JP2005025144A - Resin composition for toner, and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for toner and toner having excellent low temperature fixing property, high temperature offset resistance and blocking resistance and capable of preferably developing a color. <P>SOLUTION: The resin composition for toner contains a crystalline polymer having 180 to 280°C melting point and 25 to 150 mJ/mg endothermic heat value at the melting point measured by a differential scanning calorimeter, and noncrystalline polyester having 30 to 80°C glass transition temperature. The average particle size of the crystal grains observed by a polarization microscope is ≤5 μm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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.

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.

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.

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 easily occurs due to heat.

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 to maintain high temperature offset resistance. However, in such a method, since there is a component that does not dissolve in the polymer, unevenness is generated on the print surface after fixing with the fixing roll, so that the gloss is inferior or the low-temperature fixability is limited.

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.

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.

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.

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.

Further, since the blocking phenomenon is likely to occur when the toner is exposed to the glass transition temperature of the toner resin or higher, the polyester resin for the toner that does not easily cause the blocking phenomenon has been studied. 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.

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 will still occur. There was a problem that.

Japanese Patent No. 2988703 Japanese Patent No. 2704282 Japanese Patent Laid-Open No. 4-97366 JP-A-4-313760 Japanese Patent Publication No. 5-44032 JP-A-4-337774 Japanese Patent Laid-Open No. 10-36490

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.

In the present invention, a crystalline polymer having a melting point of 180 to 280 ° C. and an endotherm at a melting point of 25 to 150 mJ / mg measured using a differential scanning calorimeter (DSC), and a glass transition temperature of 30 to A toner resin composition containing an amorphous polyester at 80 ° C., wherein the average particle diameter of crystal particles observed with a polarizing microscope is 5 μm or less.

In the present invention, a crystalline polymer having a melting point of 180 to 280 ° C. and an endotherm at a melting point of 25 to 150 mJ / mg measured using a differential scanning calorimeter (DSC), and a glass transition temperature of 30 to A toner resin composition containing amorphous polyester at 80 ° C. and having a haze value of 60% or more measured by a method in accordance with JIS K 7105.
The present invention is described in detail below.

The resin composition for toner of the present invention contains a crystalline polymer and an amorphous polyester.
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.

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. This is because, in the resin composition for toner of the present invention, the crystalline components in the crystalline polymer having a high melting point form a physically crosslinked structure in the amorphous polyester, while the crystalline component in the crystalline polymer having a high melting point is used. A non-crystalline component and non-crystalline polyester are intertwined to form a kind of network structure. By forming such a network structure, there is little decrease in viscosity at high temperatures, and low temperature fixability and storage stability. This is considered to be because good offset resistance can be exhibited without lowering.

That is, in the resin composition for a toner of the present invention, a crystalline polymer having a high melting point capable of forming a physical cross-linked structure, and an amorphous polyester having a glass transition temperature of 30 to 80 ° C. without forming a physical cross-linked structure. In addition to improving the high temperature offset resistance, it is possible to improve the gloss and the low temperature fixability. By containing a crystalline polymer capable of forming a physical cross-linked structure and an amorphous polyester that does not form a physical cross-linked structure and has a glass transition temperature of 30 to 80 ° C., the polymer viscosity is increased. 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.

The toner using the resin composition for toner of the present invention has excellent image reproducibility.
This is because the above-described network structure is formed in the entire resin composition for toner of the present invention.
It is considered that the toner obtained in the pulverization process has stable chargeability, no fog, and excellent image reproducibility.

As a result of intensive studies, the present inventors have found that the above-mentioned network structure is formed in the resin composition for toner of the present invention by confirming the size of the crystals forming the above-mentioned physical cross-linked structure. . That is, when the crystals forming the above-mentioned physical cross-linked structure have a size of 5 μm or less, preferably 1 μm or less, and are uniformly finely dispersed in the toner resin composition, The above-described network structure is formed. As described above, the crystals having a physically crosslinked structure are uniformly finely dispersed in the resin composition for toner with a certain size or less, thereby making the network structure extremely stable and exhibiting excellent effects. It is considered a thing. Specifically, the average particle diameter of the crystal particles observed when the resin fine particles for toner of the present invention are observed with a polarizing microscope is 5 μm or less.

