JP2004151709A - Resin composition for toner and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for toner which has excellent low-temperature fixation, high-temperature offset resistance and blocking resistance and permits satisfactory color development, and to provide a toner produced by the resin composition. <P>SOLUTION: The resin composition for toner has a melting point of 180 to 280°C and comprises a crystalline polymer in which the endothermic quantity at the melting point measured by using a differential scanning calorimeter (DSC) is 25 to 150mJ/mg and a non-crystalline polyester whose glass transition temperature is 30 to 80°C. Therein, the non-crystalline polyester comprises a non-crystalline polyester having weight average molecular weight of 3,000 to 20,000 and a non-crystalline polyester having weight average molecular weight of 30,000 to 300,000. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a toner resin composition and a toner which are excellent in low-temperature fixability, high-temperature offset resistance and blocking resistance, and can perform good color development.

As a method for developing an electrostatic charge image in electrophotography or the like, a dry development method is frequently used. In the dry development method, usually, toner is charged by friction with iron powder called a carrier, glass beads, and the like, and this is attached to an electrostatic latent image on a photoreceptor by electrical attraction, and then transferred to paper, The image is fixed by a heating roller or the like and becomes a permanent visible image.

As a fixing method, a heating roller method is widely used in which a toner image of a sheet to be fixed is caused to pass through the surface of a heat fixing roller formed of a material having a releasing property with respect to toner while being in pressure contact with the surface. ing.

In the heat fixing roller method, a toner that can be fixed at a lower temperature has been demanded in order to improve economy such as power consumption and to increase copying speed.
However, when trying to improve the low-temperature fixability described above, a part of the toner adheres to the surface of the heat fixing roller and the offset phenomenon such that the toner is re-transferred to paper is likely to occur, or the resins are subjected to various environments through various environments. There is a problem that a blocking phenomenon in which toner aggregates due to heat is likely to occur.

Conventional polyester-based toners usually form a chemically crosslinked structure in a polymer by copolymerizing a polyfunctional monomer having three or more functionalities, thereby maintaining high-temperature offset resistance. However, in such a method, since there is an insoluble component in the polymer, unevenness is generated on the printing surface after fixing by the fixing roll, so that the gloss is poor and the low-temperature fixability is limited.

To solve these problems, Patent Document 1 discloses that as a binder resin for a toner, a unit derived from terephthalic acid and a linear alkylene glycol having 2 to 6 carbon atoms is 50 mol% or more based on all monomer units used. It has been proposed to use a crystalline polyester resin containing the same.
However, in this technique, since only the crystalline polyester resin is used, the fixing temperature range is narrow, and it is difficult to maintain high-temperature offset resistance and blocking resistance without impairing low-temperature fixing property.

Patent Literature 2 discloses that a binder resin of a toner is obtained by polymerizing a trivalent or higher polyvalent monomer, an aromatic dicarboxylic acid, and an aliphatic alcohol containing 50 mol% or more of an aliphatic alcohol having a branched chain. It has been proposed to use non-crystalline polyester resins.
However, in this technique, since only the non-crystalline polyester resin is used, the low-temperature fixability was not sufficient.

Patent Documents 3 and 4 propose toners containing two types of polyesters having different softening points as toner resins as toners having an excellent balance between low-temperature fixability and high-temperature offset resistance at high temperatures.
However, the compatibility of the above two types of polyesters is not sufficient, and there is a problem that the polyester having a low softening point is liable to cause blocking or to adhere to the fixing roller and to cause filming. There is also a problem that the transparency of the resin is low due to insufficient solubility.

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 of the toner.
However, this technique has a problem that a transparent resin cannot be obtained because the binder resin becomes cloudy.

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 resin for the toner, a polyester resin for the toner which does not easily cause the blocking phenomenon has been studied. As a polyester resin for a toner which has a low fixing temperature which is not so low but does not easily cause a blocking phenomenon, for example, Patent Document 6 shows that it is effective to set the composition of the polyester resin to a specific composition. No. 7 shows that it is effective to specify the composition of the polyester resin and set the glass transition temperature at 45 to 70 ° C.

However, with these techniques, although the blocking phenomenon at room temperature is less likely to occur, 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 it would.

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

The present invention has been made in view of the above circumstances, and has as its object to provide a toner resin composition and a toner that are excellent in low-temperature fixing property, high-temperature offset resistance, and blocking resistance, and that can perform good color development.

The present invention relates to 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); A resin composition for toner containing a non-crystalline polyester at 80 ° C., wherein the non-crystalline polyester has a weight average molecular weight of 3,000 to 20,000, and a weight average molecular weight of 30,000. And a non-crystalline polyester of up to 300,000.
Hereinafter, the present invention will be described in detail.

The resin composition for a toner of the present invention contains a crystalline polymer and a non-crystalline polyester.
In this specification, a crystalline polymer refers to a polymer having a sharp and distinct melting point peak when the differential heat is measured by a differential scanning calorimeter and having a crystallinity of more than 10%. The polyester means a polyester which does not show a sharp and distinct melting point peak when the differential heat is measured by a differential scanning calorimeter and has a crystallinity of 10% or less.

