]
[Glass transition temperature (Tg)]
Using a DSC-6200R manufactured by Seiko Denshi Kogyo Co., Ltd. as a differential scanning calorimeter, it was measured according to JIS K 7121 at a heating rate of 10 ° C./min. The intermediate glass transition temperature described in “)” was determined.
[0077]
[Crystal melting point (Tm)]
Using a DSC-6200R manufactured by Seiko Denshi Kogyo Co., Ltd. as a differential scanning calorimeter, 10 mg of the sample was heated at a heating rate of 10 ° C./min, measured in accordance with JIS K 7121, and the standard (9.1 “ The melting peak value described in “How to Obtain Melting Temperature”) was determined, and this was used as the crystalline melting point Tm.
[0078]
[Color tone]
The color of the resin for toner obtained in each example and comparative example was visually observed.
[0079]
[blocking]
Take 10 g of the obtained toner in a 100 mL sample bottle and leave it in a thermostatic bath at 50 ° C. for 8 hours. When there was an aggregate, the weight (% by weight) of the aggregate with respect to the toner weight was determined.
[0080]
[Filming evaluation]
After 10,000 sheets were printed, whether the toner adhered to the fixing roller was visually observed. If no toner adhered, the film was evaluated as having no filming.
[0081]
[Gross evaluation]
Using a gloss meter (gloss meter, UGV-50, manufactured by Suga Test Instruments Co., Ltd.), a test paper painted black with black toner prepared using the toner resin of the present invention is attached to a gloss meter, and the reflection angle is 75 degrees. The optical path was set so that
[0082]
[High temperature offset temperature and low temperature offset temperature]
A developer was prepared by mixing 6.5 parts by weight of the toner obtained in each Example and Comparative Example with 93.5 parts by weight of an iron powder carrier having an average particle diameter of 50 to 80 μm. As an electrophotographic copying machine, a UBIX4160AF manufactured by Konica was used so that the set temperature of the heat fixing roller could be changed up to 250 ° C.
The set temperature of the heat fixing roller was changed stepwise to obtain a copy in which the unfixed toner image was fixed on the transfer paper by the heat fixing roller at each set temperature.
It was observed whether the blank portion of the obtained copy and the fixed image were stained with toner, and a temperature region where no contamination occurred was defined as a non-offset temperature region. Further, the maximum value in the non-offset temperature region was set as the high temperature offset temperature, and the minimum value was set as the low temperature offset temperature.
[0083]
[Minimum fixing temperature of toner]
Copying was carried out by changing the set temperature of the heat fixing roller of the electrophotographic copying machine step by step, and the blank portion and the fixed image were not stained with toner without causing the fog on the blank portion and the fixed image. When the fixed image of the copy was rubbed with a sand eraser for typewriter, the case where the decrease in the density of the fixed image was less than 10% was judged as good fixing, and the minimum temperature at that time was determined.
The image density was measured using a Macbeth photometer.
[0084]
[Table 1]

[0085]
[Table 2]

[0086]
[Table 3]

[0087]
【The invention's effect】
According to the present invention, it is possible to provide a toner resin composition and a toner that are excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance, and that can perform good color development.

Claims (7)

A resin composition for a toner comprising a crystalline polymer having a melting point of 180 to 280 ° C. and an amorphous polyester having a glass transition temperature of 50 to 80 ° C. , wherein the crystalline polymer contains a crystalline polyamide. object. The toner resin composition according to claim 1, wherein the crystalline polymer further comprises a crystalline polyester.   3. The resin composition for toner according to claim 2, wherein the crystalline polyester is obtained by polymerizing a monomer mixture mainly composed of terephthalic acid and 1,4-butanediol. The amorphous polyester is obtained by polymerizing a monomer mixture containing terephthalic acid, neopentyl glycol, and ethylene glycol and / or 1,4-butanediol as main components. 2 or 3 Symbol mounting resin composition for toners. The non-crystalline polyester has a radial structure and / or a comb structure, and has an amorphous polyester having three or more ends, or a radial structure and / or a comb structure, and has three or more ends. non-crystalline polyester, mixture according to claim 1, 2, 3 or 4 SL placing toner resin composition characterized in that it is a a polyester of a linear structure having. Claim 1, 2, 3, 4 or 5 Symbol mounting resin composition for toners, wherein the crystalline polymer and the non-crystalline polyester are those compatible. Toner characterized by using the claims 2, 3, 4, 5 or 6 Symbol mounting resin composition for toners.