It does not specifically limit as a method to measure the average particle diameter of the said crystal particle, For example, it can obtain | require by the following method. That is, the resin composition for toner of the present invention is placed on a slide, heated to about 100 ° C. using a hot plate or the like, softened, and then lightly pressed with a cover glass. Thereafter, the resin is heated to 150 ° C. to recrystallize the amorphous resin, and then returned to room temperature. This is observed using a polarizing microscope having a magnification of 200 times, and the particle diameter of the distinguishable crystal particles is measured, and the average is obtained.
In order to express such a nano-order uniform fine dispersion structure and form the above-mentioned network structure, it is very important that the compatibility between the crystalline polymer and the amorphous polyester is high, It is important that the crystallinity of the crystalline polymer is high.

As a result of further intensive studies, the present inventors have found that the size and dispersion state of the crystals forming the physical cross-linked structure in the resin composition for toner of the present invention are correlated with the haze value of the resin composition. I found out. That is, when the haze value is 60% or more, the crystals forming the physical cross-linked structure are uniformly finely dispersed with a size of 5 μm or less, and such a resin composition for toner of the present invention is In addition, it is excellent in low-temperature fixability, high-temperature offset resistance and blocking resistance, and good color development can be performed. If the haze value is less than 60%, the crystals are aggregated and not uniformly dispersed, and the above-described network structure cannot be formed.
Note that the haze value is calculated by a method based on JIS K 7105.
(%) And diffuse transmittance Td (%) can be measured and calculated by the following equation (2).

The crystalline polymer has a lower endotherm of 25 mJ / mg and an upper limit of 150 mJ / mg at the melting point measured using a differential scanning calorimeter (DSC). If it is less than 25 mJ / mg, it is difficult to form the above-mentioned network structure, so the desired effect such as high-temperature offset resistance cannot be obtained. If it exceeds 150 mJ / mg, the viscosity of the polymer is sufficient when pressed by a fixing roll. However, the printed surface after fixing is uneven, resulting in poor gloss and low-temperature fixability. A preferred lower limit is 40 mJ / mg and a preferred upper limit is 100 mJ / mg.
In addition, although it does not specifically limit about the measurement conditions of a differential scanning calorimeter (DSC), For example, J
In accordance with IS K 7121, it can be measured by a method of heating 10 mg of a sample at a heating rate of 10 ° C./min.

In the toner resin composition of the present invention, the preferable lower limit of the endothermic amount at the melting point measured using a differential scanning calorimeter (DSC) is 1 mJ / mg, and the preferable upper limit is 20 mJ / mg.
If it is less than 1 mJ / mg, the above-mentioned network structure may not be formed and the desired effect such as high-temperature offset resistance may not be obtained. If it exceeds 20 mJ / mg, the viscosity of the polymer during pressurization with a fixing roll may be reduced. In some cases, the surface of the print after fixing may not be sufficiently lowered, resulting in unevenness on the printed surface, resulting in poor gloss or low temperature fixability. A more preferred lower limit is 2 mJ / mg, and a more preferred upper limit is 15 mJ / mg.