When the resin composition for a toner of the present invention is used, a toner which is excellent in low-temperature fixing property, high-temperature offset resistance and blocking resistance and can perform good color development can be produced. This is because, in the toner resin composition of the present invention, the crystalline components in the high-melting crystalline polymer form a physically crosslinked structure in the non-crystalline polyester, while the high-melting crystalline polymer in the high-melting crystalline polymer The non-crystalline component and the non-crystalline polyester are entangled to form a kind of network structure. By forming such a network structure, the viscosity decrease at high temperatures is small, and the low-temperature fixability and storage stability It is considered that good offset resistance can be developed without lowering the.

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 crosslinked structure and an amorphous polyester having a glass transition temperature of 30 to 80 ° C without forming a physical crosslinked structure are provided. By mixing, the gloss and low-temperature fixability can be improved at the same time as the high-temperature offset resistance is improved. By containing a crystalline polymer capable of forming a physical crosslinked structure and a non-crystalline polyester having a glass transition temperature of 30 to 80 ° C without forming a physical crosslinked structure, the polymer viscosity is increased due to an increase in the viscosity. It is considered that the offset property can be improved, while the viscosity of the polymer decreases when pressurized by the fixing roll, so that the smoothness of the printed surface increases, and the gloss improves and the low-temperature fixing property also improves.

Further, the toner using the resin composition for a toner of the present invention has excellent image reproducibility.
This is because the above-mentioned network structure is formed in the entire resin composition for a toner of the present invention,
This is considered to be because the toner obtained in the pulverization step has stable chargeability, has no fog, and has excellent image reproducibility.

At this time, it is preferable that the crystals having the physical crosslinked structure are uniformly and finely dispersed in the toner resin composition of the present invention in a size of 1 μm or less. When the fine crystals are finely dispersed, the network structure becomes more stable, and an excellent effect is exhibited.
In order to develop such a nano-order uniform finely dispersed structure and form the above-mentioned network structure, it is very important that the compatibility between the crystalline polymer and the non-crystalline polyester is high, It is important that the crystallinity of the crystalline polymer be high.

In the crystalline polymer, the lower limit of the heat absorption at the melting point measured using a differential scanning calorimeter (DSC) is 25 mJ / mg, and the upper limit is 150 mJ / mg. If it is less than 25 mJ / mg, the above-mentioned network structure is difficult to form, and the desired effects such as high-temperature offset resistance cannot be obtained. If it exceeds 150 mJ / mg, the viscosity of the polymer at the time of pressurization by the fixing roll is insufficient. The surface of the print after fixing has irregularities, 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.
The measurement conditions of the differential scanning calorimeter (DSC) are not particularly limited.
It can be measured by a method of heating 10 mg of a sample at a heating rate of 10 ° C./min in accordance with IS K7121.

In the resin composition for a toner of the present invention, the lower limit of the heat absorption at the melting point measured by using a differential scanning calorimeter (DSC) is preferably 1 mJ / mg, and the upper limit is preferably 20 mJ / mg.
If it is less than 1 mJ / mg, the above-mentioned network structure is not formed, and the desired effects such as high-temperature offset resistance may not be obtained. It may not be sufficiently reduced, and unevenness may occur on the printed surface after fixing, 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 the temperature is lower than 180 ° C., the hot offset resistance at high temperatures becomes insufficient, or filming is liable to occur, resulting in insufficient durability. If it exceeds 280 ° C., it is necessary to melt at a high temperature exceeding 280 ° C. at the time of mixing with the non-crystalline polyester, so that the productivity is remarkably deteriorated. A preferred lower limit is 200 ° C, a preferred upper limit is 240 ° C, and a more preferred lower limit is 22 ° C.
0 ° C.
In order to shorten the rise time (warm-up time) after the switch is turned on in a copying machine or a printer, it is necessary to quickly raise the temperature of the fixing roller to a predetermined fixing temperature. Initially, the temperature fluctuates higher 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. As the fixing temperature is lower and the anti-hot offset temperature is higher, the warm-up time can be reduced. Usually, in order to make the design width of hardware sufficiently large, the hot offset resistance temperature is required to be 180 ° C. or more. It is considered that when the melting point of the crystalline polymer is 180 ° C. or higher, the crystal part of the crystalline polymer does not melt even at a high temperature, and the above-described network structure is maintained. Further, with the speeding up of copiers and printers, a toner that does not generate fine powder even under high-speed operation and does not cause filming is desired. In particular, there is a much higher demand for durability of a non-magnetic one-component toner which is charged by mechanical contact with a blade. It is considered that when the melting point of the crystalline polymer is 180 ° C., the cohesive force of the crystal part of the crystalline polymer is increased, and the above-described network structure is strengthened, so that the durability is improved.

The lower limit of the weight average molecular weight of the crystalline polymer is preferably 30,000, and the upper limit is preferably 300,000. If it is less than 30,000, the resulting toner may have insufficient offset resistance and durability. If it exceeds 300,000, low-temperature fixability and gloss may be poor. This is considered to be because the above-mentioned network structure cannot be sufficiently formed if the ratio is outside 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.

The crystalline polymer is not particularly limited, but a crystalline polyester or a crystalline polyamide is preferred.
The crystalline polyester can be obtained by polycondensing a dicarboxylic acid and a diol.
Examples of the dicarboxylic acids include, for example, o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octylsuccinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, maleic acid, itacone Acids, decamethylenecarboxylic acids, anhydrides and lower alkyl esters thereof, and the like. Among them, terephthalic acid, naphthalenedicarboxylic acid, and anhydrides and lower alkyl esters thereof are preferably used to impart 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 and 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;

As the crystalline polyester, among others, 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 by using the same has excellent offset resistance. Further, since the toner is excellent in compatibility with the non-crystalline polyester, the toner obtained by using the same has excellent low-temperature fixability and gloss.
Since polyethylene terephthalate (PET) has a high crystal melting point, a toner obtained by using the same has excellent offset resistance particularly at high temperatures. In addition, polyethylene terephthalate (PET) is inferior in crystallization speed and crystallinity than polybutylene terephthalate (PBT), 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.

As the crystalline polyamide, 6-nylon, 6,6-nylon, 4,6-nylon,
11-nylon, 12-nylon and the like. Among them, 6-nylon and 6,6-nylon are preferable because they have high crystal cohesion and are excellent in the effect of improving high-temperature offset resistance. Further, a polyamide-polyester copolymer obtained by copolymerizing a polyester with these crystalline polyamides is also preferable because of its excellent compatibility with the non-crystalline polyester. These crystalline polyamides may be used alone or in combination of two or more.
Since the above-mentioned crystalline polyamide has a strong cohesive force between molecules, it can exhibit high-temperature offset resistance by using a small amount of the polyester and can increase the strength of the resin itself.

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 the temperature is lower than 0 ° C, the high-temperature offset resistance and the blocking resistance cannot be sufficiently obtained, and if the temperature is higher than 80 ° C, the low-temperature fixability is poor. 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.
As for the glass transition temperature of the non-crystalline polyester, aromatic dicarboxylic acids such as terephthalic acid have a function of improving the glass transition temperature, and long-chain aliphatic dicarboxylic acids such as sebacic acid and adipic acid lower the glass transition temperature. Since they have a function, the desired 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 a polyvalent carboxylic acid and a polyhydric alcohol containing at least either a divalent bent monomer capable of introducing a bent molecular structure into a molecular chain or a divalent monomer having a branched chain. It is preferable that the monomer mixture is polymerized.
A polymer obtained by polymerizing a monomer mixture containing these divalent bent monomers or divalent monomers having a branched chain can easily achieve both the desired glass transition temperature and a low softening temperature, and can achieve crystallization. It can be suppressed effectively.

Examples of the divalent bending monomer include an aromatic dicarboxylic acid having an ortho or meta position substituted with a carboxyl group, an aromatic diol having an ortho or meta position substituted with a hydroxyl group,
Any monomer capable of introducing a bent molecular structure into the molecular chain of a polymer such as a polycyclic aromatic dicarboxylic acid having a carboxyl group at an asymmetric position and a polycyclic aromatic diol having a hydroxyl group at an asymmetric position is limited to dicarboxylic acids and diols. For example, it may be an anhydride or lower ester of dicarboxylic acid, 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;
And diols such as 1,4-cyclohexanedimethanol.

Further, the 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, an alicyclic diol having a branched alkyl chain, 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.
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 2,3-propanediol and 2,4-diethyl-1,5-pentanediol; 2,2-bis (4-hydroxycyclohexyl) propane and 2,2-bis (4-hydroxycyclohexyl) propane 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 of its excellent low-temperature fixability and transparency.

The non-crystalline polyester preferably contains two types of non-crystalline polyesters having different average molecular weights. The melt viscosity of an amorphous polyester is determined by its molecular weight. If a non-crystalline polyester having a low molecular weight is used, the resulting toner has a low melt viscosity, and thus excellent low-temperature fixability can be obtained. However, when a non-crystalline polyester having a small molecular weight is used, the obtained toner is inferior in high-temperature offset resistance and storage stability, and it is difficult to knead with the crystalline polymer. The present inventors, as a result of intensive study, by using a combination of a non-crystalline polyester having a small average molecular weight and a non-crystalline polyester having a large average molecular weight, while having excellent low-temperature fixability, high-temperature offset resistance, It has been found that storage stability and kneadability with a crystalline polymer can be significantly improved.

As a combination of the two types of non-crystalline polyesters having different weight average molecular weights, a non-crystalline polyester having a weight average molecular weight of 3000 to 20,000 as a small average molecular weight, and a weight average molecular weight as a large average molecular weight Amorphous polyester of 30,000 to 300,000 is used.
When the weight average molecular weight of the non-crystalline polyester having a small average molecular weight is less than 3,000, the strength of the resin composition for a toner becomes low, resulting in insufficient durability of the obtained toner. Sex cannot be expressed. A more preferred upper limit is 8000.
If the weight average molecular weight of the non-crystalline polyester having a large average molecular weight is less than 30,000, the resulting toner will have insufficient high-temperature offset resistance, storage stability and kneadability with the crystalline polymer, and if it exceeds 300,000. In addition, the resulting toner has insufficient low-temperature fixability. A more preferred upper limit is 200,000.