The lower limit of the melting point of the crystalline polymer is 180 ° C., and the upper limit is 280 ° C. If it is lower than 180 ° C., the high temperature hot offset resistance becomes insufficient, or filming is likely to occur, resulting in insufficient durability. When it exceeds 280 ° C., it is necessary to melt at a high temperature exceeding 280 ° C. at the time of mixing with the amorphous polyester, so that the productivity is remarkably deteriorated. The preferred lower limit is 200 ° C., the preferred upper limit is 240 ° C., and the more preferred lower limit is 22 ° C.
0 ° C.
In order to shorten the rise time (warm-up time) after switching on in a copying machine or printer, it is necessary to quickly raise the fixing roller to a predetermined fixing temperature. Initially, it is hotter than a predetermined fixing temperature. Therefore, in order to perform good printing even in this state, the toner must have good hot offset resistance at high temperatures. The lower the fixing temperature and the higher the hot offset temperature, the shorter the warm-up time. Usually, in order to sufficiently increase the hardware design width, the hot offset resistance temperature is required to be 180 ° C. or higher. When the crystalline polymer has a melting point of 180 ° C. or higher, the crystal part of the crystalline polymer is not melted even at a high temperature, and the above-described network structure is maintained, so that the high temperature hot offset resistance is considered to be improved. In addition, as the speed of copying machines and printers increases, there is a demand for a toner that does not generate fine powder and does not cause filming even under high speed operation. In particular, non-magnetic one-component toner that is charged by mechanical contact with the blade has a higher demand for durability. When the melting point of the crystalline polymer is 180 ° C., the cohesive force of the crystalline part of the crystalline polymer is increased, and the above-described network structure is strengthened, so that the durability is considered to be improved.

The crystalline polymer has a preferable lower limit of the weight average molecular weight of 30,000 and a preferable upper limit of 300,000. If it is less than 30,000, the offset resistance and durability of the resulting toner may be insufficient, and if it exceeds 300,000, the low-temperature fixability and gloss may be inferior. This is considered to be because the above-described network structure cannot be sufficiently formed if it is out of this range. A more preferred lower limit is 50,000, a more preferred upper limit is 200,000, a still more preferred lower limit is 80,000, and a still more preferred upper limit is 150,000.

Although it does not specifically limit as said crystalline polymer, Crystalline polyester or crystalline polyamide is suitable.
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.

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, tetraethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,3 -Butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-
Aliphatic diols such as hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 2 , 2-bis (4-hydroxycyclohexyl) propane, 2,2-
Alkylene oxide adduct of bis (4-hydroxycyclohexyl) propane, 1,4
-Alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol.

Among the crystalline polyesters, polybutylene terephthalate (PBT),
Polyethylene terephthalate (PET) is preferred.
Since polybutylene terephthalate (PBT) has a high crystallization rate and a high degree of crystallization, a toner obtained using this has excellent offset resistance. Further, since the compatibility with the amorphous polyester is excellent, the toner obtained using the polyester has excellent low-temperature fixability and gloss.
Since polyethylene terephthalate (PET) has a high crystalline melting point, the toner obtained using this has excellent offset resistance at high temperatures. Polyethylene terephthalate (PET) is inferior to polybutylene terephthalate (PBT) in terms of crystallization speed and crystallinity, but these points can be improved by adding a crystal nucleating agent.
These crystalline polyesters may be used alone or in combination of two or more.

Examples of the crystalline polyamide include 6-nylon, 6,6-nylon, 4,6-nylon,
11-nylon, 12 nylon, etc. are mentioned. 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. A polyamide-polyester copolymer obtained by copolymerizing polyester with these crystalline polyamides is also preferable because of excellent compatibility with the amorphous polyester. These crystalline polyamides may be used alone or in combination of two or more.
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.

The lower limit of the glass transition temperature of the non-crystalline polyester is 30 ° C., and the upper limit is 80 ° C. 30
If it is less than 0 ° C., high-temperature offset resistance and blocking resistance cannot be sufficiently obtained, and if it exceeds 80 ° C., low-temperature fixability is inferior. A preferred lower limit is 50 ° C and a preferred upper limit is 65 ° C.

The non-crystalline polyester can be obtained by polycondensing a dicarboxylic acid and a diol.
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 lower the glass transition temperature. Since it has a function, the target glass transition temperature can be achieved by appropriately combining these dicarboxylic acids. However, even if an objective 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 comprises a polyvalent carboxylic acid and a polyhydric alcohol containing at least either a divalent bending monomer capable of introducing a bent molecular structure into the molecular chain or a divalent monomer having a branched chain. It is preferable to polymerize the monomer mixture containing.
A polymer obtained by polymerizing a monomer mixture containing these divalent bending monomers and divalent monomers having a branched chain can easily achieve both a desired glass transition temperature and a low softening temperature, and can be crystallized. It can be effectively suppressed.

As the divalent bending monomer, an aromatic dicarboxylic acid in which the ortho position or the meta position is substituted with a carboxyl group, an aromatic diol in which the ortho position or the meta position is substituted with a hydroxyl group,
Polycarboxylic aromatic dicarboxylic acids having a carboxyl group at an asymmetric position, polycyclic aromatic diols having a hydroxyl group at an asymmetric position, and other monomers that can introduce a molecular structure bent into the molecular chain of the polymer are limited to dicarboxylic acids and diols. For example, it may be an anhydride or lower ester of a dicarboxylic acid, a monohydroxymonocarboxylic acid, etc., for example, phthalic anhydride, o-phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,7 Dicarboxylic acids such as naphthalenedicarboxylic acid and anhydrides and lower esters thereof; monohydroxymonocarboxylic acids such as salicylic acid and 3-hydroxy-2-naphthalenecarboxylic acid; catechol,
Examples include diols such as 1,4-cyclohexanedimethanol.

A divalent monomer having a branched chain effectively suppresses crystallization of the polymer due to steric hindrance of the branched chain. Examples of the monomer having a branched chain that can effectively suppress crystallization include an aliphatic diol having a branched alkyl chain and an alicyclic diol having a branched alkyl chain. The alicyclic diol is preferably an alicyclic diol in which a plurality of alicyclic diols are linked by a branched alkylene chain.
The divalent monomer having a branched chain is not particularly limited. 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
Aliphatic diols such as 1,3-propanediol and 2,4-diethyl-1,5-pentanediol; 2,2-bis (4-hydroxycyclohexyl) propane and 2,2-bis (4-hydroxycyclohexyl) propane And alicyclic diols such as alkylene oxide adducts.
Among them, terephthalic acid, neopentyl glycol, ethylene glycol and / or
Alternatively, an amorphous polyester obtained by polymerizing a monomer mixture containing 1,4-butanediol as a main component is preferable because it is excellent in low-temperature fixability and transparency.

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. .

Thus, in order for the crystalline polymer and the non-crystalline polyester to be compatible, the glass transition temperature of the crystalline polymer is A (° C.), and the glass transition temperature of the non-crystalline polyester is B (° C.). The glass transition temperature C (° C.) of the resin composition for toner of the present invention preferably satisfies the following formula (1).

In formula (1), s represents the weight fraction of the crystalline polymer in the toner resin composition, and t represents the weight fraction of the amorphous polymer in the toner resin composition.
When the glass transition temperature of the resin composition for toner of the present invention satisfies the above formula (1), the crystalline polymer and the amorphous polyester are very well compatible.

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 may be polybutylene terephthalate (PBT) or polyethylene terephthalate (PE
T) and the non-crystalline polyester is obtained by polymerizing a monomer mixture containing terephthalic acid, neopentyl glycol, and ethylene glycol and / or 1,4-butanediol as a main component. Is well compatible.

As the content of the crystalline polymer and the non-crystalline polyester in the toner resin composition of the present invention, the preferred lower limit of the crystalline polymer content is 2% by weight, and the preferred upper limit is 30% by weight, A preferable lower limit of the content of the amorphous polyester is 98% by weight.
The preferred upper limit is 70% by weight.
When the content of the crystalline polymer is less than 2% 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 3% by weight, a more preferred upper limit is 20% by weight, a still more preferred lower limit is 5% by weight, and a still more preferred upper limit is 15% by weight.

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 high molecular weight non-crystalline polyester is not particularly limited, for example, isophthalic acid,
Examples thereof include polyethylene terephthalate composed of terephthalic acid and ethylene glycol, polyethylene terephthalate composed of 1,4-cyclohexanedimethanol, ethylene glycol and terephthalic acid.
The blending amount of the high molecular weight amorphous polyester is not particularly limited, but the preferable lower limit is 2% by weight and the preferable upper limit is 30% by weight with respect to the entire resin composition for toner. 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.