Amorphous polyester having a weight average molecular weight of 3,000 to 20,000 and a weight average molecular weight of 30,000 to
The mixing ratio with the non-crystalline polyester of 300,000 is such that the weight average molecular weight is 3000-2.
Weight average molecular weight of 30,000 to 3
It is preferable that the amount of the non-crystalline polyester of 10,000 is 10 to 60% by weight. When the compounding amount of the non-crystalline polyester having a weight average molecular weight of 3,000 to 20,000 is less than 40% by weight,
The obtained toner may have insufficient low-temperature fixability. If the amount exceeds 90% by weight, the obtained toner may have insufficient high-temperature offset resistance, storage stability, and kneading properties with a crystalline polymer. is there.

Preferably, the crystalline polymer and the non-crystalline polyester are compatible. The compatibility of the crystalline polymer and the non-crystalline polyester allows the above-mentioned network structure to be stably formed. Further, when the crystalline polymer and the non-crystalline polyester are compatible, the resin composition for toner of the present invention becomes colorless and transparent,
It can be suitably used as a resin composition for a color toner capable of performing good color development, and has a high resin strength, so that it is suitably used as a resin composition for a toner having excellent high-temperature offset resistance. be able to.
In addition, the compatibility refers to a state in which the crystalline polymer and the non-crystalline polyester are uniformly mixed, and these may be completely compatible or partially compatible. .

In order for the crystalline polymer and the amorphous polyester to be compatible with each other, the glass transition temperature of the crystalline polymer is A (° C.), and the glass transition temperature of the amorphous polyester is B (° C.). In this case, the glass transition temperature C (° C.) of the resin composition for a toner of the present invention preferably satisfies the following formula (1).

式（１）中、ｓはトナー用樹脂組成物中の結晶性ポリマーの重量分率を表し、ｔはトナー
用樹脂組成物中の非結晶性ポリマーの重量分率を表す。
本発明のトナー用樹脂組成物のガラス転移温度が上記式（１）を満たす場合には、上記結
晶性ポリマーと上記非結晶性ポリエステルとが極めて良好に相溶する。

In the formula (1), s represents the weight fraction of the crystalline polymer in the resin composition for toner, and t represents the weight fraction of the non-crystalline polymer in the resin composition for toner.
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 non-crystalline polyester are extremely compatible with each other.

Using a crystalline polyester as the crystalline polymer, further, if the crystalline polyester and the non-crystalline polyester have a common monomer component such as terephthalic acid as a constituent monomer, the compatibility can be improved. it can. For example, when the crystalline polyester is 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 main components. Are well compatible.

As for the content of the crystalline polymer and the non-crystalline polyester in the resin composition for a toner of the present invention, a preferable lower limit of the content of the crystalline polymer is 2% by weight, and a preferable upper limit is 30% by weight. A preferable lower limit of the content of the non-crystalline polyester is 98% by weight.
The preferred upper limit is 70% by weight.
If the content of the crystalline polymer is less than 2% by weight, the high-temperature offset resistance may be poor, and if it exceeds 30% by weight, the low-temperature fixability may be poor. 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 resin composition for a toner of the present invention preferably further contains a nucleating agent. By containing the crystal nucleating agent, crystallization of the crystalline polymer component can be promoted. The crystal nucleating agent is not particularly limited, and examples thereof include 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; Can be The shape of the crystal nucleating agent is not particularly limited, and may be plate-like, spherical, or amorphous.

When the resin composition for a toner of the present invention is given a 5% shear strain at 190 ° C.,
It is preferable that the change rate D of the relaxation modulus represented by the following formula (2) is 15 to 90.

緩和弾性率の変化率Ｄは、物質の弾性挙動をし、０に近づくほどゴム弾性に近い性質を有
するといえる。上記緩和弾性率の変化率Ｄが１５〜９０であることは、本発明のトナー用
樹脂組成物内においてネットワーク構造が形成されており、均一に分散した物理的架橋構
造を形成した結晶を中心に高融点の結晶性ポリマー中の非結晶性成分と非結晶性ポリエス
テルとが絡まり合った構造によりゴムライクな性質が発現していることを意味すると考え
られる。上記緩和弾性率の変化率Ｄが１５未満であると、定着ロールによる加圧時にトナ
ーの粘度が充分に低下せず、定着後の印字表面に凹凸が生じて光沢が劣り、低温定着性が
劣る。９０を超えると、上述のネットワーク構造を形成しにくいことから、充分な耐高温
オフセット性向上効果が得られない。

It can be said that the change rate D of the relaxation modulus shows the elastic behavior of the substance, and the closer to zero, the closer the property is to the rubber elasticity. When the change rate D of the relaxation modulus is 15 to 90, it means that the network structure is formed in the resin composition for a toner of the present invention, and the crystal structure having a physically cross-linked structure uniformly dispersed is formed. This is considered to mean that a rubber-like property is exhibited by a structure in which the amorphous component and the amorphous polyester in the crystalline polymer having a high melting point are entangled with each other. When the rate of change D of the relaxation modulus is less than 15, the viscosity of the toner does not sufficiently decrease upon pressurization by the fixing roll, and unevenness occurs on the printed surface after fixing, resulting in poor gloss and poor low-temperature fixability. . If it exceeds 90, it is difficult to form the above-mentioned network structure, so that a sufficient high temperature offset resistance improving effect cannot be obtained.

When the resin composition for toner of the present invention is subjected to a shear strain of 450% under the condition of 190 ° C., a shear strain represented by the following formula (3) is applied, and 0.1% after 0.02 seconds. It is preferable that the gradient K of the relaxation modulus curve after seconds is -27 or more.

式中、Ｇ（０．０２）は、剪断ひずみを与えて０．０２秒後の緩和弾性率を表し、Ｇ（０
．１）は、剪断ひずみを与えて０．１秒後の緩和弾性率を表す。

In the formula, G (0.02) represents the relaxation modulus after 0.02 seconds from the application of the shear strain, and G (0
. 1) represents the relaxation modulus after 0.1 seconds from the application of the shear strain.

The slope K of the relaxation modulus curve represents the elastic behavior of the substance, and as it approaches 0, it indicates that the material has a property closer to rubber elasticity. When the gradient K of the relaxation modulus curve is -27 or more, the crystal having the above-mentioned network structure formed in the resin composition for toner of the present invention and having the physically crosslinked structure uniformly dispersed therein is formed. It is thought that the rubber-like property is expressed by the structure in which the amorphous component in the crystalline polymer having a high melting point and the amorphous polyester are entangled. Therefore, the resin composition for a toner of the present invention in which the gradient K of the relaxation modulus curve is -27 or more is excellent in low-temperature fixing property, high-temperature offset resistance and blocking resistance, and can provide a toner that performs good color formation. Can be. If the gradient K of the relaxation modulus curve is less than -27, the formation of the network structure is considered to be insufficient, and the desired effect may not be obtained.
The relaxation elastic modulus is determined, for example, by melting a resin for toner of the present invention and then molding it into a disk having a predetermined size as a test sample, and using a relaxation elastic modulus measuring device (for example, RMS manufactured by Rheometrics Co., Ltd.). -800 etc.).

The acid value of the resin composition for a toner of the present invention is not particularly limited, but is preferably 1 to 30. Such an acid value is derived from an acidic functional group at the terminal 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 obtained toner has excellent low-temperature fixability and also has improved affinity with paper.
Since the resin composition for toner of the present invention contains only a polymer having a molecular weight of about several hundred thousand, unlike the conventional crosslinked resin composition for a toner containing a high molecular weight polymer of 1,000,000, Are relatively uniformly distributed, and higher low-temperature fixability can be obtained.

The method for producing the resin composition for a toner of the present invention is not particularly limited. For example, a method in which 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. And the like.

Using the toner resin composition of the present invention as a binder resin, if necessary, a release agent, a colorant, a charge control agent, a magnetic material, a rubbery polymer, and a styrene-acrylate copolymer for a toner. The toner can be manufactured by mixing with a resin, a carrier, a cleaning improver, and the like. Such a toner is also one of the present invention.
Since the toner of the present invention is excellent in both low-temperature fixability and high-temperature offset resistance by using the resin composition for a toner of the present invention, it does not need to contain a release agent.
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 wax; and fats such as carnauba wax, sasol wax, and montanic acid ester wax. Aliphatic ester waxes; deacidified carnauba wax; saturated aliphatic acid waxes such as baltimic acid, stearic acid, and montanic acid; unsaturated aliphatic acid waxes such as pracidic acid, eleostearic acid, and barinaric acid; Saturated alcohol waxes and aliphatic alcohol waxes such as aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melisyl alcohol; polyhydric alcohol waxes such as sorbitol A saturated fatty acid amide wax such as linoleic acid amide, oleic acid amide and lauric acid amide; a saturated fatty acid bisamide such as methylene bisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide and hexamethylenebisstearic acid amide Waxes; unsaturated acid amide waxes such as ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bis stearin Aromatic bisamide waxes such as acid amide and N, N'-distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; vinyl monomers such as styrene and acrylic acid -Modified wax obtained by graft polymerization of a polymer with a polyolefin; partial ester wax obtained by reacting a fatty acid such as behenic acid monoglyceride with a polyhydric alcohol; methyl ester wax having a hydroxyl group obtained by hydrogenating vegetable oil; ethylene Ethylene-vinyl acetate copolymer wax having a high content of components; long-chain alkyl acrylate wax such as saturated stearyl acrylate wax such as acrylic acid; aromatic acrylate wax such as benzyl acrylate wax; Among them, long-chain alkyl acrylate waxes and aromatic acrylate waxes are preferable since they have excellent compatibility with the resin composition for toner and can provide a toner with high transparency. These release agents may be used alone or in combination of two or more types. In particular, it is preferable to use two or more types of release agents having different melting points by 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, furnace black, lamp black, thermal black, acetylene black, carbon black such as channel black, aniline black, phthalocyanine blue, quinoline yellow lamp black, rhodamine-
B, azo pigments, perylene pigments, perinone pigments, anthraquinone pigments, dioxazine pigments, isoindoline pigments, isoindolinone pigments, selen pigments, indico pigments, quinophthalone, diketopyrrolopyrrole, quinacridone, etc. Is mentioned.
The preferred lower limit of the amount of these colorants is usually 1 part by weight, and the preferred upper limit is 10 parts by weight, based on 100 parts by weight of the resin composition for toner.