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.

When the resin composition for toner of the present invention gives a shear strain of 5% under the condition of 190 ° C.,
It is preferable that the rate of change D of the relaxation elastic modulus represented by the following formula (3) is 15 to 90.

It can be said that the rate of change D of the relaxation elastic modulus has the property that the elastic behavior of the substance is closer to 0, and the closer to 0, the closer to rubber elasticity. The change rate D of the relaxation elastic modulus is 15 to 90, because the network structure is formed in the resin composition for toner of the present invention, and the crystal having a uniformly dispersed physical cross-linked structure is the center. It is considered that the rubber-like property is expressed by the structure in which the amorphous component and the amorphous polyester in the crystalline polymer having a high melting point are entangled. When the change rate D of the relaxation elastic modulus is less than 15, the viscosity of the toner is not sufficiently reduced when pressed by a fixing roll, unevenness is generated on the printed surface after fixing, the gloss is inferior, and the low-temperature fixing property is inferior. . If it exceeds 90, it is difficult to form the above-described network structure, so that a sufficient high temperature offset resistance improving effect cannot be obtained.

The toner resin composition of the present invention gives a shear strain represented by the following formula (4) when a shear strain of 450% is applied under the condition of 190 ° C. It is preferable that the gradient K of the relaxation elastic modulus curve after 2 seconds is −27 or more.

In the formula, G (0.02) represents a relaxation elastic modulus 0.02 seconds after applying a shear strain, and G (0
. 1) represents the relaxation elastic modulus 0.1 seconds after applying a shear strain.

The gradient K of the relaxation elastic modulus curve represents the elastic behavior of the substance, and the closer to 0, the closer to rubber elasticity. The slope K of the relaxation elastic modulus curve is −27 or more because the above-mentioned network structure is formed in the toner resin composition of the present invention, and the crystal having the uniformly crosslinked physical crosslinked structure formed therein. It is considered that the rubber-like property is expressed by the structure in which the amorphous component in the crystalline polymer having a high melting point is entangled with the amorphous polyester. Therefore, the resin composition for a toner of the present invention having a slope K of the relaxation elastic modulus curve of −27 or more is excellent in low-temperature fixability, high-temperature offset resistance and blocking resistance, and gives a toner that produces good color development. Can do. When the slope K of the relaxation elastic modulus curve is less than −27, it is considered that the above-described network structure is not sufficiently formed, and the desired effect may not be obtained.
The relaxation elastic modulus is, for example, a test sample obtained by melting the resin for toner of the present invention and then molding it into a disk shape of a predetermined size, and a relaxation elastic modulus measuring device (for example, RMS manufactured by Rheometrics). -800 etc.).

Although it does not specifically limit as an acid value of the resin composition for toners of this invention, It is preferable that it is 1-30. Such an acid value is attributed to an acidic functional group at the end of the main chain of the crystalline polymer or the non-crystalline polyester, specifically, for example, a carboxyl group. When the acid value is in this range, the toner obtained is excellent in low-temperature fixability, and the affinity with paper is also improved.
The toner resin composition of the present invention contains only a polymer having a molecular weight of about several hundred thousand, unlike the conventional cross-linked toner resin composition containing a high molecular weight polymer of 1 million level. These functional groups are distributed relatively uniformly, and a further low-temperature fixability can be obtained.

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.

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.

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.

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, etc. Is mentioned.
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.

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. As the charge control resin, for example,
Examples thereof 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.

As said magnetic body, brand name "TAROX BL series" (made by a titanium industry company), for example
, Product name "EPT series", product name "MAT series", product name "MTS series" (
All are manufactured by Toda Kogyo Co., Ltd.), trade name “DCM Series” (manufactured by Dowa Iron Powder Co., Ltd.), trade name “KBC”
Series ”, product name“ KBI series ”, product name“ KBF series ”, product name“ KBP series ”(all manufactured by Kanto Denka Kogyo Co., Ltd.), product name“ Bayoxide E series ”(B
ayer AG).