There are two types of charge control agents, positive charge and negative charge. Examples of the positive charge control agent include a nigrosine dye, an ammonium salt, a pyridinium salt, and azine, and examples of the negative charge control agent include a chromium complex and an iron complex. Above all, an acid-modified charge control agent is preferable. If salicylic acid-modified, it is crosslinked with the resin composition for toner to exhibit rubber elasticity. A metal complex of an alkyl-substituted salicylic acid such as a di-tert-butylsalicylate chromium complex such as a zinc di-tert-butylsalicylate complex is colorless or light-colored, and thus does not affect the color tone of the toner. Further, as the charge control agent, a charge control resin (CCR) can also be suitably used. As the charge control resin, for example,
Examples include a styrene acrylic polymer obtained by copolymerizing a monomer containing a quaternary ammonium salt, an organic fluorine-based monomer, a sulfonic acid group-containing monomer, and a phenylmaleimide-based monomer.
The preferred lower limit of the amount of these charge control agents is usually 0.1 part by weight, and the preferred upper limit is 10 parts by weight, based on 100 parts by weight of the resin composition for toner.

Examples of the magnetic material include “TAROX BL series” (trade name, manufactured by Titanium Industry Co., Ltd.).
, Product name "EPT series", product name "MAT series", product name "MTS series" (
All products are manufactured by Toda Kogyo Co., Ltd.), product name “DCM Series” (manufactured by Dowa Iron Powder Co., Ltd.), product name “KBC
Series ", brand name" KBI series ", brand name" KBF series ", brand name" KBP series "(all manufactured by Kanto Denka Kogyo Co., Ltd.), brand 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, ethylene-propylene copolymer , Ethylene-propylene-diene copolymer, chlorosulfinated polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate 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, styrene 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, styrene- is used as the block copolymer.
A butadiene block copolymer, a styrene-isoprene block copolymer, or the like may be mixed, or a hydrogenated product thereof may be mixed.
Further, a rubber-like polymer consisting of 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, and a halogen group with a conjugated diene is used as a toner. Is preferred because of its excellent affinity for These block copolymers having a polar group at the terminal can be obtained by living polymerization.
The rubber-like polymer can improve the resin strength of the resin contained in the toner. Therefore, the toner containing the rubbery polymer can prevent the filming phenomenon of the toner, and can provide a toner suitable for a non-magnetic one-component toner requiring high resin strength.

Examples of the carrier include simple metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, alloys, oxides, and ferrites. The surface of the carrier may be oxidized. Further, the carrier surface is made of polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone polymer, polyester, metal complex of di-tert-butylsalicylic acid, styrene-based polymer, acrylic polymer, polyamide, polyvinyl butyral, nigrosine base It may be coated with a coloring dye, silica powder, alumina powder or the like. By coating the carrier, preferable triboelectric charging properties can be imparted to the carrier.

The cleaning property improver 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 acrylate ester polymer, fatty acid metal salt powder such as zinc stearate, calcium stearate, lead stearate, zinc oxide powder, titanium oxide powder, etc. Examples include metal oxide powder, fine silica powder, silica powder surface-treated with a silane coupling agent, a titanium coupling agent, and silicon oil, and fumed silica. Further, as the above-mentioned cleaning property improver, a sphere having a particle size 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, as measured by gel permeation chromatography. Thereby, fixability is improved. 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. This improves the water resistance.

Although the particle size of the toner of the present invention is not particularly limited, when the particle size is 5 μm or less, particularly high image quality can be obtained.
Although the water content of the toner of the present invention is not particularly limited, a preferable lower limit is 0.01% by weight.
The preferred upper limit is 0.2% by weight. If the amount is less than 0.01% by weight, production becomes difficult due to production problems, and if it exceeds 0.2% by weight, sufficient charge stability may not be obtained.
Although the angle of repose of the toner of the present invention is not particularly limited, a preferable lower limit of the angle of repose at 23 ° C. and a humidity of 60% is 1 degree, and a preferable 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) or the like.

Although the surface roughness of the toner of the present invention is not particularly limited, a 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 obtained image may be insufficient. The surface roughness is determined by measuring the printing portion of an image printed using the toner of the present invention according to JIS B060.
1 can be measured by a method defined as a method for measuring the arithmetic average roughness (Ra).

In the case where the toner of the present invention is used particularly for applications requiring excellent surface gloss, the lower limit of the viscosity of the toner of the present invention at 150 ° C. is preferably 100 mPa · s.
s, and a preferred upper limit is 50,000 mPa · s. If it is less than 100 mPa · s, the storage stability may be poor, and if it exceeds 50,000 mPa · s, sufficient surface gloss may not be obtained. A more preferred upper limit is 10,000 mPa · s.

The toner of the present invention can exhibit good fixability over a wide range from low to high temperatures, and is excellent in both low-temperature fixability, high-temperature offset resistance, and blocking resistance. It is economical because the time until the printing 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 can be speeded up. . 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.

Further, the toner of the present invention may be fixed by a fixing roller coated with a release oil. However, good fixability can be exhibited even when the release oil is not applied to the fixing roller.
Further, the crystalline polymer and the non-crystalline polyester used in the resin composition for toner of the present invention have good fixability over a wide range from low to high temperatures without being crosslinked or separately compounded with a high molecular weight resin. And a toner excellent in both low-temperature fixing property, 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 crushed than a toner using a resin for a toner containing a high molecular weight resin, exhibits sharp melting characteristics, and a glossy fixed image is obtained. .