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. The block copolymer contains styrene
A butadiene block copolymer, a styrene-isoprene block copolymer, or the like may be mixed, or these hydrogenated products 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.

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, metal complex of di-tert-butylsalicylic acid, styrene 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.

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.

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.

The particle size of the toner of the present invention is not particularly limited, but particularly high image quality can be obtained when it is 10 μm or less. More preferably, it is 5 μm or less.
The moisture content of the toner of the present invention is not particularly limited, but the preferred lower limit is 0.01% by weight.
The 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).

The surface roughness of the toner of the present invention is not particularly limited, but the preferred lower limit is 0.01 μm,
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. In addition, the surface roughness indicates the printing portion of an image printed using the toner of the present invention according to JIS B 060.
1 can be measured by a method defined as a method for measuring the arithmetic average roughness (Ra).

When the toner of the present invention is used for an application that is particularly required to have excellent surface gloss, the preferred lower limit of the melt viscosity at 150 ° C. is 100 mPa ·
s, and a preferable 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.

The toner of the present invention can express good fixability in a wide range from low temperature to high temperature, and is excellent in both low temperature fixability, high temperature offset resistance and blocking resistance. It is economical because the time until it becomes possible can be shortened, and furthermore, the sharpness of the image can be maintained even when the temperature of the roller is lowered, so that the printing speed can be increased. . Since the toner of the present invention is colorless and transparent, a desired color can be easily adjusted. The toner of the present invention is excellent in image reproducibility.

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. .

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.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
(1) Production of crystalline polyester A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer and a stirring measure are installed in a 60 L reaction vessel according to a conventional method, and terephthalic acid is used as a dicarboxylic acid component in a nitrogen gas atmosphere. 100 moles,
120 mol of 1,4-butanediol as the diol component and 0.05 mol of titanium tetrabutoxide (TBB) as the esterification condensation catalyst were charged, and the esterification reaction was carried out at 220 ° C. while distilling the produced water from the distillation column. It was. The esterification reaction was completed when water 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 pressure in the reaction system is reduced to 5 mmHg or less, 240 ° C., stirring speed 6
A condensation reaction was carried out at 0 rpm and the free diol produced by the condensation reaction was distilled out of the reaction system to obtain a high melting crystalline polyester.

(2) Production of non-crystalline polyester A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer are installed in a conventional manner in a 60 L reaction vessel, and terephthalate is used as a dicarboxylic acid component in a nitrogen gas atmosphere. 90 mol of acid, 5 mol of isophthalic acid as a bending monomer component, 5 mol of phthalic anhydride, 60 mol of neopentyl glycol as a branched monomer component, 60 mol of ethylene glycol as another diol,
As an esterification condensation catalyst, 0.05 mol of titanium tetrabutoxide (TBB) was charged and 2
The esterification reaction was carried out at 00 ° C. while distilling the produced water from the distillation column. The esterification reaction was completed when water 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 pressure in the reaction system is reduced to 5 mmHg or less, 240 ° C., stirring speed 6
A condensation reaction was performed at 0 rpm, and free diol generated by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.

(3) Production of Toner Resin Composition and Toner 10 parts by weight of crystalline polyester and 90 parts by weight of non-crystalline polyester L / D =
A toner resin composition was obtained by melt-kneading at a barrel temperature of 240 ° C. using a 37-screw extruder.
A Henschel mixer is sufficient to add 100 parts by weight of the obtained resin composition for toner with 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 toner fine powder having an average particle diameter 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.

(Comparative Example 1)
(1) Production of non-crystalline polyester A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer are installed in a conventional manner in a 60 L reaction vessel, and terephthalate is used as a dicarboxylic acid component in a nitrogen gas atmosphere. 95 mol of acid and 5 mol of trimellitic acid, 105 mol of bisphenol A propylene oxide adduct as a diol component, and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst were charged at 200 ° C. The esterification reaction was carried out while distilling from the distillation column. The esterification reaction was completed when water 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 pressure in the reaction system is reduced to 5 mmHg or less, 240 ° C., stirring speed 6
A condensation reaction was carried out at 0 rpm and the free diol produced by the condensation reaction was distilled out of the reaction system to obtain an amorphous polyester.