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance, and can provide the resin composition for toner which can perform favorable color development, and a toner.

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

(Example 1)
<Production of crystalline polyester>
A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirring device were installed in a 60-liter reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 100 mol of terephthalic acid was used as a dicarboxylic acid component.
120 mol of 1,4-butanediol as a diol component and 0.05 mol of titanium tetrabutoxide (TBB) as an esterification condensation catalyst were charged, and an esterification reaction was carried out at 200 ° C. while distilling off generated water from a distillation column. Was. The esterification reaction was terminated when no more water distilled from the distillation column.
After the completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation column was closed, the line from the vacuum pump was opened, and the pressure inside the reaction system was reduced to 5 mmHg or less, 240 ° C.
The condensation reaction was carried out at 0 rpm, and the free diol produced in the condensation reaction was distilled out of the reaction system to obtain a high melting crystalline polyester.

<Production of non-crystalline polyester (A)>
A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirring device were installed in a 60 L reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 90 mol of terephthalic acid was used as a dicarboxylic acid component, and isophthalic was used as a bent monomer component. 5 mol of acid, 5 mol of phthalic anhydride, 60 mol of neopentyl glycol as a branched monomer component, 60 mol of ethylene glycol as another diol,
0.05 mol of titanium tetrabutoxide (TBB) was charged as an esterification condensation catalyst, and 2
At 00 ° C., the esterification reaction was performed while distilling off the generated water from the distillation column. The esterification reaction was terminated when no more water distilled from the distillation column.
After the completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation column was closed, the line from the vacuum pump was opened, and the pressure inside the reaction system was reduced to 5 mmHg or less, 240 ° C.
The condensation reaction was performed at 0 rpm, and the free diol generated in the condensation reaction was distilled out of the reaction system to obtain a non-crystalline polyester (A).

<Production of amorphous polyester (B)>
A distillation column, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirring device were installed in a 60-liter reaction vessel according to a conventional method. Under a nitrogen gas atmosphere, 100 mol of terephthalic acid was used as a dicarboxylic acid component.
35 mol of cyclohexanedimethanol, 85 mol of ethylene glycol 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 performed while distilling off the generated water from the distillation column. The esterification reaction was terminated when no more water distilled from the distillation column.
After the completion of the esterification reaction, the opening of the 60 L reaction vessel to the distillation column was closed, the line from the vacuum pump was opened, and the pressure inside the reaction system was reduced to 5 mmHg or less, 240 ° C.
The 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 non-crystalline polyester (B).

<Production of resin composition for toner and toner>
10 parts by weight of the obtained crystalline polyester, 65 parts by weight of the non-crystalline polyester (A) and 25 parts by weight of the non-crystalline polyester (B) were melt-kneaded at 240 ° C. using a twin-screw extruder. A resin composition for a toner was obtained.
To 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 a magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax are sufficiently mixed with a Henschel mixer. Then, the mixture was melt-kneaded at 130 ° C., cooled, and coarsely ground. Thereafter, the resultant was finely pulverized with a jet mill (Labjet: 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. To 100 parts by weight of this toner fine powder, 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) was uniformly mixed (externally added) to produce a toner.

(Comparative Example 1)
A crystalline polymer was obtained in the same manner as in Example 1 except that 60 mol of terephthalic acid, 40 mol of isophthalic acid and 120 mol of 1,4-butanediol were used as raw material monomers.
20 parts by weight of the obtained crystalline polymer and the non-crystalline polyester (A) prepared in Example 1
80 parts by weight were melt-kneaded at 240 ° C. using a twin-screw extruder to obtain a resin composition for toner by melt-kneading.
To 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 a magenta pigment belonging to Carmine 6B, and 1 part by weight of carnauba wax are sufficiently mixed with a Henschel mixer. Then, the mixture was melt-kneaded at 130 ° C., cooled, and coarsely ground. Thereafter, the resultant was finely pulverized with a jet mill (Labjet: 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. To 100 parts by weight of this toner fine powder, 1.0 part by weight of hydrophobic silica (R972: manufactured by Nippon Aerosil Co., Ltd.) was uniformly mixed (externally added) to produce a toner.

(Evaluation)
The toner resin compositions or toners produced in Example 1 and Comparative Example 1 were evaluated by the following methods.
The results are shown in Table 1.

[Measurement of molecular weight and molecular weight distribution]
(1) As a crystalline polyester GPC measuring apparatus, HTR-C manufactured by Nippon Millipore Limited was used, and HFIP-806M (2 pieces) manufactured by Showa Denko was connected in series for the column, and the weight average molecular weight was measured. It was measured. The measurement conditions were as follows: the temperature was 40 ° C., the sample was a 0.1% by weight hydroxyfluoroisopropanol (HFIP) solution (passed through a 0.45 μm filter), and the injection amount was 100.
HFIP containing 0.68 g of TFA per 1 L was used as a carrier solvent. Standard polystyrene was used as a calibration sample.
(2) HTR-C manufactured by Nippon Millipore Limited was used as a non-crystalline polyester GPC measuring device, and KF-800P (1), KF-806M (2), KF-806M manufactured by Showa Denko KK were used as columns. 802.5 (1
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% by weight 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 a calibration sample.
(3) HTR-C manufactured by Nippon Millipore Limited was used as a resin composition for toner and a toner GPC measuring device, and KF-800P (1) and KF-806M (2) manufactured by Showa Denko were used as columns. , KF-802.5 (1
Were connected in series to measure the molecular weight and the molecular weight distribution. The measurement conditions were as follows:
At 0 ° 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 a calibration sample.