(2) Production of Toner Amorphous polyester obtained as a resin composition for toner is used as a resin composition for toner 1
00 parts by weight 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 were thoroughly mixed with a Henschel mixer, and then at 130 ° C. It was melt-kneaded, 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 toner fine powder having an average particle diameter 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.

(Comparative Example 2)
In the preparation of the resin composition for toner, a barrel temperature of 23 using a twin screw extruder with L / D = 20 was used.
A toner resin composition and a toner were obtained in the same manner as in Example 1 except that the mixture was melt kneaded at 0 ° C.

(Evaluation)
The resin composition for toner or toner prepared in Example 1 and Comparative Example 1 was evaluated by the following method.
The results are shown in Table 1.

[Measurement of molecular weight and molecular weight distribution]
(1) As a crystalline polyester GPC measurement device, HTR-C manufactured by Nihon Millipore Ltd. is used, and HFIP-806M (2) manufactured by Showa Denko KK is connected in series to the column, and the weight average molecular weight is determined. It was measured. The measurement conditions were a temperature of 40 ° C., a sample of 0.1 wt% hydroxyfluoroisopropanol (HFIP) solution (passed through a 0.45 μm filter), and an injection amount of 100
As a carrier solvent, HFIP containing 0.68 g of TFA per liter was used as a carrier solvent. Standard polystyrene was used as a calibration sample.
(2) As a non-crystalline polyester GPC measurement apparatus, HTR-C manufactured by Nippon Millipore Limited was used, and KF-800P (1), KF-806M (2), KF- manufactured by Showa Denko K.K. 802.5 (1
Were used in series, and the weight average molecular weight was measured. The measurement condition is that the temperature is 40 ° C.
The sample was a 0.2 wt% THF solution (passed through a 0.45 μm filter), the injection volume was 100 μL, the carrier solvent was THF, and standard polystyrene was used as the calibration sample.
(3) As a toner resin composition and a toner GPC measurement apparatus, HTR-C manufactured by Nippon Millipore Limited was used, and KF-800P (1), KF-806M (2) manufactured by Showa Denko Co., Ltd. were used as columns. , KF-802.5 (1
Were used in series, and the molecular weight and molecular weight distribution were measured. Measurement conditions are as follows: temperature is 40 ° C., sample is 0.2 wt% THF solution (passed through a 0.45 μm filter),
The injection volume was 100 μL, the carrier solvent was THF, and standard polystyrene was used as a calibration sample.

[Measurement of glass transition temperature (Tg)]
After the toner resin composition was held at a temperature equal to or higher than the melting point for a while, it was rapidly cooled to prepare a sample in which crystallization was completely suppressed. About this sample, using a differential scanning calorimeter (DSC-6200R, manufactured by Seiko Denshi Kogyo Co., Ltd.) at a temperature rising rate of 10 ° C./min, JIS K 712
The intermediate glass transition temperature described in the standard (9.3 “How to determine the glass transition temperature”) was determined.

[Measurement of crystal melting point (Tm) and endotherm]
Using a differential scanning calorimeter (DSC-6200R, manufactured by Seiko Denshi Kogyo Co., Ltd.), the heating rate was 10
10 mg of the sample was heated at 0 ° C./min, measured according to JIS K 7121, and the standard (9
. 1 “How to find the melting temperature”), the melting peak value is obtained and the crystal melting point Tm
In addition, the endothermic amount at the crystalline melting point Tm was determined from the DSC chart.

[Evaluation of color tone]
The color of the resin composition for toner was visually observed.

[Evaluation of average particle size of crystal particles]
The toner resin composition was placed on a preparation, heated to 100 ° C. using a hot plate or the like, softened, and then lightly pressed with a cover glass. Thereafter, the resin was heated to 150 ° C. to recrystallize the resin in an amorphous state, and then returned to room temperature. This was observed using a polarizing microscope with a magnification of 200 times, and the particle diameter of the distinguishable crystal particles was measured, and the average was obtained. The measurement was performed in 5 fields and the average value was calculated.

[Measurement of haze value]
The toner resin composition was hot-pressed at 150 degrees to produce a 1 mm thick plate sample. This sample is based on the method described in JIS K 7105.
Using C-HIIIDPK, the total light transmittance Ti (%) and the diffuse transmittance Td (%) were measured, and the haze value H was calculated by the above formula (2).

[Evaluation of blocking properties]
Take 10 g of toner in a 100 mL sample bottle, leave it in a thermostatic bath at 50 ° C. for 8 hours, and then screen with a 250 μm filter using a powder tester (manufactured by Hosokawa Micron) to observe whether aggregates remain on the filter. When there was an aggregate, the weight (% by weight) of the aggregate with respect to the toner weight was determined.

[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.

[Gross evaluation]
Using a gloss meter (gloss meter, UGV-50, manufactured by Suga Test Instruments Co., Ltd.), a test paper painted black with toner was attached to the gloss meter, the optical path was set so that the reflection angle was 75 degrees, and the gloss level was measured.

[Measurement of high temperature offset temperature and low temperature offset temperature]
A developer was prepared by mixing 6.5 parts by weight of toner 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.

[Measurement of minimum fixing temperature of toner]
Copying is performed by changing the set temperature of the heat fixing roller of the electrophotographic copying machine step by step, and the margin part and the fixed image are not stained with toner without fogging the margin part and the fixed image.
When the fixed image of the obtained copy was rubbed with a sand eraser for typewriters, the case where the decrease in 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.

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 (13)

A crystalline polymer having a melting point of 180 to 280 ° C. and an endotherm at a melting point of 25 to 150 mJ / mg measured using a differential scanning calorimeter (DSC); and a glass transition temperature of 3
A toner resin composition comprising an amorphous polyester at 0 to 80 ° C., wherein the average particle diameter of crystal particles observed by a polarizing microscope is 5 μm or less . A crystalline polymer having a melting point of 180 to 280 ° C. and an endotherm at a melting point of 25 to 150 mJ / mg measured using a differential scanning calorimeter (DSC); and a glass transition temperature of 3
A toner resin composition comprising an amorphous polyester at 0 to 80 ° C., comprising JI
A resin composition for toner, wherein a haze value measured by a method according to S K 7105 is 60% or more. 3. The resin composition for toner according to claim 1, wherein the endothermic amount at the melting point measured using a differential scanning calorimeter (DSC) is 1 to 20 mJ / mg. The crystalline polymer has a weight average molecular weight of 30,000 to 300,000.
Or 3. A resin composition for toner according to 3. The crystalline polymer is a crystalline polyester.
The resin composition for toner according to the description. 6. The resin composition for toner according to claim 5, wherein the crystalline polyester is polybutylene terephthalate. 6. The resin composition for toner according to claim 5, wherein the crystalline polyester is polyethylene terephthalate. The resin composition for toner according to claim 1, wherein the crystalline polymer is crystalline polyamide. 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. The resin composition for toner according to 2, 3, 4, 5, 6, 7 or 8. The resin composition for a toner according to claim 1, wherein the crystalline polymer and the non-crystalline polyester are compatible with each other. When the glass transition temperature of the crystalline polymer is A (° C.) and the glass transition temperature of the amorphous polyester is B (° C.), the glass transition temperature C (° C.) of the resin composition for toner is represented by the following formula (1). 11. The resin composition for toner according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

In formula (1), s represents the weight fraction of the crystalline polymer in the toner resin composition, and t represents the weight fraction of the amorphous polymer in the toner resin composition. An acid value is 1-30, The 1, 2, 3, 4, 5, 6, 7, 8, 9, 1 characterized by the above-mentioned.
12. A resin composition for toner according to 0 or 11. A toner comprising the resin composition for toner according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.