[Measurement of glass transition temperature (Tg)]
After holding the resin composition for a toner 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. This sample was subjected to JIS K 712 at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC-6200R, manufactured by Seiko Instruments Inc.).
1, and the intermediate glass transition temperature described in the standard (9.3 “How to determine glass transition temperature”) was determined.

[Measurement of crystal melting point (Tm) and endothermic amount]
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC-6200R), the temperature was raised at a rate of 10
10 mg of the sample was heated at a rate of ° C./min, measured according to JIS K 7121, and measured according to the standard (9
. 1 "How to determine the melting temperature") and determine the melting peak value, and use this as the crystal melting point Tm.
The endothermic amount at the crystal melting point Tm was determined from the DSC chart.

[Measurement of acid value]
JIS K except that tetrahydrofuran (THF) was used instead of ethyl alcohol.
The acid value was determined by a method according to 6751.

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

[Evaluation of blocking property]
Take 10 g of the toner in a 100 mL sample bottle, leave it in a thermostat at 50 ° C. for 8 hours, and sieve through a 250 μm filter using a powder tester (manufactured by Hosokawa Micron Corporation) to observe whether aggregates remain on the filter. If there was an aggregate, the weight (% by weight) of the aggregate relative to the weight of the toner was determined.

[Filming evaluation]
After printing 10,000 sheets, it was visually observed whether or not the toner adhered to the fixing roller. If no toner was observed, the toner was evaluated as having no filming.

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

[Measurement of high temperature offset temperature and low temperature offset temperature]
6.5 parts by weight of the toner was mixed with 93.5 parts by weight of an iron powder carrier having an average particle diameter of 50 to 80 μm to prepare a developer. As the electrophotographic copying machine, a modified 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 or not the blank portion and the fixed image of the obtained copy were stained by the toner, and a temperature region where no stain was generated was defined as a non-offset temperature region. Further, the maximum value in the non-offset temperature region was defined as a high temperature offset temperature, and the minimum value was defined as a low temperature offset temperature.

[Measurement of minimum fixing temperature of toner]
The copying is performed by gradually changing the set temperature of the heat fixing roller of the electrophotographic copying machine, and the margin and the fixed image are not stained by the toner without fogging of the margin and the fixed image.
When the fixed image of the obtained copy was rubbed with a sand eraser for a typewriter, a case where the decrease in the density of the fixed image was less than 10% was determined to be good, and the minimum temperature at that time was determined.
The image density was measured using a Macbeth photometer.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in low-temperature fixability, high-temperature offset resistance, and blocking resistance, and can provide the resin composition for toner which can perform favorable color development, and a toner.

Claims (13)

A crystalline polymer having a melting point of 180 to 280 ° C. and an endotherm of 25 to 150 mJ / mg at a melting point measured using a differential scanning calorimeter (DSC);
A non-crystalline polyester having a temperature of 0 to 80 ° C.,
The non-crystalline polyester contains a non-crystalline polyester having a weight average molecular weight of 3000 to 20,000 and a non-crystalline polyester having a weight average molecular weight of 30,000 to 300,000. Composition. As for the non-crystalline polyester, the compounding amount of the non-crystalline polyester having a weight average molecular weight of 3,000 to 20,000 is 40 to 90% by weight, and the compounding amount of the non-crystalline polyester having a weight average molecular weight of 30,000 to 300,000 is 10 The resin composition for a toner according to claim 1, wherein the amount is from 50 to 50% by weight. The resin composition for a toner according to claim 1, wherein an endothermic amount at a melting point measured by using a differential scanning calorimeter (DSC) is 1 to 20 mJ / mg. 3. The crystalline polymer has a weight average molecular weight of 30,000 to 300,000.
Or the resin composition for toner according to item 3. The crystalline polymer is a crystalline polyester, wherein the crystalline polymer is a crystalline polyester.
The resin composition for a toner according to the above. The resin composition for a toner according to claim 5, wherein the crystalline polyester is polybutylene terephthalate. The resin composition for a toner according to claim 5, wherein the crystalline polyester is polyethylene terephthalate. The resin composition for a toner according to claim 1, 2, 3, or 4, wherein the crystalline polymer is a crystalline polyamide. 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 main components. 9. The resin composition for a 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 non-crystalline polyester is B (° C.), the glass transition temperature C (° C.) of the resin composition for a toner is represented by the following formula (1). The resin composition for a toner according to claim 1, wherein the resin composition satisfies the following.

In the formula (1), s represents the weight fraction of the crystalline polymer in the resin composition for toner, and t represents the weight fraction of the non-crystalline polymer in the resin composition for toner. The acid value is 1 to 30, wherein the acid value is 1 to 30, 3, 7, 8, 9, 1.
12. The resin composition for toner according to 0 or 11. 13. A toner comprising the resin composition for toner according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.